Baker

Coke Formation
on Metal Surfaces
In Coke Formation on Metal Surfaces; Albright, L., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
Coke Formation
on Metal Surfaces
Lyle F. Albright, EDITOR
Purdue University
R. T . K. Baker, EDITOR
Exxon
Engineering Company
Basedona symposium jointly sponsored

by theACSDivisions of Petroleum and
Industrial and Engineering Chemistry
at the 182nd Meeting
of the American Chemical Society
New York, New York,
August 27, 1981.
ACS SYMPOSIUM SERIES 202

AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1982

Library of Congress Cataloging in Publication Data
Coke formation on metal surfaces.
(ACS symposium series, ISSN 0097-6156; 202)
"Based on a symposium jointl
ACS Divisions of Petroleu
Engineering Chemistry at th g
American Chemical Society, New York, New York,
August 23-28, 1981."
Includes bibliographies and index.
1. MetalsSurfacesCongresses. 2. Metals at high
temperaturesCongresses. 3. CokeCongresses.
I. Albright, Lyle Frederick, 1921- . II. Baker,
R. T. K., 1938- . III. American Chemical Society
Division of Petroleum Chemistry. IV. American
Chemical Society. Division of Industrial and Engi-
neering Chemistry. V. American Chemical Society.
National Meeting (182 : 1981 :New York, N.Y.)
VI. Series.
TA459.C545 1982 665.5'3 82-16335
ISBN 0-8412-0745-3 ACSMC8 202 1-318
1982
Copyright 1982
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PRINTED IN THE UNITED STATES OF AMERICA

ACS Symposium Series
M . Joa
Advisory Board
David L. Allara Marvin Margoshes
Robert Baker Robert Ory
Donald D . Dollberg Leon Petrakis
Robert E. Feeney Theodore Provder
Brian M . Harney Charles N. Satterfield
W . Jeffrey Howe Dennis Schuetzle
James D . Idol, Jr. Davis L. Temple, Jr.
Herbert D . Kaesz Gunter Zweig

FOREWORD
The ACS SYMPOSIUM SERIES was founded in 1974 to provide
a medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that in order to save time the
papers are not typeset but are reproduced as they are sub-
mitted by the authors in camera-ready form. Papers are re-
viewed under the supervision of the Editors with the assistance
of the Series Advisory Board and are selected to maintain the
integrity of the symposia; however, verbatim reproductions of
previously published papers are not accepted. Both reviews
and reports of research are acceptable since symposia may
embrace both types of presentation.

PREFACE
C/OKE FORMATION is AN UNDESIRABLE SIDE E F F E C T of many chemical

operations because it leads to costly decoking steps, reduced efficiency of
operation, and increased rates of metal corrosion and erosion. There is,
therefore, a tremendous incentive to minimize or at least better control coke
deposition in numerous commercial units.
A symposium about coke formation on metal surfaces has been long
overdue, so we were delighted when the Divisions of Petroleum Chemistry
and of Industrial and Engineerin
Society agreed to sponsor such a symposium. Our objective was to gather
key experts from around the world to promote a valuable interchange of
ideas. In addition, we hoped that the results could be published and made
available to individuals who could not attend the symposium.
Ten of the papers included in this book were presented at the original
symposium. In each case, the paper has been reviewed and, in several
cases, been modified to include 1982 findings. Five papers were added to
describe coking results that are considered highly important. Consequently,
this book discusses recent investigations and the latest thinking on coke
formation due to thermal and catalytic processes on metal surfaces.
In conclusion, we want to thank all who made possible the symposium
and this subsequent publication: the Divisions of Petroleum Chemistry and
of Industrial and Engineering Chemistry for their sponsorship; the authors
without whom it could never exist; the reviewers; and finally those who
worked behind the scenes. In this latter category are our two secretaries,
Mrs. Phyllis Beck (West Lafayette) and Mrs. M . Evan (Linden) who as a
result, were burdened with considerably more than their normal duties
require.
L Y L E F. A L B R I G H T
Purdue University
School of Chemical Engineering
West Lafayette, IN 47907
R. T . K. B A K E R
Exxon Research and Engineering Company
Corporate Research Science Laboratories
Linden, NJ 07036
July 1982
ix

1
Filamentous Carbon Formation over Iron Surfaces
R. T . K . B A K E R and D . J. C . Y A T E S
Exxon Research and Engineering Company, Corporate Research Science Laboratories,
Linden, N J 07036
J. A . D U M E S I C
University of Wisconsin, Chemical Engineering Department, Madison, WI 53706
It i s w e l l known that the surface s t a t e of a

metal can have
c a t a l y z e the formatio
hydrocarbon conversion process. In t h i s work we
have examined the e f f e c t of oxygen and steam
pretreatments of i r o n surfaces on t h e i r ability to
c a t a l y z e carbon filament formation during r e a c t i o n
of such surfaces with hydrocarbons. Pretreatment
of i r o n i n steam a t 700C r e s u l t e d i n the
conversion of the metal to FeO, and t h i s oxide was
found to be a tremendously a c t i v e c a t a l y s t f o r
carbon filament growth when reacted with acetylene
or ethane at 700C. On the other hand, the
activity of Fe O , formed by r e a c t i o n of i r o n with
2 3
oxygen, was about the same as that of the metal

when treated with these hydrocarbons. From t h i s
study it is concluded that the key to the high FeO
activity i s that it is a precursor f o r a high
surface area Fe c a t a l y s t formed i n situ. I t was
a l s o found that Fe C is not an a c t i v e c a t a l y s t f o r
3
carbon filament formation.
The accumulation of carbon on metal surfaces when heated i n

the presence of carbon containing gases i s a s e r i o u s problem
encountered i n a number of commercial processes. Although carbon
appears to deposit on most surfaces there are some m a t e r i a l s which
are more v u l n e r a b l e than others since they contain c o n s t i t u e n t s
which c a t a l y z e carbon formation. The highest c a t a l y t i c a c t i v i t y
i s e x h i b i t e d by the ferromagnetic metals and i n p a r t i c u l a r ,
i r o n . Furthermore i t i s w e l l known that the surface s t a t e of such
metals can have a dramatic e f f e c t on t h e i r a b i l i t y to c a t a l y z e the
formation of carbon.
0097-6156/82/0202-0001$06.50/0
1982 American Chemical Society

2 COKE FORMATION
Carbon d e p o s i t s normally have a complex s t r u c t u r e containing

s e v e r a l d i f f e r e n t growth forms, which can be grouped under three
headings: amorphous, filamentous, and g r a p h i t i c p l a t e l e t s
(1^, 2_, 3).
Of these three forms the l e a s t understood i s amorphous
carbon. A v a i l a b l e evidence suggests that condensation and
p o l y m e r i z a t i o n r e a c t i o n s play a major r o l e i n amorphous carbon
formation. Although some hydrogen i s removed during condensation,
a s i g n i f i c a n t amount remains i n the d e p o s i t , but as the
temperature i s r a i s e d , dehydrogenation r e a c t i o n s reduce the
hydrogen content to <1% ( 4 ) . Although there does not appear to
be any g e n e r a l method of preventing amorphous carbon accumulation
on a s u r f a c e , there i s l i t t l e doubt that such m a t e r i a l would be
r e a d i l y removed by treatment i n a i r at 500C.
Filamentous carbo i produced b th c a t a l y t i decompositio
of carbon containing gase
the t y p i c a l appearance o
c a t a l y s t p a r t i c l e l o c a t e d at the t i p of the f i l a m e n t , which during
the r e a c t i o n was c a r r i e d away from the support surface by the
growth process. Although i t i s not d i f f i c u l t to accept that such
growths could occur on a supported metal c a t a l y s t system, where
metal c r y s t a l l i t e s ( 0 . 5 to 5 . 0 nm diameter) are d i s p e r s e d on non-
m e t a l l i c oxide supports, i t i s hard to understand how the
filaments are produced on bulk metal s u r f a c e s . T h i s i s an area
which o b v i o u s l y r e q u i r e s a g r e a t d e a l of work and before s o l v i n g
the problem i t w i l l f i r s t be necessary to e s t a b l i s h the c r i t e r i a
c o n t r o l l i n g the n u c l e a t i o n of small p a r t i c l e s on metal s u r f a c e s .
A mechanism has been p o s t u l a t e d to account f o r the growth of
filamentous carbon produced from metal c a t a l y z e d decomposition of
acetylene 5 , _ 6 ) . This mechanism, which i s o u t l i n e d i n the
schematic diagram, F i g u r e 2, i n v o l v e s the d i f f u s i o n of carbon
through the c a t a l y s t p a r t i c l e from the h o t t e r leading face, on
which exothermic decomposition of the hydrocarbon occurs, to the
c o o l e r t r a i l i n g f a c e s , at which carbon i s deposited from
s o l u t i o n . Excess carbon buildup occurs at the exposed p a r t i c l e
face and i s transported by s u r f a c e d i f f u s i o n around the p e r i p h e r a l
surfaces of the p a r t i c l e to form an outer s k i n on the f i l a m e n t .
If filament s k i n formation i s slow because s u r f a c e d i f f u s i o n of
carbon i s slow, the a v a i l a b l e c a t a l y s t surface f o r s o r p t i o n and
decomposition of hydrocarbon decreases; the temperature g r a d i e n t
and the carbon d i f f u s i o n r a t e are both reduced slowing the growth
rate. E v e n t u a l l y growth ceases when the leading face i s covered
by a l a y e r of carbon, preventing f u r t h e r hydrocarbon
decomposition. The p o s t u l a t e that d i f f u s i o n of carbon through the
p a r t i c l e i s the r a t e - c o n t r o l l i n g step i n the process i s supported
by measurements of the a c t i v a t i o n energy f o r filament growth,
which c o r r e l a t e with those f o r d i f f u s i o n of carbon through the
corresponding metals, Table 1. A major c r i t i c i s m of t h i s
mechanism being accepted as a g e n e r a l e x p l a n a t i o n f o r the filament
growth process i s that i t f a i l s to account f o r filaments produced
by p y r o l y s i s of methane, an endothermic decomposition ( 7 ) .

BAKER ET AL. Filamentous Carbon Formation
Figure 1. Transmission electron micrograph of filaments showing the catalyst

particles at their heads.
Figure 2. Schematic of the proposed mechanism of carbon filament formation.

4 COKE FORMATION
Table I
Comparison of Measured A c t i v a t i o n Energies f o r
Filament Growth with Those f o r Carbon
Diffusion i
CATALYST ACTIVATION ENERGY FOR
CATALYZED FILAMENT DIFFUSION
GROWTH OF CARBON
1
(KCAL MOLE" ) 1
(KCAL MOLE" )
NICKEL 34.7 (5) 33.0-34.8 (15)
ot-IRON 16.1 (6) 10.5-16.5 (16)
NICKEL-IRON 33.6 (8) 34.0 (17)
COBALT 33.0-33.3 (6) 34.7 (18)
VANADIUM 27.6 (21) 27.8 (19)
MOLYBDENUM 38.8 (21) 41.0 (20)
CHROMIUM 27.1 (6) 26.5 (22)

1. BAKER ET AL. Filamentous Carbon Formation 5
Other mechanisms have been proposed f o r filamentous carbon

growth, and other filament s t r u c t u r e s have been observed. One of
the most common v a r i a t i o n s i n the b a s i c filament type i s the
s p i r a l conformation, examples of which are shown i n Figure 3.
Boehm (8) has put forward an i n t e r e s t i n g approach to account f o r
growth of s p i r a l filaments produced during the i r o n - c a t a l y z e d
d i s p r o p o r t i o n a t i o n of carbon monoxide, which i s shown
s c h e m a t i c a l l y i n Figure 4. He suggests that s p i r a l s occur when
the d i f f u s i o n path l e n g t h i n the c a t a l y s t p a r t i c l e v a r i e s ; t h i s i s
probably t r u e , but s p i r a l s w i l l a l s o form i f the v a r i a t i o n of
d i f f u s i o n path length i s not symmetrical about the a x i s of
symmetry of the p a r t i c l e . Two s i t u a t i o n s where t h i s c o n d i t i o n
would a r i s e are (a) i f the c a t a l y s t p a r t i c l e i s not symmetrical,
or (b) i f the p a r t i c l e i s symmetrical but the f l u x of carbon atoms
i s between n o n - p a r a l l e l f a c e s Then provided th particl
maintains i t s shape, th
A further modificatio growt proces
with filaments which are formed by an e x t r u s i o n mode. In t h i s
case, filaments do not grow from a f r e e p a r t i c l e but from a
p a r t i c l e which remains attached to the support s u r f a c e . This
s i t u a t i o n probably a r i s e s from a strong i n t e r a c t i o n between the
metal p a r t i c l e and the support. A mechanism was proposed by Baker
and Waite (9) f o r the e x t r u s i o n f i l a m e n t s produced from the Fe-
Pt/C H2 system d e p i c t e d s c h e m a t i c a l l y i n F i g u r e 5.
2 In t h i s
system, Pt was believed to segregate to the p a r t i c l e surface and
form an apron around a core of Fe. I t was assumed that, under the
p r e v a i l i n g r e a c t i o n c o n d i t i o n s , decomposition of acetylene
occurred predominantly on the P t - r i c h r e g i o n of the p a r t i c l e .
They suggested that t r a n s p o r t of carbon through the c a t a l y s t took
place by a consecutive process: rapid d i f f u s i o n through Pt
followed by slower d i f f u s i o n through the Fe component to be
p r e c i p i t a t e d on the upper surface of the p a r t i c l e as a f i l a m e n t .
In a recent study, Baker and C h l u d z i n s k i (10) used the b a s i s
of t h i s proposed mechanism to develop methods of i n h i b i t i n g the
growth of filamentous carbon. The approach was aimed at the
i n t r o d u c t i o n of a d d i t i v e s i n t o the metal c a t a l y s t p a r t i c l e s , which
had the p o t e n t i a l of reducing the r a t e of the c r i t i c a l steps
involved i n the growth process i . e . , carbon s o l u b i l i t y or carbon
d i f f u s i o n through the c a t a l y s t p a r t i c l e . Among s e v e r a l a d d i t i v e s
i n v e s t i g a t e d , s i l i c a was the most e f f e c t i v e as i t reduced the
r a t e s of both of these processes.
The g r a p h i t e p l a t e l e t d e p o s i t i s formed i n d i r e c t l y , at the
expense of the other two d e p o s i t forms and a l s o r e q u i r e s the
p a r t i c i p a t i o n of a metal c a t a l y s t . I t has been found that i f the
temperature of a metal f o i l , coated with carbon d e p o s i t , i s r a i s e d
to about 1000C, a s i g n i f i c a n t f r a c t i o n of the carbon i s taken
i n t o s o l u t i o n by the metal. On subsequent cooling t h i s carbon i s
p r e c i p i t a t e d as h i g h l y c r y s t a l l i n e g r a p h i t e , underlaying excess
amorphous and filamentous m a t e r i a l remaining on the s u r f a c e . T h i s
p l a t e l e t d e p o s i t i s the most o x i d a t i o n r e s i s t a n t of the three

6 COKE FORMATION
Figure 3. Spiral filaments produced

from the cobalt-acetylene system.

BAKER ET A L . Filamentous Carbon Formation
Figure 4. Schematic of growth mechanism of filamentous carbon on iron carbide.

Key: left, on rectangular carbide particle; and right, on carbide particle with two
active faces at oblique angles. (Reproduced, with permission, from Ref. 8.)
C H
2 2
C C
(c) (d)
Figure 5. Stages in the growth of filaments via the extrusion mode from Pt-Fe/
CH.
2 2 (Reproduced, with permission, from Ref. 9. Copyright 1975, Journal of
Catalysis.)

COKE FORMATION
forms of carbon d e s c r i b e d here and i t i s u n l i k e l y that i t would be

a l l removed during a commercial decoking o p e r a t i o n . I f , however,
oxygen can gain access to the graphite/metal i n t e r f a c e , then the
l a t t e r may f u n c t i o n as a c a t a l y s t f o r carbon g a s i f i c a t i o n and
enhance carbon removal.
Figure 6 i s a h y p o t h e t i c a l p l o t showing the r e l a t i v e r a t e s of
formation of the three types of carbon as a f u n c t i o n of r e a c t i o n
temperature and provides an i n d i c a t i o n of the t y p i c a l composition
of the carbonaceous deposit produced on a metal surface when
exposed to a hydrocarbon environment at a given temperature.
One of the most u s e f u l t o o l s a v a i l a b l e f o r c h a r a c t e r i z i n g
carbonaceous d e p o s i t s i s c o n t r o l l e d atmosphere e l e c t r o n microscopy
(CAEM) (11). T h i s technique enables one to f o l l o w the changes
taking p l a c e i n a s o l i d while i t i s undergoing r e a c t i o n with a
gaseous environment at e l e v a t e d temperatures Capitalizin th
different oxidation characteristic
i t i s p o s s i b l e to s e l e c t i v e l y
u n t i l only a metal r e s i d u e remains. In t h i s way an o v e r a l l
p i c t u r e can be b u i l t - u p of which components were present i n the
o r i g i n a l coke deposit and i n some cases g a i n an i n s i g h t i n t o the
mechanism of i t s formation.
In the present i n v e s t i g a t i o n a v a r i e t y of i n s i t u techniques,
i n c l u d i n g CAEM, have been used along with the more conventional
bulk approaches to compare the c a t a l y t i c r e a c t i v i t y of Fe, FeO and
?&23 p r e c u r s o r s f o r the formation of filamentous carbon from
ethane and a c e t y l e n e .
Experimental
C o n t r o l l e d Atmosphere Transmission E l e c t r o n Microscopy.

D e t a i l s of the CAEM technique are a l r e a d y w e l l documented(ll), so
only a b r i e f d e s c r i p t i o n w i l l be given here. The key design
feature i s the a b i l i t y to operate at r e l a t i v e l y high gas pressure
i n the specimen r e g i o n while maintaining very low pressure i n the
r e s t of the microscope. T h i s c o n d i t i o n i s a t t a i n e d by the
i n c o r p o r a t i o n of a g a s - r e a c t i o n stage i n t o a JEM-120 t r a n s m i s s i o n
e l e c t r o n microscope. With t h i s arrangement i t i s p o s s i b l e to
c o n t a i n gas i n the v i c i n i t y of the specimen at pressures up to 400
Torr and a l s o heat the specimen at temperatures up to 1300PC.
Part of the t r a n s m i s s i o n image passes through a hole i n the
standard viewing screen and impinges on a high s e n s i t i v i t y
phosphor screen. The image i s focussed onto a "Plumbicon"
t e l e v i s i o n camera l o c a t e d o u t s i d e the vacuum chamber. The output
from the camera i s d i s p l a y e d on a TV monitor and simultaneously
recorded on video tape. T h i s f a c i l i t y provides immediate r e c a l l
of i n f o r m a t i o n and the p r o v i s i o n of making permanent records on
16 mm c i n e f i l m .
The technique not only provides a q u a l i t a t i v e p i c t u r e of the
changes i n appearance of the specimen undergoing r e a c t i o n , but i n
many cases i t i s p o s s i b l e to perform d e t a i l e d k i n e t i c a n a l y s i s on

CARBON TYPES AS A FUNCTION OF TEMPERATURE

TEMPERATURE: C
Figure 6. Hypothetical plot showing the relative rates of formation of three types of carbon
deposit as a function of temperature. Key: , graphitic; , amorphous; and , fila-
mentous.
10 COKE FORMATION
such sequences. Unfortunately the m o d i f i c a t i o n s which have to be

made to the microscope to accomodate the g a s - r e a c t i o n stage and
the presence of a gas l i m i t the r e s o l v i n g power of the instrument
to 2.5 nm.
S i n g l e c r y s t a l g r a p h i t e obtained from Ticonderoga, New York
State, was used as the support medium of the r e a c t i o n s studied i n
this investigation. The c r y s t a l s were r e l e a s e d from the pyroxene
mineral i n which they were embedded by the method described by
Hennig (12). They were f i r s t cleaved between g l a s s s l i d e s coated
with ' B r i t f i x ' polystyrene cement, and then r e l e a s e d and washed
with acetone. The c r y s t a l s were mounted on g l a s s s l i d e s with
aqueous p o l y v i n y l - p y r r o l i d o n e (PVP) adhesive. The PVP was allowed
to dry and the c r y s t a l s f u r t h e r cleaved with "Scotch" tape.
Successive l a y e r s were removed u n t i l an o p t i c a l l y transparent
p o r t i o n of the c r y s t a l remained a f f i x e d to the s l i d e Such
c r y s t a l s were good e l e c t r o
c r y s t a l s were r e l e a s e d fro
and picked up on the microscope specimen heater ribbons and
dried. Specimens were prepared according to two procedures. In
the f i r s t , p a r t i c l e s of bulk FeO d e r i v e d from the macro-scale
experiments and Fe^C, which was prepared as a powder, were
s e p a r a t e l y deposited onto t r a n s m i s s i o n s e c t i o n s of s i n g l e c r y s t a l
g r a p h i t e s u b s t r a t e s by a d u s t i n g technique. In the second method
i r o n was deposited as a t h i n f i l m on g r a p h i t e from a
s p e c t r o g r a p h i c a l l y pure wire, at a r e s i d u a l pressure of 5 10"
Torr from a heated tungsten f i l a m e n t . The d e s i r e d s t a r t i n g s t a t e
of the i r o n was obtained by (a) n u c l e a t i n g i n hydrogen at 675C to
ensure i r o n was i n the completely reduced s t a t e , or (b) treatment
i n 5 Torr oxygen at 600c f o r 1 hour to form Fe 03 2 A l l specimens
were subsequently reacted i n 2 Torr a c e t y l e n e .
In a separate set of experiments carbonaceous d e p o s i t s
produced i n the macro-scale s t u d i e s were c h a r a c t e r i z e d by
o x i d i z i n g the m a t e r i a l s under c o n t r o l l e d c o n d i t i o n s i n the CAEM.
These samples were made by s p r i n k l i n g loose fragments of the
deposit onto the t r a n s m i s s i o n specimens of g r a p h i t e . Every e f f o r t
was made to prevent the i n t r o d u c t i o n of any f o r e i g n matter i n t o
the samples.
Mossbauer Spectroscopy. The Mossbauer spectroscopy c e l l used

i n t h i s work was constructed with 131 Teflon-coated Kapton
(Dupont) windows which allowed f o r transmission by -rays.
Constant a c c e l e r a t i o n s p e c t r a were obtained with an A u s t i n Science
A s s o c i a t e s , Inc. S-600 Mossbauer spectrometer equipped with an
electromagnetic Doppler v e l o c i t y motor. The source was 50 m Ci of
"^Co d i f f u s e d i n t o a palladium matrix, and i t was obtained from
New England Nuclear, Inc. The pulses from the p r o p o r t i o n a l
counter d e t e c t o r (Reuter Stokes) were a m p l i f i e d , shaped and gated
using A u s t i n Science A s s o c i a t e s e l e c t r o n i c s . These shaped pulses
were then sent to a Tracor Northern NS-900 multichannel
analyzer. The MCA was i n t e r f a c e d d i r e c t l y to a PDP-11 m i n i
computer, g r e a t l y f a c i l i t a t i n g data storage and a n a l y s i s .

The sample was a 0.0127 mm t h i c k i r o n f o i l , of 99.99% p u r i t y ,

cut i n t o d i s k s (2.5 cm d i a m e t e r ) . Room temperature Mossbauer
s p e c t r a were taken i n the i n i t i a l s t a t e , a f t e r treatment at 800C
f o r 30 minutes i n 1 atm. argon saturated with water at room
temperature, and f i n a l l y a f t e r r e a c t i o n i n 1 atm. a c e t y l e n e a t
750C f o r 0.5 minute. V e l o c i t i e s were c a l i b r a t e d u s i n g the known
Mossbauer parameters of m e t a l l i c i r o n at 25C, and zero v e l o c i t y
i s with respect to t h i s standard absorber.
Macro-Scale Experiments. For studying filamentous carbon

formation on a macro-scale, the f o l l o w i n g apparatus was used. The
r e a c t o r was a fused s i l i c a tube (2.54cm i n diameter) which was
90cm long and e x t e r n a l l y heated v i a a three zone furnace, which
was 61cm long o v e r a l l . The center zone was 46cm long and i t could
be held at a set temperatur 1C
The m e t a l l i c i r o n use
of a f o i l , 0.013 cm t h i c and had a s t a t e d p u r i t y o 99.99
( M a t e r i a l s Research Corp., Orangeburg, NY). The f o i l was cut i n t o
p i e c e s 3 cm 0.6 cm. Before each experiment the metal f o i l s were
cleaned according to the f o l l o w i n g procedure: i n i t i a l immersion
i n 190 proof e t h y l a l c o h o l , treatment i n t o l u e n e , then e t h y l
a l c o h o l again, washing i n b o i l i n g d i s t i l l e d water, and then e t h y l
a l c o h o l , and f i n a l l y d r y i n g i n a i r .
W e l l - d e f i n e d samples of FeO were prepared by t r e a t i n g the
i r o n f o i l s with steam at temperatures above 700C. Identification
of the oxide was accomplished using Mossbauer and Auger e l e c t r o n
s p e c t r o s c o p i e s , and x-ray d i f f r a c t i o n techniques. Auger s p e c t r a
of the f o i l s were obtained using a P h y s i c a l E l e c t r o n i c s Model 549
combination ESCA-Auger Spectrometer. Spectra were taken u s i n g a
5KV primary beam voltage and the r e l a t i v e atomic c o n c e n t r a t i o n s of
Fe and 0 were obtained by measuring the peaks at 703eV f o r Fe, and
at 503eV f o r 0. The procedure o u t l i n e d i n r e f e r e n c e (13) was
followed f o r c a l c u l a t i n g the q u a n t i t a t i v e compositions of these
two elements.
As most Auger e l e c t r o n s have energies below 1000eV(14), t h e i r
escape depth i s small, u s u a l l y l e s s than 5 nm, which has the
consequence that the Auger spectrum i s an average composition of
the surface of the sample down to t h i s depth. N e v e r t h e l e s s , the
s p e c t r a l i n f o r m a t i o n i s obtained mainly from the f i r s t 2 or 3
l a y e r s of the sample. Data c o l l e c t e d i n t h i s manner showed that
f o r depths down to 600 nm the composition was i n the range FeOQ
Fe e t v c a
to O o . 9 2 ^ P i l spectrum i s shown i n F i g u r e 7, which was
obtained a f t e r 25 minute argon i o n s p u t t e r i n g , at a depth of
325 nm. Apart from a small peak due to embedded Ar atoms, the
only peaks other than Fe and 0, are very small peaks of S i and
F e 0
C. This p a r t i c u l a r sample had a composition of o.92*
Other p o r t i o n s of these samples were ground to a powder and
examined by conventional x-ray d i f f r a c t i o n techniques, which
showed only peaks due to FeO. The ?&23 u s e ( i
* n
^t n s w
o r k was
i n i t i a l l y i n the form of a powder, s t a t e d p u r i t y 99.8% ( F i s c h e r

12 COKE FORMATION

1. BAKER ET A L . Filamentous Carbon Formation 13
S c i e n t i f i c Co.) and was pressed i n t o s e l f - s u p p o r t i n g wafers,

2.5 cm i n diameter.
A f t e r the specimens were loaded i n t o the furnace tube, they
were heated i n N t o 700C, p r i o r to i n t r o d u c t i o n of ethane. With
2
the tube s t i l l maintained at 700C, ethane was admitted at a flow

r a t e of 94 cm /mi and the r e a c t i o n allowed to continue f o r
periods of between 1.0 t o 6.0 hours. The weight of deposited
carbon was determined by d i f f e r e n c e of the s t a r t i n g and f i n a l
specimen weights. In a d d i t i o n , the chemical s t a t e of i r o n i n the
FeO a n d F e ^ ^ precursors was determined by room temperature
Mossbauer spectroscopy a f t e r 2.Oh of r e a c t i o n i n e t h a n e a t
700C.
RESULTS
C o n t r o l l e d Atmospher
i n i t i a l experiments m i c r o - s i z e d pieces of FeO, supported on
g r a p h i t e , were heated d i r e c t l y i n 2 Torr a c e t y l e n e . At 500C the
f i r s t signs of a change i n the p r o f i l e of the oxide were detected
and t h i s became more rapid at 575C as filaments s t a r t e d to appear
from the edges. These f i l a m e n t s , which ranged from 2.5 to 5 nm i n
width and up to 5000 nm i n l e n g t h , grew by rapid e x t r u s i o n , with
the c a t a l y s t p a r t i c l e remaining embedded i n the FeO mass. As the
temperature was g r a d u a l l y r a i s e d filamentous growth became more
p r o l i f i c and the vehemence of the r e a c t i o n o f t e n r e s u l t e d i n
rupture and fragmentation of the FeO s e c t i o n s i n t o s m a l l e r
p a r t i c l e s , which r e s u l t e d i n the exposure of f u r t h e r a c t i v e
regions. Experiments were terminated at 800C as the amount of
d e p o s i t was so heavy that i t was impossible to d i s c e r n the growth
of i n d i v i d u a l f i l a m e n t s .
In a second s e r i e s of experiments, an evaporated i r o n f i l m on
g r a p h i t e was heated i n 1.0 Torr H at 675C f o r 1 hour to ensure
2
complete r e d u c t i o n to the m e t a l l i c s t a t e . A f t e r evacuation of the

H , and cooling to room temperature, acetylene was introduced at a
2
pressure of 2.0 T o r r . Upon subsequent r e h e a t i n g , f i l a m e n t s were

observed at 615C. These f i l a m e n t s a l l grew by the commonly
observed mode; i . e . the c a t a l y s t p a r t i c l e r e s p o n s i b l e f o r the
growth remained at the head of a filament so that during the
growth process i t was c a r r i e d away from the support. In t h i s case
there was a s i g n i f i c a n t l y wider s i z e range of f i l a m e n t s compared
to those formed on FeO, being 2.5 t o 50 nm at 650C. Although the
number and s i z e of f i l a m e n t s increased as the temperature was
slowly r a i s e d to 825C, i t was q u i t e apparent that the number of
f i l a m e n t s formed i n t h i s system was f a r l e s s than that produced
from the i n t e r a c t i o n of FeO with a c e t y l e n e .
The remainder of the specimens were pretreated i n 5 Torr 0 2
at 600C f o r 1 hour, c o n d i t i o n s where the metal i s expected to

form F e 0 g . When these specimens were exposed to 2 Torr
2
acetylene, filamentous carbon formation was not detected u n t i l

700C. Even a t t h i s temperature, r e a c t i o n was r e s t r i c t e d to only

14 COKE FORMATION
a few p a r t i c l e s , the m a j o r i t y remaining q u i t e i n a c t i v e even a t

temperatures up to 900C. The f i l a m e n t s that were formed grew by
the e x t r u s i o n mode, as with FeO.
F i n a l l y , p a r t i c l e s of Fe^C, supported on g r a p h i t e were
reacted i n 2 T o r r a c e t y l e n e . I n c o n t r a s t to the behavior of
previous systems, Fe^C d i d not c a t a l y z e the formation o f
filamentous carbon. Indeed the p a r t i c l e s showed very l i t t l e
change i n appearance on heating up t o 900C.
The CAEM technique was a l s o used to c h a r a c t e r i z e the
carbonaceous d e p o s i t s produced i n the macroscale s t u d i e s . I n t h i s
case fragments of the v a r i o u s d e p o s i t s were d i s p e r s e d onto
t r a n s m i s s i o n specimens o f g r a p h i t e and subsequently heated i n 5
Torr 0 During t h i s r e a c t i o n the v a r i o u s carbonaceous components
2
of the d e p o s i t o x i d i z e d a t d i f f e r e n t r a t e s and numerous d e t a i l s

became evident. At 600C the amorphous carbon was removed leaving
behind a predominantly
s t r u c t u r e s , which forme
width from 5 to 35 nm, and were up to 1x10 nm i n l e n g t h . Upon
f u r t h e r o x i d a t i o n up to 750C, v i r t u a l l y a l l the carbonaceous
m a t e r i a l had disappeared leaving a residue of metal or metal oxide
particles.
Mossbauer Spectroscopy Experiments. The Mossbauer spectrum

of the as received i r o n f o i l i s presented i n F i g u r e 8A and shows
the six-peaked p a t t e r n c h a r a c t e r i s t i c of the pure metal. Figure
8B i s the spectrum recorded a f t e r treatment with steam a t 800C
and c l e a r l y demonstrates the dramatic change i n the nature of the
specimen. Although the six-peak s p e c t r a l p a t t e r n of m e t a l l i c i r o n
s t i l l remains, i t i s c l e a r that i t i s now no longer the major
component; the m a j o r i t y of i r o n has been converted to another
phase.
The corresponding s p e c t r a l component i s a q u a d r u p o l e - s p l i t
doublet having the following Mossbauer parameters: quadrupole
s p l i t t i n g of 0.58 mms~ and isomer s h i f t r e l a t i v e t o m e t a l l i c i r o n
of 0.94 mms These parameters are i d e n t i c a l to those of FeO
(23, 24). Measurements of the t o t a l areas under the Fe and FeO
peaks showed that only 12% o f the i r o n remained i n the m e t a l l i c
s t a t e a f t e r the steam treatment, assuming that Fe and FeO have
equal r e c o i l - f r e e f r a c t i o n s . F i n a l l y , the specimen was heated i n
1 atm acetylene at 750C and the spectrum shown i n Figure 8C was
recorded. Compared to the spectrum c o l l e c t e d a f t e r treatment i n
steam, the acetylene treatment leads to an i n c r e a s e i n the amount
of m e t a l l i c i r o n a t the expense of FeO. This can be made more
q u a n t i t a t i v e from measurements of the areas under the Mossbauer
s p e c t r a peaks which shows that Fe now accounts f o r 23% of the Fe
species present. Also apparent i n Figure 8C i s a small amount of
the six-peak p a t t e r n c h a r a c t e r i s t i c o f Fe^C (25), as shown by the
stick-diagram i n t h i s F i g u r e .

BAKER E T A L . Filamentous Carbon Formation
Fe C3
LU
>
<
-7.5 -5.0 -2.5 0 2.5 5.0 7.5 10.0
V E L O C I T Y (mm/s)
Figure 8. Room temperature Mossbauer spectra of a metallic iron foil after treat
ments in steam and acetylene. Key: A, metallic iron foil as received; B, from foil
after treatment in steam at 800C; and C, sample of after treatment in acetylene
at 7500C.

16 COKE FORMATION
Macro-Scale Experiments. Figure 9 shows a comparison of the

v i s u a l changes i n appearance of Fe and FeO f o i l s accompanying the
d e p o s i t i o n of carbon from ethane at 700C. I n s p e c t i o n of the
d e p o s i t derived from FeO showed no t r a c e s of the o r i g i n a l f o i l .
E v i d e n t l y during the r e a c t i o n the f o i l had undergone complete
d i s i n t e g r a t i o n i n t o small p a r t i c l e s i n t i m a t e l y mixed with
carbon. Table 2 summarizes the y i e l d s of carbon which were
measured on the three types of specimens s t u d i e d . I t should be
emphasized that the data obtained f o r &23 a r
P e r o D a D
^ y higher
than they should be as the i n i t i a l surface area of the s t a r t i n g
powder was much higher than that of e i t h e r of the f o i l
specimens. Nevertheless, i t i s obvious that FeO i s by f a r the
most a c t i v e surface f o r carbon growth. Portions of a l l these
d e p o s i t s were subsequently o x i d i z e d i n the CAEM where the carbon
was found to be predominantly filamentous.
The Mossbauer s p e c t r o s c o p i
precursors a f t e r r e a c t i o
presence of only m e t a l l i c i r o n and i r o n carbide (Fe^C) i n both
samples, as can be seen i n Figure 10. Important i s the
o b s e r v a t i o n that n e i t h e r FeO nor ?&23 c a n e
^ detected i n e i t h e r
sample. For the FeO precursor, 14% of the i r o n i s present as
m e t a l l i c i r o n a f t e r r e a c t i o n i n ethane, while l e s s than 5% of the
i r o n i s m e t a l l i c f o r the f ^ O ^ precursor. ( I t i s not known at
present, however, whether the d i f f e r e n c e i n the amount of m e t a l l i c
i r o n f o r the FeO and ?&23 P r e c u r s o r s s
* s i g n i f i c a n t since the
amount of m e t a l l i c i r o n f o r a g i v e n precursor varied from sample
to sample).
Discussion
The macro-scale i n v e s t i g a t i o n s showed that pretreatment of an

i r o n surface with steam at 700C induces a dramatic increase i n
the c a t a l y t i c a c t i v i t y f o r carbon d e p o s i t i o n from hydrocarbons.
Spectroscopic a n a l y s i s (Auger and Mossbauer) combined with weight
increase measurements prove that treatment of i r o n with steam at
700C r e s u l t s i n the conversion of the surface of the i r o n to
FeO. At 800C, t h i s process i s not j u s t l i m i t e d to the uppermost
surface l a y e r s but penetrates to an a p p r e c i a b l e depth of the
m a t e r i a l a f t e r a three hour treatment. Indeed Mossbauer
spectroscopy data shows that nearly a l l of a 0.013 cm Fe f o i l i s
transformed to FeO i n t h i s time at 800C. I t should be mentioned
that the r e a c t i o n of steam with i r o n to produce FeO may be
p o s s i b l e at temperatures above 570C ( 3 ) . The nonstoichiometric
nature of FeO has been the subject of considerable number of
papers. It i s known, however, that the d e f e c t s present i n t h i s
m a t e r i a l are vacant c a t i o n s i t e s and trapped p o s i t i v e holes (26).
Comparison of the carbonaceous d e p o s i t s produced on the
macro- and micro-scale specimens shows that they are very s i m i l a r
i n nature, the major c o n s t i t u e n t being filamentous carbon.
Previous work on the formation of t h i s type of carbon on supported

Figure 9. Changes in appearance of Fe and FeO foils accompanying the deposi

tion of carbon from ethane at 700C.
Table I I
Carbon F o r m a t i o n from C a t a l y z e d
D e c o m p o s i t i o n o f E t h a n e a t 700C
Carbon Formed 10~* g / c n r / h
State of Iron Average High Low
Fe 114 148 60
FeO 1380 1870 1080
Fe P *
2 3 271 440 174
*Note: The ?&23 w a s

u s e d a s a p r e s s e d powder, w i t h q u i t e a h i g h
s u r f a c e a r e a , w h i l e t h e F e a n d FeO were f o i l s o f
e s s e n t i a l l y g e o m e t r i c s u r f a c e a r e a . The r a t e s a r e
c a l c u l a t e d on t h e e x t e r n a l a r e a o f t h e w a f e r s and t h u s t h e
r a t e s g i v e n a b o v e f o r F e 2 0 a r e p r o b a b l e t o o h i g h on a
3
p e r cm^ b a s i s .

18 COKE FORMATION
-10.0 -5.0 0 5.0 10.0
VELOCITY (mm/s)
Figure 10. Room temperature Mossbauer spectra of the Fe O and FeO pre-
2 s
cursors after reaction in ethane at 700C for 2 hours. Key: A, Fe O precursor;

2 s
and B, FeO precursor.

metal p a r t i c l e s thus becomes extremely r e l e v a n t to the current

i n v e s t i g a t i o n . A c o n s i d e r a b l e body of i n f o r m a t i o n concerning t h i s
type of carbonaceous d e p o s i t has been b u i l t up over recent years
2).
In the present macro-scale experiments the f i l a m e n t s have
been formed f o l l o w i n g r e a c t i o n of ethane with i r o n and i r o n
oxides. The decomposition of ethane to elemental carbon and
hydrogen i s endothermic (27) and so, at f i r s t s i g h t , i t appears
that the experimental r e s u l t s are i n c o n f l i c t with the above
mechanism of filament growth. However, e a r l i e r work (28) has
shown that the m a j o r i t y of carbon formed from ethane a r i s e s from
the decomposition product e t h y l e n e . The l a t t e r decomposes
1
e x o t h e r m i c a l l y (27) (- H f o r C H at 725C i s 9.2 k c a l . m o l e " )
2 4
so that t h i s mechanism i s not contravened. A s i m i l a r r a t i o n a l e

was used by Keep, Bake
formation of carbon f i l a m e n t
decomposition of propane.
The key to the extremely high a c t i v i t y f o r filament
p r o d u c t i o n found with FeO may w e l l r e s i d e i n the d e f e c t s t r u c t u r e
of t h i s compound. In such a s t r u c t u r e the oxygen atoms i n the
surface w i l l be r e a d i l y a c c e s s i b l e to e x t r a c t i o n by protons
generated by the hydrocarbon decomposition r e a c t i o n and as a
r e s u l t the oxide could r a p i d l y a t t a i n at the s u r f a c e an i r o n r i c h
sponge-like arrangement i . e . the r o l e of FeO i s that of a
precursor f o r a high s u r f a c e area Fe c a t a l y s t formed i n - s i t u .
This hypothesis i s supported by the Mossbauer spectroscopy d a t a
which c l e a r l y shows that Fe i s being produced at the expense of
FeO as carbon i s being d e p o s i t e d . In a d d i t i o n , the i r o n i n both
the FeO and F e 0 p r e c u r s o r s i s present as m e t a l l i c i r o n and i r o n
2 3
c a r b i d e a f t e r r e a c t i o n i n ethane, i n d i c a t i n g that the chemical

s t a t e of i r o n i s e s s e n t i a l l y the same i n both samples a f t e r
r e a c t i o n ; t h e r e f o r e the dramatic d i f f e r e n c e s i n r e a c t i v i t y of
these two p r e c u r s o r s f o r carbon d e p o s i t i o n must be traced to
d i f f e r e n c e s i n e f f e c t i v e s u r f a c e areas. This i s d e s p i t e the f a c t
that the FeO was prepared from a low s u r f a c e area f o i l of m e t a l l i c
i r o n while the F e 0 g was present as a higher s u r f a c e area
2
powder. This suggests that small m e t a l l i c p a r t i c l e s are formed

from the FeO p r e c u r s o r . T h i s leads to the rapid p r o d u c t i o n of
many t h i n carbon f i l a m e n t s having small i r o n p a r t i c l e s at t h e i r
growing t i p s . The m e t a l l i c i r o n p a r t i c l e s formed from the F e 0 ^
2
p r e c u r s o r , on the other hand, are e v i d e n t l y much l a r g e r than those

formed from FeO. This leads to the slower growth of a s m a l l e r
number of wider carbon f i l a m e n t s . A s i m i l a r concept was proposed
by Guinot et a l (30) who suggested that fragmentation of an i r o n -
n i c k e l low s u r f a c e area c a t a l y s t by the carbon d e p o s i t i o n from CO
d i s p r o p o r t i o n a t i o n was a necessary step i n order to account f o r
the high r a t e of r e a c t i o n .
F i n a l l y , the CAEM s t u d i e s show that Fe3C i s n o t a n a c t i v e
c a t a l y s t f o r carbon filament formation. This o b s e r v a t i o n i s a l s o
supported by the Mossbauer spectroscopy d a t a which show that the

20 COKE FORMATION
i r o n carbide c o n c e n t r a t i o n increases as c a t a l y t i c a c t i v i t y de
clines. T h i s f i n d i n g does not preclude the p o s s i b i l i t y that Fe3C
might c a t a l y z e the formation of other forms of carbon d e p o s i t .
Acknowledgments
The authors would l i k e to thank M. Estadt and J.J. C h l u d z i n s k i

f o r t h e i r a s s i s t a n c e with the microscopy s t u d i e s ; J. McHenry who
c a r r i e d out the macro-scale experiments; and J. P h i l l i p s and
W.M. Shen ( U n i v e r s i t y of Wisconsin) who k i n d l y performed the M o s s
bauer spectroscopy work presented here.
Literature Cited
1. Palmer, H. B. and Cullis,

Carbon"; V o l . 1, (P. L. Walker, J r . ed.), p.265, Dekker,
New York, 1965.
2. Baker, R. T. K. and H a r r i s , P.S. "Chemistry and Physics of
Carbon"; V o l . 14, (P. L. Walker, J r . and P. A. Thrower, eds.),
p. 83, Dekker, New York, 1978.
3. Gainey, B. W.; U.S. Energy Research and Development Admin.
Report GA-A13982, UC-77.
4. Lahaye, J., Badie, P., and Ducret, J.; Carbon (1977), 15, 87.
5. Baker, R. . ., Barber, . ., Feates, F. S., H a r r i s , P. S.,
and Waite, R. J.; J. C a t a l . (1972), 26, 51.
6. Baker, R. . ., H a r r i s , P. S., Thomas, R. B., and Waite, R. J.,
J. C a t a l . (1973), 30, 86.
7. Rostrup-Neilson, J. R. "Steam Reforming C a t a l y s t s " , Teknisk
F o r l a g A/S (Danish T e c h n i c a l P r e s s , I n c . ) , Copenhagen, 1975.
8. Boehm, H. P.; Carbon (1973), 11, 583.
9. Baker, R. T. K. and Waite, R. J.; J. C a t a l . (1975), 37, 101.
10. Baker, R. T. K. and C h l u d z i n s k i , J. J., J r . ; J. C a t a l . (1980),
64, 464.
11. Baker, R. T. K. and H a r r i s , P. S.; J. Phys. . (1970), 5, 793.
12. Hennig, G. R. "Chemistry and Physics of Carbon", V o l . 2
(P. L. Walker, J r . , ed.), Dekker, p. 1, New York, 1966.
13. Davis, L. . "Handbook of Auger E l e c t r o n Spectroscopy", 2nd
Ed., Publ. P h y s i c a l E l e c t r o n i c s I n d u s t r i e s Inc., Eden P r a i r i e ,
Minn., 1976.
14. Chang, C. C.; Surf. S c i . (1971), 25, 53.
15. Diamond, S. and Wert, C.; Trans. AIME (1967), 239, 705.
16. Morgan, D. W. and K i t c h e n e r , J. .; Trans. Faraday Soc. (1964),
50, 51.
17. Smith, R. P.; Trans. Met. Soc. AIME (1966), 236, 1224.
18. Kovenskuj, J. J.; Phys. Metlas M e t a l l a g e (USSR) (1963), 16, 107.
19. Schmidt, F. A. and Warner, J. C.; J. Less-Common Metals
(1972), 26, 325.
20. Rudman, P.S.; Trans. Met. Soc. AIME (1967), 239, 1949.

21. Baker, R. T. ., Dudash, M. S., C h l u d z i n s k i , J. J., Jr. and

Simoens, J. A. Unpublished r e s u l t s .
22. B a r i s o n , . V., Gruzin, P. L. and Zemskii, S. V.; Zashch.
P o k r y t i y a Metal (1968), 2, 104.
23. Johnson, D. P.; S o l i d S t a t e Comm. (1969), 7, 1785.
24. Greenwood, . . and Gibb, T. C. Mssbauer Spectroscopy,
Chapman and Hall L t d . , London 1971.
25. Raupp, G. B. and Delgass, W. N.; J. C a t a l . (1979), 58, 348.
26. J e t t e , . R. and Foote, F.; J. Chem. Phys. (1933), 1, 29.
27. S t u l l , D. R., Westrum, E. F., and Sinke, G. G. "The Chemical
Thermodynamics of Organic Compounds", Wiley, New York, 1969.
28. A l b r i g h t , L. F., and McConnell, C. F. "Thermal Hydrocarbon
Chemistry" (Eds. A. G. Oblad, H. G. Davis, and R. T. Eddinger)
Advances in Chemistry S e r i e s 183 p 205 Amer Chem Soc.
Washington, D.C. (1979)
29. Keep, C. W., Baker
(1977), 47, 232.
30. Guinot, J., Audier, M., Coulon, M, and Bonnetain, L.;
Carbon (1981), 19, 95.
RECEIVED July 30, 1982.

2
Inhibition of Coke Formation in Ethylene
Steam Cracking
D . E . B R O W N , J. T . K . C L A R K , A . I. F O S T E R , J. J. M c C A R R O L L and
M . L . SIMS
The British Petroleum Company p.l.c., Research Centre Sunbury, Chertsey Road,
Sunbury-on-Thames, Middlesex, United Kingdom
This paper describe

a silica c o a t i n g proces
formation in the p y r o l y s i s s e c t i o n of ethylene steam
crackers (ESC). The coating process utilises the
chemical vapour d e p o s i t i o n of an a l k o x y s i l a n e in
steam c a r r i e r gas to produce a t h i n , impervious,
adherent and amorphous silica f i l m on the i n t e r n a l
surfaces o f high a l l o y s t e e l tubing a t 700-800C.
E v a l u a t i o n in a laboratory s c a l e ethylene steam
c r a c k i n g r e a c t o r employing a t y p i c a l ESC feedstock
(LDF 160) has revealed that the coking r a t e can be
reduced by up to x10 in short term t e s t s and by
x3-4 in longer term t e s t s .
The steam c r a c k i n g o f h y d r o c a r b o n s ( e g n a p h t h a ) t o p r o d u c e
t h e l o w e r o l e f i n s ( e t h y l e n e , p r o p y l e n e , butnes) a n d b u t a d i e n e
i s the basic petroleum chemicals operation. Such steam c r a c k i n g
p l a n t s u f f e r s coke d e p o s i t i o n problems t h a t r e s t r i c t performance.
The c r a c k i n g o p e r a t i o n i n v o l v e s h e a t i n g n a p h t h a d i l u t e d w i t h
steam in r a d i a n t l y h e a t e d c o i l s o f h i g h a l l o y s t e e l t u b i n g t o
t e m p e r a t u r e s o f t y p i c a l l y 850C. D u r i n g c r a c k i n g , coke
d e p o s i t i o n o c c u r s in t h e c o i l s and a s s o c i a t e d downstream
e x c h a n g e r s . The c o k e , w h i c h f o r m s t o d e p t h s o f s e v e r a l mm,
reduces heat t r a n s f e r and n o r m a l l y l i m i t s r u n l e n g t h t o f o u r t o
e i g h t weeks. The c r a c k i n g f u r n a c e must t h e n be t a k e n o f f - s t r e a m
f o r d e c o k i n g , u s u a l l y by s t e a m - a i r o x i d a t i o n , w i t h c o n s e q u e n t i a l
loss o f production. Also, frequent decoking operations present
a d d i t i o n a l f u e l and u t i l i t i e s c o s t s , and p r o b a b l y a f f e c t
coil life. A r e s e a r c h programme was u n d e r t a k e n t o i n v e s t i g a t e
t h e c o k e d e p o s i t i o n phenomena a n d t o d e v e l o p a p o t e n t i a l method
for i t s inhibition.
0097-6156/82/0202-0023$06.50/0

24 COKE FORMATION
ESC Plant Materials Investigation
The r e s e a r c h programme was i n i t i a t e d t h r o u g h a n i n v e s t i g a t i o n

of r a d i a n t c o i l a l l o y s and d e p o s i t e d coke. Radiant c o i l s are
c o n s t r u c t e d in h i g h a l l o y s t e e l s ( e g I n c o l o y 8 0 0 , HK 4 0 , 34 C T ) ,
w i t h i r o n , n i c k e l a n d chromium a s m a j o r components a n d a r a n g e o f
m i n o r c o n s t i t u e n t s s u c h a s s i l i c o n , t i t a n i u m a n d manganese.
S o f t X - r a y a p p e a r a n c e p o t e n t i a l s p e c t r o s c o p y (SXAPS) s t u d i e s
o f r a d i a n t c o i l a l l o y s were c a r r i e d o u t t o d e t e r m i n e s u r f a c e
compositions r e s u l t i n g from exposure t o a range o f environments.
I n p a r t i c u l a r , t h e o x i d e s u r f a c e f i l m s g e n e r a t e d in o x i d i s i n g
c o n d i t i o n s a t h i g h t e m p e r a t u r e s (>800C) r e v e a l e d t h e s e g r e g a t i o n
t o t h e s u r f a c e o f m e t a l s f o r m i n g s t a b l e o x i d e s in p r e f e r e n c e
to m e t a l s f o r m i n g l e s s s t a b l e o x i d e s . T h i s e f f e c t was a l s o f o u n d
on t h e i n t e r n a l s u r f a c e s o f a n aged I n c o l o y 800 r a d i a n t c o i l
f r o m a c o m m e r c i a l ESC
h i g h t e m p e r a t u r e steam
shows t h e SXAPS s p e c t r u m o f t h e s u r f a c e o x i d e , w h i c h ( t a k e n
together w i t h the bulk a l l o y composition) demonstrates the
g e n e r a l o b s e r v a t i o n o f a t r e n d in t h e r a t i o o f s u r f a c e o x i d e
composition t o bulk metal composition f o r the m e t a l l i c a l l o y i n g
e l e m e n t s o f T i > C r > Fe > N i , in l i n e w i t h d e c r e a s i n g o x i d e
stability.
Coke d e p o s i t s f r o m a c o m m e r c i a l ESC p l a n t were a l s o e x a m i n e d .
B u l k m e t a l s c o n c e n t r a t i o n s were d e t e r m i n e d by a s h i n g a t 900C
p r i o r t o emission spectroscopy a n a l y s i s . High l e v e l s of metals
were f o u n d a t t h e r a d i a n t c o i l - c o k e i n t e r f a c e d u e , p r e s u m a b l y ,
to o x i d e s p a l l a t i o n , b u t c o n c e n t r a t i o n s o f m e t a l s ( p r i m a r i l y
chromium, i r o n a n d t i t a n i u m , t o t a l l i n g c a 2 0 0 ppm) were a l s o f o u n d
i n t o t h e b u l k o f t h e coke and a t t h e c o k e - p r o c e s s stream
i n t e r f a c e ( T a b l e I ) . SXAPS e x a m i n a t i o n o f c o k e h e a t e d u n d e r
vacuum f o r s e v e r a l h o u r s a t 900C a l s o r e v e a l e d t h e a p p e a r a n c e
o f up t o 1% c o n c e n t r a t i o n o f m e t a l s a t t h e s u r f a c e o f some c o k e
s a m p l e s , a n d s i g n i f i c a n t l y chromium, i r o n a n d t i t a n i u m were
again the metals observed.
TABLE I
BULK ANALYSIS OF METALS IN COKE DEPOSITS FROM COMMERCIAL
ETHYLENE STEAM CRACKER ( I N ppm)
Sample Ca Ti Cr Mn Fe Ni
Coke f r o m c e n t r a l s e c t i o n 82 27 105 5 53 6
between metal tube and
gas p h a s e i n t e r f a c e s
Coke f r o m g a s phase 11 3 22 3 175 <1

interface

2. BROWN E T AL. Inhibition of Coke Formation 25

26 COKE FORMATION
The p r e s e n c e o f m e t a l s in ESC p l a n t c o k e has been r e p o r t e d

by A l b r i g h t and c o w o r k e r s ( 1 ) , who have d e m o n s t r a t e d t h a t s u c h
m e t a l s c a n c a t a l y s e t h e f o r m a t i o n o f a d d i t i o n a l c o k e . B a k e r and
c o w o r k e r s ( 2 , 3 , 4 ) have p r o v i d e d i n s i g h t i n t o one mechanism f o r
t h e p r o p a g a t i o n o f c o k e d e p o s i t i o n f r o m model h y d r o c a r b o n s
( e g C 2 H 2 , C^HQ) o n t o m e t a l f o i l s . U s i n g c o n t r o l l e d atmosphere
e l e c t r o n m i c r o s c o p y i t was r e v e a l e d t h a t m e t a l c a t a l y s t p a r t i c l e s
can become d e t a c h e d f r o m t h e s u r f a c e and be c a r r i e d away by t h e
growth of f i l a m e n t o u s carbon, w i t h the p a r t i c l e s remaining a t the
filament tips. O t h e r r e s e a r c h e r s have o b s e r v e d a w i d e r a n g e o f
c o k e m o r p h o l o g i e s in p y r o l y s i s (5) and steam c r a c k i n g (6) o f a
range of hydrocarbons over s t e e l s u r f a c e s , s u g g e s t i n g t h a t the
o v e r a l l d e p o s i t i o n p r o c e s s in c o m m e r c i a l s t e a m c r a c k i n g i s
complex.
S e v e r a l s t u d i e s (7,8) hav i n d i c a t e d t h a t th propensit f
t r a n s i t i o n metals f o r c a t a l y s i n
decreasing s t a b i l i t y o
p r o p e n s i t y a l o n g t h e s e r i e s T i < C r < Fe < N i . However, t h e
e x a m i n a t i o n o f t h e ESC r a d i a n t c o i l r e v e a l e d o n l y low l e v e l s o f
n i c k e l in t h e s u r f a c e o x i d e and more p a r t i c u l a r l y v i r t u a l l y no
n i c k e l in t h e c o k e s a m p l e s . T h e r e f o r e , i r o n and p o s s i b l y chromium,
w h i c h a r e b o t h p r e s e n t a t t h e c r a c k e r c o i l s u r f a c e and w i t h i n t h e
c o k e , a r e more l i k e l y t o be r e s p o n s i b l e f o r c a t a l y s e d c o k e
formation. T h i s i s s u p p o r t e d by r e s e a r c h o f A l b r i g h t and
c o w o r k e r s (5) on t h e p y r o l y s i s o f h y d r o c a r b o n s o v e r I n c o l o y 800
s u r f a c e s , w h i c h f o u n d i r o n t o be t h e p r e d o m i n a n t m e t a l in t h e
coke.
I n summary, t h e s e i n v e s t i g a t i o n s s u g g e s t e d t h a t coke
d e p o s i t i o n in ESC p l a n t i s e n h a n c e d by c a t a l y t i c i n t e r a c t i o n o f
m e t a l s f r o m t h e r a d i a n t c o i l w a l l s , a v i e w l a t e r s u p p o r t e d by
h i g h r e s o l u t i o n s t u d i e s . T h i s l e d t o an e x a m i n a t i o n o f
means o f p a s s i v a t i n g a l l o y s u r f a c e s .
S u r f a c e P a s s i v a t i o n o f ESC Radiant C o i l Alloys
M e t h o d s have been s u g g e s t e d f o r t h e p a s s i v a t i o n o f r e a c t o r s .
P r e s u l p h i d i n g t r e a t m e n t s have been r e p o r t e d (9) t o r e d u c e c o k e
f o r m a t i o n d u r i n g e t h a n e and p r o p a n e p y r o l y s i s . However,
a l t h o u g h LDF f e e d s t o c k c o n t a i n s s m a l l q u a n t i t i e s o f s u l p h u r ,
c o m m e r c i a l ESC p l a n t n o r m a l l y r e l i e s on p r e o x i d a t i o n d u r i n g t h e
steam/air decoking o p e r a t i o n s to produce a p r o t e c t i v e s u r f a c e
oxide f i l m . Conoco (10) have c l a i m e d t h a t h i g h t e m p e r a t u r e s t e a m
pretreatments are p a r t i c u l a r l y e f f e c t i v e f o r h e a t - r e s i s t i n g a l l o y
s t e e l s c o n t a i n i n g a t l e a s t 1% s i l i c o n . This research demonstrated
t h a t steam o x i d a t i o n o f a r a n g e o f HK and HU a l l o y s p r o d u c e d
i n c r e a s i n g r e s i s t a n c e to c a r b u r i s a t i o n with i n c r e a s i n g s i l i c o n
c o n t e n t o v e r t h e r a n g e 1-2.5%. M o s t p a r t i c u l a r l y , s e v e r a l h o u r s
p r e t r e a t m e n t w i t h steam a t 955C o f an e t h a n e c r a c k i n g f u r n a c e
in 2.0% S i HK a l l o y s i g n i f i c a n t l y i n c r e a s e d p l a n t o n - s t r e a m t i m e
t h r o u g h reduced coke d e p o s i t i o n . I t was presumed t h a t t h e s e

2. BROWN ET AL. Inhibition of Coke Formation 27
i m p r o v e m e n t s were a s s o c i a t e d w i t h t h e f o r m a t i o n o f a s u r f a c e
f i l m c o m p r i s i n g s i l i c o n o x i d a t i o n compounds.
A programme o f work t o examine t h e e f f e c t s o f steam
o x i d a t i o n on c o m m e r c i a l ESC p l a n t a l l o y s was t h e r e f o r e c a r r i e d
o u t , in w h i c h t h e c o m p o s i t i o n o f t h e s u r f a c e f i l m s was p r o b e d
by X - r a y p h o t o e l e c t r o n s p e c t r o s c o p y ( X P S o r ESCA). Coupons o f
18/8 s t a i n l e s s s t e e l , I n c o l o y 800, HK 40 a n d s u b s e q u e n t l y t u b e s
o f a h i g h s i l i c o n - c o n t a i n i n g drawn a l l o y ( I m m a c u l a t e 5) were
t r e a t e d f o r s e v e r a l h o u r s in s t e a m a t t e m p e r a t u r e s in e x c e s s o f
900C I n a l l c a s e s t h e o x i d e s u r f a c e was e n r i c h e d in s i l i c a
through s e g r e g a t i o n from t h e bulk a l l o y . Figure 2 displays
t h e XPS s p e c t r u m o f s t e a m - t r e a t e d HK 4 0 , t h e a l l o y w h i c h showed
the h i g h e s t s u r f a c e c o n c e n t r a t i o n s o f s i l i c a . I t may a l s o be
n o t i c e d t h a t n i c k e l was c o m p l e t e l y removed (<1%) f r o m t h e o x i d e
s u r f a c e , t h o u g h s u b s t a n t i a l c o n c e n t r a t i o n s of i r o n manganese
and chromium were s t i l
These e x p e r i m e n t s
o f steam p r e t r e a t m e n t may be p a r t i a l l y a s s o c i a t e d w i t h t h e
generation of a s i l i c a - r i c h oxide. However, b r i e f a t t e m p t s t o
increase the surface c o n c e n t r a t i o n t o approach a continuous
s i l i c a l a y e r e x c l u d i n g a l l t h e a l l o y i n g m e t a l s (by v a r i a t i o n s
in p r e o x i d a t i o n c o n d i t i o n s ) met w i t h f a i l u r e , e x h i b i t i n g b u l k
inhomogeneity and o x i d e s p a l l a t i o n problems. F u r t h e r , many
ESC p l a n t s a r e c o n s t r u c t e d w i t h r a d i a n t c o i l a l l o y s l o w in s i l i c o n
c o n t e n t , a n d s o p r e o x i d a t i o n c a n o n l y be c o n s i d e r e d a p a r t i a l
palliative. Hence, a t t e n t i o n t u r n e d t o t h e p r o s p e c t o f c o a t i n g
the i n t e r n a l s u r f a c e s o f r a d i a n t c o i l s w i t h a t h i n , continuous
layer of s i l i c a .
Silica Coating of Steel Alloys
S i m u l t a n e o u s d e v e l o p m e n t was u n d e r t a k e n o f a method f o r
s i l i c a c o a t i n g s t e e l s and a t e s t t o demonstrate t h a t t h e coke
f o r m a t i o n r e a c t i o n was s u r f a c e s e n s i t i v e a n d r e d u c e d by t h e
deposition of a s i l i c a film.
Mindful of the d i f f i c u l t y of coating the i n t e r n a l surfaces
o f l o n g ESC r a d i a n t c o i l s , a c h e m i c a l v a p o u r d e p o s i t i o n (CVD)
r o u t e was s e e n a s p r e s e n t i n g t h e b e s t a p p r o a c h . The d e p o s i t i o n
o f s i l i c a by CVD o n t o s i l i c o n i s w e l l known in t h e e l e c t r o n i c s
i n d u s t r y ( 1 1 ) , b u t h a d n o t been e x t e n s i v e l y a p p l i e d t o m e t a l s .
A p r o c e s s was c o n c e i v e d (12,13) whereby a s i l i c a c o a t i n g i s
p r o d u c e d on p r e o x i d i s e d s t e e l s u b s t r a t e s by t h e d e c o m p o s i t i o n o f
an a l k o x y s i l a n e in a c a r r i e r g a s . This process o f f e r s the
advantages t h a t t h i n , adherent and impervious f i l m s o f s i l i c a
can be d e p o s i t e d a t h i g h t e m p e r a t u r e s , u s i n g steam a s a c a r r i e r
gas u n d e r c o n d i t i o n s s i m i l a r t o d e c o k i n g / c r a c k i n g o p e r a t i o n s .
R e a c t i o n o f t h e o r g a n o - s i l i c o n compounds w i t h a n o x i d i s i n g a g e n t
is not required.
An a p p a r a t u s f o r s i l i c a c o a t i n g s t e e l c o u p o n s by t h i s method
i s shown in F i g u r e 3. B r i e f l y , a n a l k o x y s i l a n e ( e g t e t r a e t h y l -

COKE FORMATION
240 ' U ' 60 ' 80 ' 1040 1240 44

KINETIC ENERGY ( eV)
Figure 2. XPS of steam treated 40.

VENT SILICA S A M P L E
BALL AND SOCKET HOLDER
JOINT
AND SAMPLE
PYREX
SILICA
REACTOR STANTON
VESSEL REDCROFT
WITH LOW M A S S
SILICA FURNACE
RINGS IN (max temp
CONDENSATE PREHEATER 1000 C)
COLLECTOR SECTION
PREHEATER
(QUARTZ HEATING TAPE
max temp 700C)
BUTTRESS JOINT
TRACE HEATING
"Vie in O.D. TUBE

(STAINLESS S T E E L
TC PROBE TO'PERFUSOR'
SYRINGE PUMP FOR TEOS)
TWO STAINLESS S T E E L SUPER H E A T E R S

(12 in 11/2 in O.D. ) PACKED WITH
STAINLESS S T E E L R A S C H I G RINGS.
3
/ 8 in O.D. STAINLESS
S T E E L PIPE WORK

Figure 3. A pparatus used for silica coating steel coupons.
30 COKE FORMATION
o r t h o s i l i c a t e ) i s i n j e c t e d ( 1 % by w e i g h t ) i n t o a p r e h e a t e d s t e a m
f l o w w h i c h p a s s e s i n t o t h e c o a t i n g v e s s e l where s t e e l s u b s t r a t e s
a r e r a d i a n t l y h e a t e d t o 600-850C. S i l i c a f i l m s , l a r g e l y
amorphous in c h a r a c t e r , have been d e p o s i t e d w i t h a w i d e r a n g e
of t h i c k n e s s e s , although p r o t e c t i v e , continuous c o a t i n g s w i t h a
f u s e d b a l l - l i k e t o p s u r f a c e ( F i g u r e 4) can be p r o d u c e d as t h i n
as 1 m i c r o n o r l e s s .
P r e o x i d a t i o n o f t h e s t e e l s u b s t r a t e i s an e s s e n t i a l f e a t u r e
to m a i n t a i n c o a t i n g adherence o v e r the wide temperature ranges
and h o s t i l e e n v i r o n m e n t s e x p e r i e n c e d in t e s t s ; t h i s c a n be
a c c o m p l i s h e d in a c o n t r o l l e d manner w i t h i n t h e c o a t i n g a p p a r a t u s
or s e p a r a t e l y p r i o r t o sample i n t r o d u c t i o n . M e t a l l u r g i c a l
e x a m i n a t i o n o f s i l i c a c o a t e d s t e e l s has r e v e a l e d no d e l e t e r i o u s
a c t i o n on t h e b u l k a l l o y , as w o u l d be p r e d i c t e d s i n c e t h e c o a t i n g
is deposited d i r e c t l y a th i n e r t oxide Indeed s i l i c coatin
has been f o u n d t o p r o t e c
a t t a c k in h i g h t e m p e r a t u r
A l t h o u g h no d e t a i l e d s t u d y has been c a r r i e d o u t , i t w o u l d a l s o
appear p o s s i b l e t h a t the impervious s i l i c a f i l m s w i l l reduce
d e g r a d a t i o n o f t h e a l l o y m e c h a n i c a l p r o p e r t i e s by p r e v e n t i n g
carburisation.
A t e s t t o d e m o n s t r a t e t h a t t h e c o k e f o r m a t i o n r e a c t i o n was
s u r f a c e s e n s i t i v e was d e v e l o p e d , b e i n g b a s e d a r o u n d a S a t o r i u s
4102 m i c r o b a l a n c e u s i n g f l o w i n g h y d r o c a r b o n : s t e a m a t m o s p h e r e s .
A s c h e m a t i c d i a g r a m o f t h e a p p a r a t u s i s shown in F i g u r e 5.
C o k i n g r a t e measurements were made on HK 40, I n c o l o y 800, n i c k e l
f o i l , q u a r t z and s i l i c a c o a t e d HK 40, f r o m 57% (wt) steam:
e t h a n e , 7 2 % (wt) steam: e t h a n e , and 4 9 % (wt) s t e a m : 3 2 % (wt)
hexane:ethane m i x t u r e s . H i g h steam c o n c e n t r a t i o n s were u s e d in an
a t t e m p t t o compensate f o r t h e r e l a t i v e l y l o n g h o t - z o n e r e s i d e n c e
times of s e v e r a l seconds. The p r o c e d u r e i n v o l v e d a t e m p e r a t u r e
programme o f : - 900C f o r one h o u r t o a l l o w e q u i l i b r a t i o n o f t h e
s y s t e m , f o l l o w e d by 860C, 880C, 920C, 940C, 980C, e t c f o r t h e
t i m e n e c e s s a r y t o measure t h e c o k i n g r a t e (10-60 m i n u t e s ) ;
o c c a s i o n a l r e p e a t measurements o f t h e low t e m p e r a t u r e r a t e s were
made. F i g u r e 6 shows t h e A r r h e n i u s p l o t o b t a i n e d f o r t h e s t e a m :
h e x a n e : e t h a n e m i x t u r e on b o t h c o a t e d and u n c o a t e d HK 40, and
t y p i f i e s t h e r e s u l t s o b t a i n e d f o r a l l gas c o m p o s i t i o n s . Below a
c e r t a i n t e m p e r a t u r e , w h i c h depended on s u c h f a c t o r s as t h e steam
c o n c e n t r a t i o n and r e s i d e n c e t i m e , t h e p l o t s d i v e r g e d w i t h t h e
c o k i n g r a t e s on t h e m e t a l s u r f a c e s h i g h e r t h a n on t h e q u a r t z and
s i l i c a coated surfaces. Hence in t h e F i g u r e shown t h e r a t e
on HK 40 was f o u r t o s i x t i m e s h i g h e r t h a n t h a t on s i l i c a c o a t e d
HK 40 a t 830C. From t h e s e t e s t s i t became c l e a r t h a t u n d e r
c e r t a i n c o n d i t i o n s o f t e m p e r a t u r e , s t e a m c o n c e n t r a t i o n and f l o w
r a t e , c o k e f o r m a t i o n was c a t a l y s e d by t h e m e t a l s u b s t r a t e and a
s i l i c a c o a t i n g would c o n s i d e r a b l y reduce the r a t e of c o k i n g .
However, more c o m p l e x f e e d s t o c k s and l o w e r r e s i d e n c e t i m e s
(0.1-0.2 s ) a r e t y p i c a l l y u s e d in c o m m e r c i a l ESC p l a n t , m a k i n g a
d e t a i l e d i n v e s t i g a t i o n o f c o a t i n g p e r f o r m a n c e in a l a b o r a t o r y
s i m u l a t e d ESC r e a c t o r n e c e s s a r y .

BROWN ET AL. Inhibition of Coke Formation
Figure 4. SEM of silica coated steel.

32 COKE FORMATION
-BALANCE RING MAIN

HOUSIN
C H (C H )|
2 6 2 4
, N2l20ml/min fr CYLINDER
SOLENOID
C Hg
2
VALVE
BY-PASS
r FOR
SATURATOR SATURATOR / S T E A M x
TO CONDENSER
AND VENT EVAPORATOR^'T' ^ 0
KEY -
HEATED PRESSURE REGULATOR
LINE TO i N E E D L E VALVE
REACTOR <g> STOP VALVE
N2OR C H
2 6 60ml/min
P R E S S U R E GAUGE
1H 0
2 120-240ml/min
Figure 5. Schematic of microbalance system for coking studies under flowing

conditions on coupons.

2. BROWN ET A L . Inhibition of Coke Formation 33
8-5 8-7 8-9 \91 9-3

\
1 0 / TEMPERATURE
4
Figure 6. Microbalance coking runs in ethane.hexane:steam (49 wt%). Key:

H b uncoated 40; and - - , SiC 51 silica coated HK 40.

34 COKE FORMATION
Coke I n h i b i t i o n in a L a b o r a t o r y ESC Reactor
The l a b o r a t o r y ESC r e a c t o r i s shown in F i g u r e 7. With t h i s

a p p a r a t u s i t was p o s s i b l e t o c a r r y - o u t in s i t u c o n s e c u t i v e s i l i c a
c o a t i n g , steam c r a c k i n g , and d e c o k i n g o p e r a t i o n s in a 2 f t l o n g
3/8" OD c r a c k e r t u b e . M o s t o f t h e work was c a r r i e d o u t u s i n g
I n c o l o y 800 t u b i n g , t h o u g h a few r u n s were a l s o c a r r i e d o u t u s i n g
I m m a c u l a t e 5 t u b i n g , w h i c h i s e q u i v a l e n t t o an A I S I 310
s p e c i f i c a t i o n w i t h a c o m p o s i t i o n s i m i l a r t o c a s t HK 40 a l l o y .
S i l i c a c o a t i n g was c a r r i e d o u t as w i t h c o u p o n s , by i n j e c t i n g
1% by w e i g h t t e t r a e t h o x y s i l a n e i n t o steam j u s t p r i o r t o t h e
p r e o x i d i s e d c r a c k e r t u b e t o p r o d u c e 0.5-1.0 t h i c k c o a t i n g s
a l o n g t h e w h o l e o f t h e t u b e h o t z o n e . The steam c r a c k i n g r u n s
u s e d a t y p i c a l ESC f e e d s t o c k , LDF 160 ( 3 6 % i s o - p a r a f f i n s , 2 3 %
n - p a r a f f i n s , 3 4 % n a p h t h e n e s , 7% a r o m a t i c s , 78 ppm s u l p h u r w i t h
a total fraction boilin
c r a c k i n g zone o f 0.12 s
t h e c r a c k i n g c o n d i t i o n s . The c r a c k e d gas c o m p o s i t i o n f o r
d i f f e r e n t c r a c k i n g t e m p e r a t u r e s was measured by gas c h r o m a t o g r a p h y
and i s shown in F i g u r e 8. Clearly, cracking s e v e r i t y increased
w i t h t e m p e r a t u r e , and c r a c k i n g in t h e t e m p e r a t u r e r a n g e
800-900C was t a k e n t o r e p r e s e n t a r e a s o n a b l e s i m u l a t i o n o f
c o m m e r c i a l ESC p l a n t . F i n a l l y , t h e d e c o k i n g o p e r a t i o n , when u s e d ,
u t i l i s e d a i r a t 600-800C.
Coke d e p o s i t i o n measurements were made on b o t h u n c o a t e d and
c o a t e d t u b e s , n o r m a l l y by measurement o f w e i g h t d i f f e r e n c e b e f o r e
and a f t e r s t a n d a r d s i x h o u r s t e a m c r a c k i n g r u n s . In a l l cases
t h e u n t r e a t e d t u b e s were p r e t r e a t e d in steam f o r a t l e a s t one h o u r
a t 750-850C b e f o r e c r a c k i n g began t o f o r m a s u r f a c e o x i d e l a y e r
in a s i m i l a r manner t o t h a t f o u n d in ESC p l a n t . The coke y i e l d s
o b s e r v e d , e x p r e s s e d a s ppm o f t h e t o t a l f e e d s t o c k , o v e r b o t h
u n c o a t e d and s i l i c a c o a t e d t u b e s a t v a r i o u s c r a c k i n g t e m p e r a t u r e s
a r e shown in F i g u r e 9. A f a s t , catalysed, coking reaction with
an a p p a r e n t a c t i v a t i o n e n e r g y o f a b o u t 27 k c a l / m o l was o b s e r v e d
in t h e u n c o a t e d I n c o l o y 800 t u b e s . O n l y a low c o k e f o r m a t i o n
r a t e was o b s e r v e d on t h e s i l i c a c o a t e d t u b e s up t o 900C.
Thus a t 850C, up t o a f a c t o r o f 10 r e d u c t i o n in c o k i n g r a t e was
o b t a i n e d by s i l i c a c o a t i n g . Above 900C t h e c o a t i n g was l e s s
e f f i c i e n t , and t h i s was s u b s e q u e n t l y p a r t i a l l y a s c r i b e d t o s e v e r e
deformation of the c r a c k e r tube c a u s i n g c o a t i n g s p a l l i n g . T h i s
s i t u a t i o n was t o some e x t e n t a l l e v i a t e d by p r e a n n e a l i n g t h e
tube a t the c r a c k i n g temperature p r i o r t o s i l i c a c o a t i n g .
The e f f e c t o f t h e d e c o k i n g o p e r a t i o n on c o k e f o r m a t i o n in
s u b s e q u e n t c r a c k i n g r u n s was a l s o s t u d i e d and t h e r e s u l t s shown
p i c t o r i a l l y in F i g u r e 10. On an u n c o a t e d I n c o l o y 800 t u b e , t h e
h i g h coke y i e l d remained a p p r o x i m a t e l y c o n s t a n t throughout
f o u r s u c c e s s i v e steam c r a c k i n g / a i r d e c o k i n g c y c l e s . T h i s t u b e
was s u b s e q u e n t l y c o a t e d w i t h s i l i c a t o p r o d u c e an i m m e d i a t e x l O

25psi RELIEF
VALVE AND VENT
TC
PROBE
S A M P L E TUBE
CRACKER FURNACE

WATER

LIQUID PRODUCT
COLLECTOR
Figure 7. Laboratory-scale ethylene steam cracker.

COKE FORMATION
LU
LL
Figure 8. Product gas composition vs. cracking temperature with Incoloy 800.
Key: Q, ethane; X, methane; ethylene; and A, propylene.
770 800 850 900 950
TEMPERATURE (C )
Figure 9. Coke yield vs. cracking temperature. Key: X, uncoated Incoloy 800;
O, silica coated Incoloy 800; and A, silica coated Incoloy 800 preannealed at
running temperature.

5000
ffi 4000
CRACKER
TUBE
3000
SILICA
COATED
2000
LU
o 1000

RUN
Figure 10. Coke yields at 850 C in successive steam cracking/air decoking cycles
in Incoloy 800 tube.

38 COKE FORMATION
r e d u c t i o n in c o k e f o r m a t i o n w h i c h was b r o a d l y m a i n t a i n e d o v e r
t h r e e f u r t h e r steam c r a c k i n g / a i r d e c o k i n g c y c l e s , i n d i c a t i n g no
d e l e t e r i o u s a c t i o n upon t h e c o a t i n g .
An o p p o r t u n i t y was t a k e n t o examine t h e s t r u c t u r e o f t h e c o k e
deposits using o p t i c a l microscopy, SEM and h i g h r e s o l u t i o n
TEM. The l a t t e r f a c i l i t y was p r o v i d e d by Dr G.R. M i l l w a r d o f
t h e U n i v e r s i t y o f C a m b r i d g e , u s i n g a P h i l l i p s EM 300 f i t t e d w i t h
a high r e s o l u t i o n stage. The i n i t i a l c o k e d e p o s i t i o n d u r i n g t h e
f i r s t few h o u r s o f c r a c k i n g p r o d u c e d a smooth, h a r d c a r b o n s k i n ,
w h i c h was t h i c k e r and more b r i t t l e in t h e u n c o a t e d t u b e
(Figure 11). TEM s t u d i e s o f t h e d e p o s i t f r o m t h e u n c o a t e d t u b e
r e v e a l e d b o t h p o o r l y o r d e r e d c a r b o n and a m i n o r i t y component
o f r e l a t i v e l y w e l l o r d e r e d g r a p h i t i c c a r b o n ( F i g u r e s 12 and 1 3 ) ,
whereas the d e p o s i t from the s i l i c a c o a t e d tube r e v e a l e d o n l y
the p o o r l y ordered carbon Th greate degre f orderin in
the coke from uncoated tube
catalysed formation process
S u b s e q u e n t l y , w i t h l o n g e r c r a c k i n g t i m e s , c r a c k s a p p e a r e d in
the hard carbon s k i n w i t h f u r t h e r coke growth emanating a l o n g
these c r a c k s . A f t e r 70 h o u r s on s t r e a m t h i s s e c o n d a r y c o k e
g r o w t h , w h i c h had a l e s s d e n s e w h i s k e r y n a t u r e , c o m p l e t e l y
c o v e r e d t h e u n c o a t e d t u b e b u t was s t i l l l o c a l i s e d on t h e s i l i c a
coated tube ( F i g u r e 14). TEM e x a m i n a t i o n o f t h i s s e c o n d a r y
d e p o s i t o c c a s i o n a l l y r e v e a l e d w e l l - d e f i n e d f i l a m e n t o u s type
d e p o s i t s w i t h p a r t i c l e s a t t h e f i l a m e n t t i p s ( F i g u r e 15) a s
o b s e r v e d by B a k e r and c o w o r k e r s ( 2 , 3 , 4 ) . However, u n d e r t h e
TEM t h e d e p o s i t s t i l l p r i m a r i l y r e v e a l e d t h e p o o r l y and
r e l a t i v e l y w e l l o r d e r e d c a r b o n s e e n in F i g u r e s 12 and 13, p o s s i b l y
t h r o u g h f i l a m e n t t h i c k e n i n g by a c o n d e n s a t i o n mechanism (14)
Thus, s i l i c a c o a t i n g appears t o r e t a r d b o t h the f o r m a t i o n
o f t h e h a r d c a r b o n s k i n and t h e g r o w t h o f t h e s e c o n d a r y ( l e s s
d e n s e ) c o k e d e p o s i t a t c r a c k s in t h e s k i n , w i t h t h e o v e r a l l
r e s u l t t h a t in c r a c k i n g r u n s up t o t h r e e d a y s in l e n g t h in t h e
l a b o r a t o r y ESC r e a c t o r t h e c o k e f o r m a t i o n i s i n h i b i t e d by a
f a c t o r o f 3-4 compared t o u n c o a t e d t u b e s .
Conclusion
A p r o c e s s f o r f o r m i n g t h i n , a d h e r e n t s i l i c a c o a t i n g s in
h i g h a l l o y s t e e l t u b i n g has been d e v e l o p e d . The s i l i c a c o a t i n g s
s u b s t a n t i a l l y r e d u c e t h e r a t e o f c o k e f o r m a t i o n in l a b o r a t o r y
p y r o l y s i s t u b e s o p e r a t i n g u n d e r e t h y l e n e steam c r a c k i n g
conditions.

BROWN ET A L . Inhibition of Coke Formation
Figure 11. Optical micrographs of coke deposits after six hours cracking. Key:
A, silica coated; and B, uncoated.

40 COKE FORMATION
Figure 12. TEM of hard coke skin from uncoated Incoloy 800 tube.
Figure 13. TEM of hard coke skin from uncoated Incoloy 800 tube.

Figure 14. Optical micrographs of coke deposits after 70 h cracking. Key: A,

uncoated; and B, silica coated.

COKE FORMATION
Figure 15. TEM of filamentous coke deposit (particles arrowed).

Literature Cited
1. A l b r i g h t , L.F.; Yu, Y.C.; Welther, K.; Proc. 85th American

I n s t i t u t e of Chemical Engineers National Meeting, 4th June
1978.
2. Baker, R.T.K.; Barber, M.A.; Feates, F.S.; H a r r i s , P.S.;
Waite, R.J.; J. C a t a l y s i s (1972) 26, 51.
3. Baker, R.T.K.; H a r r i s , P.S.; Thomas, R.B.; Waite, R.J.;
J. C a t a l y s i s (1973) 30, 86.
4. Keep, C.W.; Baker, R.T.K.; France, J.A. J. C a t a l y s i s (1977)
47, 232.
5. A l b r i g h t , L.F.; McConnell, C.F.; Welther, K.; Thermal
Hydrocarbon Chemistry, E d i t o r s , A.G. Oblad, H.G. Davis,
and R.T. Eddinger, Advances in Chemistry S e r i e s #188,
pp 175-191, Amer.
6. Lahaye, J.; Badie
7. Tama, Y.; Nishiyama, Y.; Takahashi, G. Koygo Kagaku Zasshi
(1967) 70, 889.
8. Lobo, L.S.; Trim, D.L.; F i g u e i r e d o , J.L. Proc. Fifth
I n t e r n a t i o n a l Congress on C a t a l y s i s , Miami Beach 1972,
Paper 79.
9. Crynes, B.K., A l b r i g h t , L.F., Ind. Eng. Chem. Process
Develop (1969) 8, 25.
10. C o n t i n e n t a l Oil Company, UK Patent 1 332 569 P u b l i s h e d
3 Oct 1973.
11. See f o r example Gregor, L.V., P h y s i c s o f Thin F i l m s (1966)
3, 131.
12. Brown, D.E.; C l a r k , J.T.K.; M c C a r r o l l , J.J.; Sims, M.L.;
(The British Petroleum Co L t d ) , UK Patent 1 483 144,
Published 17 Aug 1977.
13. Brown, D.E.; C l a r k , J.T.K.; M c C a r r o l l , J.J.; Sims, M.L.;
(The British Petroleum Co L t d ) , US Patent 4 099 990,
Published 11 J u l y 1978.
14. O b e r l i n , .; Endo, M., J. C r y s t a l Growth (1976), 32, 335.
RECEIVED June 28, 1982.

3
Surface Effects on the Steam Cracking of
Propane
A. H O L M E N and O. A. LINDVAAG
Norwegian Institute of Technology, Department of Industrial Chemistry,
N-7034 Trondheim-NTH Norway
D. L. TRIMM
University of New South Wales, School of Chemical Engineering and Industrial Chemistry,
P.O. Box 1, Kensington, 2033 Australia
The e f f e c t o f s u r f a c e
the steam c r a c k i n g o f propan
ture o f the surface near the r e a c t o r inlet has a s i g n i f i c a n t e f f -
ect on the r e a c t i o n products while the surface near the e x i t does
not. The m a t e r i a l o f the r e a c t o r tube appears t o c a t a l y z e gas
phase r e a c t i o n s as w e l l as coke formation and gasification. P r e -
treatment o f the r e a c t o r tube a l t e r s the chemical nature o f the
surface and, as a r e s u l t , a l t e r s the e f f e c t o f the m a t e r i a l on
the r e a c t i o n products.
The steam c r a c k i n g o f hydrocarbons i s one o f the most impor-

tant sources o f light o l e f i n s f o r the chemical i n d u s t r y(1).The
o v e r a l l r e a c t i o n is a high temperature p y r o l y s i s process in which
a range o f products are formed in the gas phase as a r e s u l t o f a
f r e e r a d i c a l chain r e a c t i o n . Tars and coke are a l s o formed as s i d e
products to the main r e a c t i o n . Steam is present mainly as an i n e r t
d i l u e n t (2), although it may help t o g a s i f y t a r s and carbon pro-
duced during the r e a c t i o n (1, 3). Because o f the formation o f coke
deposits on industrial r e a c t o r s u r f a c e s , the r e a c t o r must be r e -
moved from o p e r a t i o n from time t o time and the coke l a y e r burned
out with oxygen/steam mixtures.
Although the major r e a c t i o n s occur in the gas phase, surface
r e a c t i o n s can be very important in these systems. The absence or
presence o f a surface p l a y s an important r o l e in the formation o f
s o l i d products such as coke (4 - 8 ) . There i s a l s o good evidence
that the w a l l can have a s i g n i f i c a n t e f f e c t on gas phase r e a c t i -
ons, a t l e a s t in part as a r e s u l t o f the i n i t i a t i o n or t e r m i n a t i o n
of f r e e r a d i c a l chains thereon (9., JTO). Given the nature o f the
f r e e r a d i c a l chains, both the chemical nature and the p h y s i c a l
form (1J_ - 16.) o f the surface can i n f l u e n c e the r e a c t i o n and i t s
products.
0097-6156/82/0202-0045$06.00/0

46 COKE FORMATION
The present s t u d i e s were i n i t i a t e d in order to i n v e s t i g a t e

the e f f e c t o f the r e a c t o r s u r f a c e on the product d i s t r i b u t i o n and
on the tendency f o r coke formation during the steam c r a c k i n g o f
propane in a t u b u l a r r e a c t o r . A t t e n t i o n has been focused on c o r r e
l a t i n g v a r i o u s e f f e c t s which can a r i s e in the system. Previous
s t u d i e s o f the p y r o l y s i s o f propane has been reviewed r e c e n t l y
(17 > 18), and the f i n d i n g s o f the present work are r e l a t e d to
these s t u d i e s l a t e r in t h i s paper.
Coke formation w i l l always be a p o t e n t i a l problem in any high
temperature process i n v o l v i n g hydrocarbons. Coke and t a r s formed
during r e a c t i o n can deposit on r e a c t o r s u r f a c e s or in quench heat
exchangers, and s e v e r a l e f f e c t s have been observed in a steam c r a
cker tube (, 9_) As the r e a c t i o n proceeds the tube w i l l accumu
l a t e coke towards the r e a c t o r e x i t while the i n l e t zone remains
r e l a t i v e l y coke f r e e , a
with the formation o f t a r
adsorb and react on t h i s bare metal, and the components o f the gas
phase in the r e a c t o r should and do r e f l e c t t h i s i n t e r a c t i o n
(4, 9^, JO). Since carbon formation depends on the nature o f the
gas phase s p e c i e s , these i n t e r a c t i o n s should a l s o i n f l u e n c e coke
formation towards the e x i t o f the r a c t o r . Again, t h i s i s found
to be the case ( 4, 9_ - JJ_)
As a r e s u l t o f these c o n s i d e r a t i o n s , i t would be expected
that surface e f f e c t s during steam c r a c k i n g would be apparent in
the formation o f gaseous, l i q u i d and s o l i d products. The present
s t u d i e s show that t h i s i s indeed the case.
EXPERIMENTAL
Coke formation has been studied in a conventional flow appa

r a t u s . A schematic diagram o f the experimental apparatus i s shown
in Figure 1. Coke formation i s measured on f o i l s o f d i f f e r e n t ma
t e r i a l s hanging from one arm o f the microbalance ( C . I . Mark 2B)
in such a way that the f o i l i s in the constant temperature zone
of the r e a c t o r . The amount o f coke deposited on the f o i l s i n c l u
des the d e p o s i t i o n o f coke formed in the gas phase as w e l l as the
coke formed on the s u r f a c e .
The tubular r e a c t o r i s made o f s t a i n l e s s s t e e l (Uddeholm
S t a i n l e s s 24, 18-2689) with an i n s i d e diameter o f 22mm. The l e n g t h
of the r e a c t o r i s 37 cm, with a constant temperature zone o f c a .
16 cm ( + 3 C). Experiments have a l s o been c a r r i e d out in a t u
bular r e a c t o r made o f quartz ( i . e . quartz as a l i n i n g in the
s t e e l r e a c t o r ) . The i n s i d e diameter o f the quartz r e a c t o r i s
14.8 mm. The dimensions o f the f o i l hanging in e i t h e r r e a c t o r were
u s u a l l y ca. 8 mm 28 mm and the weight about 0,3 gram i f a s t e e l
f o i l was used.
A l l the experiments were c a r r i e d out with steam and/or n i t r o
gen as d i l u e n t s . Steam was f e d to the r e a c t o r by evaporating water
i n t o a stream o f n i t r o g e n . A stream o f n i t r o g e n i s always main-

HOLMEN ET A L . Steam Cracking of Propane
s:
Sts?
11
5
3
0c
#
American Chemical
Society Library
1155 16th St. N. w.
ACS Symposium Series;WHMngton, D. C.
American Chemical 20036
Society: Washington, DC, 1983.
48 COKE FORMATION
tained through the microbalance in order to p r o t e c t the balance

against c o r r o s i v e atmospheres. The e x i t gas from the r e a c t o r was
quenched and the gas volume measured before complete gas a n a l y s i s
using two o n - l i n e gas chromatographs. The permanent gases ( H , N^, 2
CO, C0 ) were separated on a 2 m column (1/4") packed with

2
Porapak (80/100 mesh), followed by a 3 m column (1/4") packed

with 13X molecular sieve (30/50 mesh). Hydrocarbons were
separated on a 3 m column (1/8") packed with squalane on Alumina
H (100/120 mesh).
Two d i f f e r e n t pre-treatments of the f o i l and o f the r e a c t o r
surface have been used: e i t h e r p r e r e d u c t i o n or p r e o x i d a t i o n (with
oxygen). During p r e r e d u c t i o n each f o i l was reduced f o r 18 h in
flowing hydrogen at 770C and 1 h at the a c t u a l experimental
temperature p r i o r to the run. With s t e e l f o i l s i t was impossible
to o x i d i z e the f o i l to
heating in oxygen (850C
text.
RESULTS
Experiments were c a r r i e d out (a) in which the m a t e r i a l o f the

r e a c t o r tube remained constant and the formation o f coke was mea
sured on f o i l s of d i f f e r e n t m a t e r i a l s and (b) in which the mater
i a l of the r e a c t o r tube was v a r i e d and coke formation was measured
on a f o i l of the same m a t e r i a l . Both p r e r e d u c t i o n and p r e o x i d a t i o n
of the r e a c t o r system have been used as standard pretreatment in
d i f f e r e n t cases.
Not s u r p r i s i n g l y , the f i r s t geometry gave very s i m i l a r r e
s u l t s in a l l cases. Using the quartz r e a c t o r , coke formation was
measured on f o i l s f a b r i c a t e d from s t a i n l e s s s t e e l , c o b a l t , molyb
denum, copper and q u a r t z . T y p i c a l e x i t gas compositions are shown
in Figure 2 and r a t e s of coke formation on the f o i l s a f t e r p r e r e
duction are shown in F i g u r e 3 The nature of the f o i l does not
have any s i g n i f i c a n t i n f l u e n c e on the e x i t gas composition. On
the other hand i t i s c l e a r that the coke formation on f r e s h f o i l s
i s dependent of the f o i l m a t e r i a l . However, t h i s i n i t i a l v a r i
a t i o n in coke d e p o s i t i o n on the f o i l s i s s u b s t a n t i a l l y decreased
as the f o i l s become more covered in coke. T h i s coke o r i g i n a t e s at
l e a s t in part in the gas phase and encapsulates the f o i l and
breakaway metal p a r t i c l e s (20). I t i s i n t e r e s t i n g to note that
the higher i n i t i a l r a t e s were not observed on f o i l s made of
quartz or molybdenum: in f a c t , the r a t e f o r coke formation seems
to increase somewhat as the r e a c t i o n proceeds on these f o i l s .
The e f f e c t of r e a c t o r m a t e r i a l was s t u d i e d u s i n g three
d i f f e r e n t s u r f a c e s . These were quartz and o x i d i z e d and reduced
s t a i n l e s s s t e e l (Uddeholm 24 c o n t a i n i n g 17,2% Cr, 11,5% N i ,
2,7% Mo, 1,7% , 0,5% S i and 66,4% F e ) . Previous s t u d i e s have
revealed that the surface of the o x i d i z e d s t e e l c o n t a i n s Fe and
Ni oxides together with the Cr oxide, while the s u r f a c e e n r i c h
ment by Mn and Cr oxides i s very pronounced during r e d u c t i o n o f

3. HOLMEN E T A L . Steam Cracking of Propane 49
_
CH A
C
2 4
H
-

-
< 1 1

70 80 90
CONVERSION (%)
Figure 2. Exit gas composition from steam cracking of propane in quartz reactor
with steel (Sandvik 15RelO) as the foil material after 10 min on stream. Conditions:
temperature range, 800-870C; feed gas composition, 29 mol% C H , 32% H 0, 3 8 2
and 39% N ; and total feed rate, 0.42 L gas/min.

2
10 20 30 U0 50 60 70 80 90 100 110
TIME ( m i n )
Figure 3. Coke formation during steam cracking of propane in the quartz reactor
at 850C on foils made from different materials. Key: O, steel; V , Co; A , Mo;
, Cu; and , quartz. Conversion of C H 98%. Feed gas as in Figure 2.
S 8

50 COKE FORMATION
the s t e e l s u r f a c e . (The content of Ni and Fe in the surface o f

the reduced s t e e l i s l e s s than 0.3 wt-%) (20). Coke formation was
measured from d e p o s i t i o n on f o i l s made from a steam cracker tube
m a t e r i a l (Sandvik 15Re10 c o n t a i n i n g 24,5% Cr, 20,5% N i , 1,8%
and 52,5% F e ) . Some experiments have a l s o been performed with
f o i l s made of n i c k e l . T y p i c a l e x i t gas compositions are shown in
F i g u r e s 4 and 5. The amount of coke deposited on the f o i l s are
summarised in Figures 6, 7, 8 and 9
I t i s seen that coke formation on the sample of f o i l i s de
pendent on the m a t e r i a l of the t u b u l a r r e a c t o r as i s the product
gas composition. With the s t e e l r e a c t o r , p r e o x i d a t i o n leads to a
s u b s t a n t i a l increase in the coke formation on the s t e e l f o i l
(Figures 6 and 7 ) . The e f f e c t of p r e o x i d a t i o n i s even more pron
ounced with Ni as the f o i l m a t e r i a l (Figure 8). On the other
hand, p r e o x i d a t i o n does not lead to a high rate of coke forma
t i o n on the s t e e l f o i l i
r e a c t o r (Figure 9).
G a s i f i c a t i o n of the f i r s t coke deposit l a i d down on a new
f o i l always r e s u l t e d in higher r a t e s f o r coke formation during
subsequent runs (Figure 9) However, i t has so f a r been impossi
ble to e s t a b l i s h a r e l a t i o n s h i p between repeated coke formation/
g a s i f i c a t i o n and the r a t e s f o r coke formation during the runs
f o l l o w i n g the f i r s t g a s i f i c a t i o n .
I t was found that carbon oxides do not form in the quartz r e
actor whereas a large amount of carbon oxides was formed in the
preoxidized s t e e l reactor (Table I ) . The content of other products
in the e x i t gas i s a l s o dependent of the r e a c t o r surface ( F i g u r e s
2, 4 and 5 ) . Increasing content of hydrogen was a l s o observed when
the same s t e e l r e a c t o r was used f o r a l a r g e number of experimental
runs with repeated coke f o r m a t i o n / g a s i f i c a t i o n . S i m i l a r e f f e c t s
have a l s o been observed in a t u b u l a r r e a c t o r f i l l e d with pieces o f
the r e a c t o r m a t e r i a l (Table II) during p y r o l y s i s of ethane and
ethylene. The o x i d i z e d surface d i d not e f f e c t the conversion o f
ethane very much, but the s e l e c t i v i t y of ethylene formation was
reduced from about 80% in the untreated r e a c t o r to about 15% when
the surface was pretreated with oxygen.
DISCUSSION
The present s t u d i e s have been concerned with the o v e r a l l e f

f e c t of s u r f a c e s on r e a c t i o n s o c c u r i n g during steam c r a c k i n g . The
formation of gaseous and s o l i d products has been r e l a t e d to the
nature of the r e a c t o r s u r f a c e . Steam c r a c k i n g i s , however, a high
temperature p y r o l y s i s r e a c t i o n in which free r a d i c a l intermedi
ates play an important r o l e . No attempt has been made to r e l a t e
the experimental r e s u l t s to the nature and amount of free r a d i
c a l s present in the system.
Coke formation on the f o i l s i s found to be dependent not only
on the nature of the f o i l but a l s o on the m a t e r i a l of the t u b u l a r
r e a c t o r . E s s e n t i a l l y , the s t u d i e s involved three r e a c t o r surface

35 h
70 80 90

CONVERSION (%)
CONVERSION (%)
Figure 4. Exit gas composition from steam cracking

of propane in the prereduced steel reactor with steel Figure 5. Exit gas composition from steam cracking
(Sandvik 15RelO) as the foil material after 10 min on of propane. Comparisons between prereduced and pre-
stream. Conditions: temperature range, 800S70C; oxidized systems. Conditions as in Figure 4.
3 8 2
feed gas composition, 29 mol% C H , 32% H 0, and
2
39% N ; and total feed rate, 0.92 L/min.
2!
8
to
>


3. HOLMEN E T AL. Steam Cracking of Propane 53
1.00
TIME (min)
Figure 7. Coke formation during steam cracking of propane at 840C on a steel

foil (Sandvik 15Re 10) in a preoxidized steel reactor. The reactor surface and the
foil were preoxidized for 95 min using 46% 0 in N at 840C.
2 2 Conversion of
C H :89%.
3 8 Feed gas as in Figure 4.
4.0
E
3.0
<
1 2.0
LL

1.0 h
20 30 40 50
TIME (min)
Figure 8. Coke formation during steam cracking of propane at 840C on Ni-foils

in the steel reactor. Key: O, preoxidized; and Q prereduced. Conversion of
C H :80%.
3 8 Feed gas as in Figure 4.

54 COKE FORMATION
0.12
^^^"^ 0 9-2
CM

. 0.10

NO
0.08 n^-cr"" "^- 0

PO 9-3
<
: 0.06

LL
LU
0.04

0.02
I I
10 20 30
TIME (min)
Figure 9. Coke formation during steam cracking of propane at 850C on steel

foils (Sandvik 15RelO) in a preoxidized quartz reactor.
The foil and the reactor were preoxidized for 155 min at 850C and the coke deposit
was burned out between each of the runs: PO 9-1, PO 9-2 and PO 9-3. Conversion of
C H :98%. Feed gas as in Figure 2.
3 8
TABLE I .
C o n t e n t o f c a r b o n o x i d e s in t h e e x i t gas f r o m steam c r a c k i n g
o f p r o p a n e in d i f f e r e n t r e a c t o r s . C o m p o s i t i o n o f t h e f e e d :
29 m o l - % C H , 32 m o l - % H 0 and 39 m o l - % N - I n l e t r e s i d e n c e
3 g 2 2
t i m e = 8 . 2 s e c . (= r e a c t o r v o l u m e / f e e d r a t e ) .
Conversion Temperature E x i t gas, mol-%
Reactor/
pretreatment C H , %
3 8 C co 2 CO
Steel reactor/
preoxidized 88.5 840 0.7 17.2
Quartz r e a c t o r /
preoxidized 96.7 855 - -

TABLE I I .
E f f e c t of pretreatment of a s t e e l r e a c t o r s u r f a c e (Sandvik 15Re10) on the product

gas composition during p y r o l y s i s of ethane and ethylene at 750 C with a constant
feed r a t e = 0.58 1/min. Dimensions of the r e a c t o r tube: length = 88 cm and i n s i d e
diameter =0.92 cm. The r e a c t o r tube was f i l l e d w i t h pieces of the r e a c t o r m a t e r i a l :
3.92 g or approximately 130 cm .
Feed Pretreatment E x i t gas composition, mol-% Conversion Selectivity
H, CH. C H C H C H
% C H , %
2 4
4 2 6 2 4 3 6
Ethane New tube. 13.1 0.52 74.1 12.1 0.06 14.4 81.1
Ethane With 0 -
2
27.3 0.45 66.8 5.4 0.01 19.9 32.4
Ethylene With 0 ~
2
77.0 0.26 2.9 19.8 0.04 70.1 -
Ethylene With H ~
2
50.3 0.44 2.1 46.9 0.12 40.9 -
Ethylene After 5 runs- 2.8 0.81 1.4 93.8 0.44 5.8 -

During the heating p e r i o d the tube was exposed to an i n e r t atmosphere (argon).
^0.2 1 0 /min in 15 min at 750C. ^0,5 1 H^min in 30 min at 750C. -Feed gas
2

about 8 min. during each run, no gas supply between the runs.
56 COKE FORMATION
compositions, and a l l of these gave s i g n i f i c a n t d i f f e r e n c e s in the

gas and s o l i d products (Table I and F i g u r e s 2, 5, 6, 7 and 9)
With a s t e e l r e a c t o r i t i s shown that p r e o x i d a t i o n of the
f o i l and the r e a c t o r surface r e s u l t s in much higher coke formation
on the f o i l compared with prereduction of the r e a c t o r system
(Figures 6 and 7 ) T h i s i s not s u r p r i s i n g since Fe and Ni present
on the o x i d i z e d surface are known to be good c a t a l y s t s f o r carbon
formation (2J). Prereduced f o i l s , which contain mostly Cr and Mn
on the surface, produce much l e s s coke. In agreement with t h i s ,
the coke deposit from the p r e o x i d i z e d f o i l surface contains Fe
( c h a r a c t e r i s t i c of c a t a l y t i c coke formation) whereas the deposit
on the prereduced f o i l s contains e f f e c t i v e l y no Fe (20).
Using the quartz l i n e r , coke formation on the f o i l s was sub-
s t a n t i a l l y l e s s and so were the d i f f e r e n c e between the coke forma-
t i o n of preoxidized an
be c a t a l y t i c a l l y i n e r t
should not and does not r e f l e c t the chemical nature of the sur
f a c e . Gaseous and s o l i d products obtained in the quartz r e a c t o r
are shown in Figures 2, 3 and 9 The gas phase product spectrum
i s t y p i c a l of a quartz r e a c t o r (Figure 2) and i s unaffected by
the f o i l m a t e r i a l . The i n i t i a l rate of coke formation on the f o i l
depends on the f o i l m a t e r i a l , but the rate of coke formation on
a l l f o i l s appears to approach a value s i m i l a r to that f o r coke
formation on coke.
The r e s u l t s i n d i c a t e that the e f f e c t of the r e a c t o r surface
depends on the l o c a t i o n in the r e a c t o r . At the r e a c t o r e x i t the
tube m a t e r i a l becomes covered in coke, and any d i f f e r e n c e s due to
the chemistry of the o r i g i n a l s u r f a c e s would be expected to de-
crease with time on stream as seen by reference to Figure 3 and
e v e n t u a l l y disappear. However, due to the absence of coke forma-
t i o n over a length of r e a c t o r equivalent to the i n d u c t i o n period
(4, J9), the i n f l u e n c e of the chemical nature of the r e a c t o r tube
at the r e a c t o r i n l e t w i l l p e r s i s t .
However, i t i s the analyses of the gas phase products which
i s p a r t i c u l a r l y i n t e r e s t i n g . I t i s c l e a r from these experiments
that carbon oxides are formed only on s t e e l r e a c t o r s (Table I ) ,
and t h i s agrees with the f i n d i n g s of Dunkleman and A l b r i g h t (J2),
who suggested that a l l carbon oxides r e s u l t from g a s i f i c a t i o n at
a s u r f a c e . In support of t h i s , most carbon oxides are formed on
p r e - o x i d i z e d s t e e l s , which c o n t a i n s i g n i f i c a n t q u a n t i t i e s of
i r o n in the s u r f a c e : both i r o n and i r o n oxides are known to be
good g a s i f i c a t i o n c a t a l y s t s .
In a d d i t i o n , some of the formation of carbon oxides may be
due to steam reforming r e a c t i o n s . The amount of hydrogen produced
in the r e a c t i o n was considerably higher over a p r e - o x i d i z e d sur-
face, while the amount of hydrocarbons was lower (Figures 2 and
5). I t could w e l l be that some of these e f f e c t s are due to steam
reforming r e a c t i o n s catalyzed by n i c k e l exposed in the p r e o x i d i -
zed s u r f a c e . These r e a c t i o n s would lead to the e f f e c t s observed:

3. HOLMEN ET AL. Steam Cracking of Propane
nCO + (n + m/2)H (
C0 2 + H 2
CH 4 + H0 2
with the production of hydrogen being favoured at the tempera-

tures associated with steam c r a c k i n g . N i c k e l and i r o n are known
to be b e t t e r c a t a l y s t s f o r t h i s r e a c t i o n than chromium or mangan-
ese and these are b e t t e r than quartz (22). As a r e s u l t , the p r o d -
u c t i o n of hydrogen should decrease and the amount of hydrocarbon
should increase as the r e a c t i o n i s c a r r i e d out over d i f f e r e n t
surfaces in the f o l l o w i n g o r d e r : p r e - o x i d i z e d a l l o y surface (Ni
and Fe on the surface) > pre-reduced a l l o y surface (Cr and Mn on
the surface) > quartz (no metals on the surface of the
As seen in Figures 2 an
mentally.
The r e s u l t s show c l e a r l y the importance of the chemical n a -
ture of the a c t u a l surface in determining the product spectrum
observed during steam c r a c k i n g . The surface has an important be-
a r i n g on both the s o l i d and gaseous products of the r e a c t i o n . I t
would be very i n t e r e s t i n g to e s t a b l i s h the exact mechanism by
which t h i s occurs, but the f r e e r a d i c a l intermediates i n v o l v e d
are not amenable to study using the present system.
Acknowledgments
The support of t h i s work by the Royal Norwegian Council f o r

S c i e n t i f i c and I n d u s t r i a l Research i s g r a t e f u l l y acknowledged.
Literature Cited
1. Zdonik, S.B.; Green, E.J.; H a l l e e , C.P. "Manufacturing

E t y l e n e " . Petroleum P u b l i s h i n g Corp. 1970. T u l s a , Oklahoma.
2. Goossens, A.G.; Dente, M . ; R a n z i , E . H y d r . P r o c . 1970.
57 (9), 227.
3 Bennett, M.J.; P r i c e , J.B. "Behaviour In Simulated Cracker
Environments of HK40 S t e e l , Silica and an ESC-Tube Coke".
14th B i e n n i a l American Carbon Conference E x t . Abstract
Progr. 1979. 137 - 8 .
4. Trimm, D . L . C a t a l . Rev. - Sci. Eng. 1977. 15 (2), 155.
5. Sundaram, K.M.; Froment, G . F . Chem. Eng. Sci. 1979. 34, 635.
6. Newsome, D.S.; Leftin, H . P . "Coking Rates in a Laboratory
P y r o l y s i s Furnace". 72nd Annual AIChE Meeting. San F r a n c i s c o .
Nov. 25-29. 1979. Paper no 21d.
7. A l b r i g h t , L.F.; Yu, Y.C.; Welther, K. "Coke Formation During
P y r o l y s i s O p e r a t i o n " . 85th N a t i o n a l AIChE Meeting. June 4-8,
P h i l a d e l p h i a . Paper no 15E.
8. Lahaye, J.; Badie, P . ; Ducret, J. Carbon 1977. 15, 87.
9. T s a i , C.H.; A l b r i g h t , L . F . "Surface Reactions Occurring

58 COKE FORMATION
During P y r o l y s i s o f L i g h t P a r a f f i n s " . ACS Symp. Ser. 1976.

32, 274.
10. Crynes, B.L.; A l b r i g h t , L.F. Ind. Eng. Chem. Process. Des.
Dev. 1969. 8 ( 1 ) , 25.
11. Leathard, D.A.; P u r n e l l , J.A. " P a r a f f i n P y r o l y s i s " . Annual
Review Phys. Chem. 1970. 21, 197.
12. Dunkleman, J.J.; A l b r i g h t , L.F. "Surface E f f e c t s During Pyro
lysis of Ethane in Tubular Flow Reactors". ACS Symp. Ser.
1976. 32, 241.
13. Trimm, D.L.; Holmen, .; Lindvg, O.A. J. Chem. Tech. B i o -
t e c h n o l . 1981. 32, 241.
14. Shah, Y.T.; S t u a r t , E.B.; Sheth, K.D. Ind. Eng. Chem., Pro-
cess Des. Dev. 1976. 15 ( 4 ) , 518.
15. L a i d l e r , K.J.; Sagert, N.H.; Wojciechowski, B.W. Proc. Roy.
Soc. (London). 1962 270A 242
16. Tamai, Y.; Nishiyama
16.
17. Volkan, A.R.; April, G.C. Ind. Eng. Chem., Process Des.
Dev. 1977. 16 (4), 429.
18. A l b r i g h t , L.F. I b i d . 1978. 17 (3), 377.
19. Trimm, D.L.; Turner, C.J. J. Chem. Tech. B i o t e c h n o l 1981.
31, 195.
20. Holmen, .; Trimm, D.L. "Coke Formation during Cracking o f
Hydrocarbons. Part I I . In press.
21. Lobo, L.S.; Trimm, D.L.; F i g u e i r e d o , J.L. Proc. 5th I n t .
Congr. C a t a l . 1973. 1125.
22. C a t a l y s t Handbook. Wolfe Scientific Texts (London). 1970.

4
Oxidation of an Ethylene Steam Cracker
Pyrolysis Tube Deposit in Water Vapor and
Its Enhancement by Inorganic Catalysts
M . J. B E N N E T T and J. B. PRICE
Materials Development Division, AERE Harwell, Didcot, Oxon, 11 ORA,

United Kingdom
G a s i f i c a t i o n of a carbonaceous deposit formed on

a r a d i a n t l y heated ethylene steam cracker p y r o l y s i s
tube, in water vapour, at 721-1056C was chemically
c o n t r o l l e d . Oxidation rates were l i n e a r between
10-85% burn o f f and increased p r o p o r t i o n a l l y with
water vapour p a r t i a l pressure (38-362 mm Hg). The
a c t i v a t i o n energy and pre-exponential f a c t o r were
-1 9 -2 -1
57 Kcal mole and 3.6 x 10 mg cm min respectively.
G a s i f i c a t i o n was catalysed by inorganic i m p u r i t i e s
entrained in the deposit and was promoted by hydrogen
and butane.
Contamination of the deposit surface with Pb, Fe,
Co and Ni ( i n the m e t a l l i c s t a t e ) , Na, K, Li, Rb and
Cs carbonates or oxides, and Ba and Sr oxides
enhanced g a s i f i c a t i o n , at 900C, by up to a f a c t o r of
135. C a t a l y s i s derived from oxygen t r a n s f e r
mechanisms. A f u r t h e r nineteen elements had no
s i g n i f i c a n t influence.
A p r i n c i p a l f a c t o r governing the operating c y c l e of ethylene

steam crackers (ESC) i s coke formation on the i n s i d e surfaces of
the r a d i a n t l y heated p y r o l y s i s tubes. Steam i s used as the c a r r i e r
f o r the hydrocarbon feedstock as i t i s known e m p i r i c a l l y to
minimise t h i s coking. I t i s probable that the observed d e p o s i t i o n
i s a net process representing the d i f f e r e n c e between formation and
removal, p r i m a r i l y by thermal o x i d a t i o n . A fundamental requirement
of any d e t a i l e d understanding of the o v e r a l l processes involved,
t h e r e f o r e , i s knowledge of the o x i d a t i o n behaviour of such
d e p o s i t s . Although s e v e r a l studies have been undertaken on various
carbons considered to simulate ESC p y r o l y s i s tube coke (e.g. (1))
no relevant information has been published f o r plant m a t e r i a l . To
provide these data, t h e r e f o r e , the o x i d a t i o n behaviour of a coke
formed on an ESC tube has now been examined in water vapour.
This chapter not subject to U.S. copyright.

InPublished 1982 on American
Coke Formation Chemical
Metal Surfaces; Society.
Albright, L., et al.;
60 COKE FORMATION
I t i s now w e l l e s t a b l i s h e d (2-4) that the o x i d a t i o n of carbon

can be c a t a l y s e d by c e r t a i n metals and inorganic compounds;
although information i s less comprehensive f o r water vapour. As a
consequence the e f f e c t i v e n e s s of a number of elements in promoting
the o x i d a t i o n of the radiant heater tube coke in t h i s environment
has been surveyed.
Experimental
The carbonaceous deposit was formed on the w a l l of a r a d i a n t l y

heated HK40 s t e e l p y r o l y s i s tube in an ethylene steam cracker from
a naphtha hydrocarbon feedstock. I t was derived from a region in
which the temperature of the gas was 820-830C, while that of the
underlying tube w a l l was 920-930C. The tube had been operated f o r
3 years on a c y c l e c o n s i s t i n g of ^ 5 0 days cracking followed by
decoking to burn out th
The deposit examined was
f i n a l cracking operations. I t s p h y s i c a l and chemical
c h a r a c t e r i s t i c s have been described (5).
The o x i d a t i o n of randomly selected deposit samples, of
approximate s i z e 5 mm 5 mm, was followed using a CI E l e c t r o n i c s
Mk 2 c o n t r o l l e d atmosphere microbalance.
Argon, used both as the c a r r i e r gas f o r the oxidant, water
vapour, and a l s o as a purge gas was obtained from a l i q u i d supply.
It was p u r i f i e d by passage through BTS c a t a l y s t and magnesium
p e r c h l o r a t e to remove oxygen and water vapour r e s p e c t i v e l y . Water
vapour was added at a prescribed p a r t i a l pressure ()>
between 58-362 mm Hg, by passing the p u r i f i e d argon through a
heated water s a t u r a t o r . Hydrogen, or any other gas required, was
then added to the r e a c t i o n gas, which at 1 atm pressure passed up
over the sample suspended w i t h i n an e x t e r n a l l y heated s i l i c a
r e a c t i o n v e s s e l . Dry argon flowed continuously through the
balance head and was exhausted, together with the e x i t gases from
the r e a c t i o n v e s s e l , through a side arm located just above the
furnace. This procedure protected the balance mechanism from
water vapour and r e a c t i o n products and a l s o prevented condensation
on the hangdown rods.
The experimental procedure was to b r i n g the sample up to
constant temperature (between 721-1056C) in dry argon and then
change to the r e a c t i o n gas. Oxidation was followed by the
continuous measurement of the l o s s in sample weight.
Surface contamination with inorganic s a l t s was c a r r i e d out by
b o i l i n g deposit samples f o r 10 mins in e i t h e r a 30wt.% o r
saturated s a l t s o l u t i o n , whichever was the lower c o n c e n t r a t i o n .
A f t e r c o o l i n g in the s o l u t i o n the samples were removed and d r i e d
under an i n f r a - r e d lamp at*^150C. With c e r t a i n s a l t s ( t i n ,
bismuth and zirconium), which were unstable on b o i l i n g , the samples
were soaked in the appropriate s o l u t i o n overnight and were a i r
d r i e d . Where p o s s i b l e , s a l t s of organic acids were chosen as they
decomposed in dry argon to the r e s p e c t i v e metal oxides at

4. B E N N E T T A N D PRICE Oxidation of a Pyrolysis Tube 61
temperatures below 500C. Other s a l t s (e.g. h a l i d e s and sulphates)

could have contaminated the deposit substrate with anions which
could have a f f e c t e d the o x i d a t i o n k i n e t i c s . The heat treatment of
the sample was continued u n t i l constant sample weight was a t t a i n e d
at the o x i d a t i o n temperature before the r e a c t i o n gas was admitted.
The o x i d a t i o n was then followed in an i d e n t i c a l manner to that
already described.
Results
In the k i n e t i c p l o t s ( F i g u r e s 1-3, 5 and 6) the measurements

of o x i d a t i o n ( i . e . the l o s s of sample weight) were normalised in
terms of both the i n i t i a l sample weight and the geometric surface
area. The r e s p e c t i v e s c a l e s are given on the l e f t and r i g h t hand
s i d e s of each f i g u r e .
E f f e c t of Sample Containmen
experiments e s t a b l i s h e d that, with the experimental procedures and
c o n d i t i o n s studied, g a s i f i c a t i o n was c o n t r o l l e d by chemical
k i n e t i c s and not gas access. For experimental convenience the
samples were contained w i t h i n a s i l i c a c r u c i b l e . To ensure that
t h i s would not impede gas movement e i t h e r to or from the o x i d i s i n g
s u r f a c e , the o x i d a t i o n behaviour of a contained sample was compared
with that of a sample f r e e l y suspended w i t h i n the environment. At
the highest temperature (1056C), there was no s i g n i f i c a n t
d i f f e r e n c e over 70% burn o f f between e i t h e r the k i n e t i c s or r a t e s
=
of o x i d a t i o n of the samples in water vapour ( p ^ O 58 mm Hg).
A l l subsequent specimens were exposed, therefore, w i t h i n s i l i c a
c r u c i b l e s , except when the samples were contaminated with the
a l k a l i s a l t s , where gold c r u c i b l e s were used.
The second experimental parameter examined was the rate of gas
supply to the specimen. Varying the argon c a r r i e r flow rate from
1
156 to 1000 cm^min" had no marked e f f e c t upon the o x i d a t i o n
behaviour of the deposit in water vapour at e i t h e r 815C (with
20 = 362 mm Hg) or 1050C (with p^Q - 58 and 362 mm Hg) (Figure 1).
In the m a j o r i t y of the l a t e r experiments the argon flow rate was
1
maintained at 500 cnAnin"" .
E f f e c t of Deposit S t r u c t u r e . The deposit consisted of two
l a y e r s with widely d i f f e r e n t concentrations of entrained i n o r g a n i c
i m p u r i t i e s ( 5 ) . The inner, t h i n , l a y e r of filamentous m a t e r i a l
contained the bulk of the inorganic i m p u r i t i e s analysed in the
deposit; the p r i n c i p a l c o n s t i t u e n t s being 0.7 wt.% Fe, 0.1 wt.% Ni
and 0.15 wt.% Cr. The corresponding l e v e l s in the outer, t h i c k e r
pyrocarbon l a y e r were considerably smaller, being 200 ppm Fe, 50
ppm Ni and 50 ppm Cr. Gas permeability through the deposit was
low (5) so that only the outer deposit surface would have been
o x i d i s e d in s e r v i c e , p r o v i d i n g , of course, there were no r a d i a l
cracks through the deposit.
To examine the e f f e c t of the inner l a y e r , the o x i d a t i o n of "as
r e c e i v e d " deposit was compared with that of m a t e r i a l from which the
inner layer had been removed by abrasion on s i l i c o n carbide papers,

to

w

>
Figure 1. Effect of argon carrier flow role upon the deposit oxidation by water vapor at 1056C. H
Key to water vapor partial pressure: O, 58 mm Hg; and , 362 mm Hg.
as
4. BENNETT AND PRICE Oxidation of a Pyrolysis Tube 63
with a f i n a l abrasion in one experiment with 45 urn diamond. The

exposure conditions covered the middle and upper temperatures (863
and 1056C) and the minimum and maximum water vapour p a r t i a l
pressures (38 and 362 mm Hg) of the ranges studied. As shown in
Figure 2 there was no marked e f f e c t of the abrasion. Although t h i s
was a somewhat a r b i t r a r y process and the inner l a y e r had a v a r i a b l e
thickness, the abrasion would have removed the bulk of the inner
l a y e r together with the associated inorganic i m p u r i t i e s . Unless
stated otherwise a l l other samples o x i d i s e d were of "as received"
deposit.
E f f e c t of Water Vapour P a r t i a l Pressure. The i n f l u e n c e of

water vapour p a r t i a l pressure was examined a t 815 and 1056C. A t
the lower temperature one sample was o x i d i s e d at s u c c e s s i v e l y
i n c r e a s i n g p a r t i a l pressure (100 196 d 362 respectively)
On both occasions when
r e a c t i o n r a t e . I f ther simpl powe p
i e e r a t e t n e n nm a
the o x i d a t i o n rate and p ^ O * ^ (2^ > y
be determined by comparison of the o x i d a t i o n r a t e s , r ^ and r , 2
1 t o a n c t n u s
at the i n s t a n t of change of PjÔ Pi P2 * > also
at the same extents of o x i d a t i o n , from the expression,
P
2 / 2
= l o g / log
r P
l / l
Experimentally, f o r the increase in P H 0 196 mm Hg,

2
f r o m 1 0 0t 0
and from 196 t o 362 mm Hg, the o x i d a t i o n rates were 1.3 and
2.7 mg/gh and 1.6 and 3.4 mg/gh r e s p e c t i v e l y . The corresponding
values derived f o r were 1.1 and 1.2, suggesting that the rate was
d i r e c t l y p r o p o r t i o n a l to water vapour p a r t i a l pressure.
At 1056C a d i f f e r e n t , but complementary, procedure was used
to i n v e s t i g a t e the e f f e c t of P H 0 2
o n r e a
c t i o n rate.
Separate deposit samples were oxidised in s i x d i f f e r e n t water
vapour pressures between 38 and 362 mm Hg (Figure 3 ) . The
o x i d a t i o n k i n e t i c s were a l l of a s i m i l a r form, in that i n i t i a l l y ,
the rate decreased with burn o f f up to 5-10% removal and then was
e s s e n t i a l l y l i n e a r up to nearly 90% burn o f f before decreasing
with greater a t t a c k . The l a s t change was undoubtedly associated
with the diminution of the sample s i z e so that the p r o p o r t i o n a l i t y
r e l a t i o n s h i p with the i n i t i a l sample weight or surface area no
longer a p p l i e d . The mean r e a c t i o n rates increased in d i r e c t
proportion with P H O (Figure 4), as observed at 815C.
2
E f f e c t of Temperature. The o x i d a t i o n of separate samples in

362 mm Hg water vapour pressure was examined at nine temperatures
between 721 and 1056C (Figures 5 and 6). At a l l temperatures,
except at 959C and p o s s i b l y the lowest temperature 721C, the
o x i d a t i o n k i n e t i c s already described a p p l i e d . At 721C o x i d a t i o n
was continued only up to 10% burn o f f , so that the k i n e t i c s could

8
W
ON
2
>

Effect of deposit structure on oxidation behavior.

Figure 2.

-
os
*
s
4^
LA
I
W

>
W

H
H

COKE FORMATION
10 in -i co f^J
q 6uu 3iVd N0I10V3U

s,
-4
4^
ON
w
'
m
W
W
>
H
H

00
t-H
W
>


4. BENNETT AND PRICE Oxidation of a Pyrolysis Tube 69
not be e s t a b l i s h e d with c e r t a i n t y . At 959C the k i n e t i c s were

d i f f e r e n t , in that the weight loss vs time curves were sigmoidal.
Thus, a f t e r the i n i t i a l period during which the o x i d a t i o n rate
decreased, i t then g r a d u a l l y increased with time up to 80% burn
o f f and f i n a l l y decreased f o r the reasons already o u t l i n e d . To
examine the temperature dependence, average l i n e a r r e a c t i o n r a t e
constants were c a l c u l a t e d at the end of the exposure, or 80% burn
o f f , whichever was the g r e a t e r . The r e s u l t a n t Arrhenius p l o t
1
(Figure 7) gave values of the a c t i v a t i o n energy as 57 K c a l mole"
1
and of the pre-exponential f a c t o r as 3.6 10^ g cm^min"" . m
E f f e c t of Hydrogen. The i n f l u e n c e of hydrogen a d d i t i o n s t o

the environment was examined at 900 and 1056C. With the
experimental procedure employed, i n c r e a s i n g p ^ could only
be accomplished by concurrentl decreasin ^-t th
lower temperature a deposi
Hg p a r t i a l pressure wate vapou hydroge stepwis
i n c r e a s i n g p a r t i a l pressures from 19.4 to 209 mm Hg (Figure 8).
The water vapour p a r t i a l pressures then decreased r e s p e c t i v e l y from
354 t o 262 mm Hg and the P H / P H 0 r a t i o s ranged from 0.005 to 0.80.
2 2
The i n i t i a l hydrogen a d d i t i o n enhanced the rate of attack but i t s

i n f l u e n c e diminished with time. The pattern was repeated by
s u c c e s s i v e l y smaller extents on each subsequent increase in
2 The increased rates due to these hydrogen a d d i t i o n s
always exceeded, however, any reductions in rate r e s u l t i n g from the
corresponding stepwise P H Q decrease. On removal of the
2
hydrogen, which was accompanied by an increase in the water vapour

p a r t i a l pressure, the o x i d a t i o n rate decreased but was a c c e l e r a t e d
again on the readmission of hydrogen.
At 1056C the e f f e c t of hydrogen was examined on the o x i d a t i o n
behaviour of separate samples and in some experiments i t was added
continuously throughout the exposure (Figure 9 ) . A hydrogen
p a r t i a l pressure o f 19.4 mm Hg had no apparent i n f l u e n c e upon the
deposit o x i d a t i o n in 353-362 mm Hg p a r t i a l pressure water vapour.
However, the r e a c t i o n rates were extremely r a p i d , which could have
masked any r e l a t i v e l y small e f f e c t of hydrogen. At a lower
PH 0 (36.3-38.0 mm Hg) the a d d i t i o n of hydrogen, at a p a r t i a l
2
pressure of 34.5 mm Hg, e i t h e r continuously throughout o x i d a t i o n o r

a f t e r an i n i t i a l period of o x i d a t i o n in water vapour alone,
enhanced the g a s i f i c a t i o n rate considerably. Immediately the
hydrogen a d d i t i o n was discontinued, the o x i d a t i o n rate decreased to
that f o r the P H O alone.
2 Hydrogen exerted a s i m i l a r
i n f l u e n c e upon the o x i d a t i o n behaviour of an abraded sample, as i t
had done upon that of the complete deposit.
E f f e c t o f Butane. The i n f l u e n c e of butane a d d i t i o n s upon the

o x i d a t i o n behaviour of abraded samples was examined at 793, 838 and
p
882C. For the majority of the experiments, the PButane/ H20
r a t i o was changed by maintaining PButane * altering
a n (
2

w
>


5
*
*
4^
?
w
<
w
w
S!
>
*
2

>


P
NOTE: CURVE - WAS FOR AN CURVE CURVE H 0 2 H / 2 P (
ABRADED SAMPLE WHILE SECTION mm Hg mm Hg 2

H 0
THE REMAINDER WERE
-ooo- THROUGHOUT 362 0
FOR THE COMPLETE
t M THROUGHOUT 353 194 0 055
DEPOSIT
0 TO ( A ) 36 3 34 5 0 95
AFTER0 36 3 0
0 TO 38 0 0
900 r - AFTER 36 3 34-5 095
-OCK> THROUGHOUT 38 0 0
0 TO ( S 38 0 0
AFTER 36 3 34 5 0-95
800 L -
700r- 00
'> 600h
I 500h
LU
4001
in
H50
_
3001-

200 h -
1 00

l I I I I I I I I I I I I I l I I I l I I I I I I I I
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310
TIME' MINUTES
Figure 9. Effect of hydrogen upon deposit oxidation by water vapor at 1056C.

The v a r i a t i o n in r e a c t i o n rate constant with PButane^PÔ

at each of the r e s p e c t i v e temperatures i s shown in Figure 10. At
t n e r e
each temperature with i n c r e a s i n g PButane^PHoO *ction
rate constant increased, went through a maximum and then decreased.
r a t i o r o r
The PButane/PHoO the maximum decreased with i n c r e a s i n g
temperature. In i n t e r p r e t i n g these r e s u l t s i t should be r e c a l l e d
that the basic experimental measurement was of sample weight
change. The i n i t i a l butane a d d i t i o n s promoted the rate of sample
weight l o s s due to o x i d a t i o n , but with i n c r e a s i n g PButane^PÔ
t h i s was g r a d u a l l y exceeded by weight gain due to carbon
deposition. SEM examination confirmed the occurrence of l i m i t e d
filamentary d e p o s i t i o n on specimen surfaces exposed to
p
Butane/PH20 = a
l l three temperatures (6).
t a
The maximum
i n f l u e n c e of butane on o x i d a t i o n at each temperature i s given by
the d i f f e r e n c e between the maximum r e a c t i o n rate constant and that
a t =
PButane/pH?0 0.1. O
which the o x i d a t i o n rat
316-345 mm Hg was increased by a butane p a r t i a l pressure of 16-415
mm Hg at 793, 838 and 882C were 3.5, 5.9 and 4.3 r e s p e c t i v e l y .
Influence of Inorganic Contaminants. The e f f e c t of gross

inorganic contamination of the ESC deposit surface was examined
upon i t s o x i d a t i o n , in water vapour, at 900C. The i n f l u e n c e of
t h i r t y - o n e elements, in e i t h e r an oxidised or elemental c o n d i t i o n ,
was studied. In the majority of the experiments, a f t e r an i n i t i a l
exposure to water vapour alone, hydrogen was added such that i t s
p a r t i a l pressure was increased stepwise over the subsequent
exposure. During t h i s period there was a corresponding decrease in
Pjl20 The ranges of p j ^ n d P H 2 / P H 2 O a
* ^ r e comparable u s e ( w
to those whose i n f l u e n c e had been examined already on the deposit

o x i d a t i o n , at the same temperature. P e r i o d i c c o n t r o l experiments
( i . e . with untreated deposit samples) were c a r r i e d out to e s t a b l i s h
that cross contamination had not a r i s e n .
The inorganic contaminants could be d i v i d e d i n t o two groups,
f i r s t l y , those which exerted, at most, a small i n f l u e n c e and
secondly, those which s u b s t a n t i a l l y enhanced g a s i f i c a t i o n .
Experimental data f o r the nineteen elements f a l l i n g in the f i r s t
group summarise the s a l t used in the surface treatment, the
probable chemical state of the element during deposit o x i d a t i o n ,
taking i n t o account the P H 2 / P H 2 O 8 covered and r a n e
the number of atoms of the element per i n i t i a l surface carbon s i t e .

The average o x i d a t i o n rates f o r surfaces contaminated with boron,
magnesium, aluminium, phosphorus, calcium, vanadium, chromium,
manganese, i r o n (as oxide), copper, z i n c , zirconium, molybdenum,
s i l v e r , cadmium, t i n , lanthanum, cerium and bismuth e i t h e r f e l l
w i t h i n , or were up to 50% above the range of the values f o r
untreated deposit (Table 1).
The experimental data f o r the eleven elements which catalysed
the o x i d a t i o n rate markedly, by f a c t o r s up to 135, are summarised

74 COKE FORMATION
Or-
I
c

(N
E l

en
i-
z
<

<
-6h
O 793C
838C
882C
1 2 3 A 5 6
BUTANE PARTIAL PRESSURE/WATER VAPOUR PARTIAL PRESSURE
P(BUTANE)
RATIO p ( H 2 0 ) 0 0 05 1-2 3 2 4-3 4-6 6-8
(BUTANE )(mm Hg) 0 16 415 415 415 415 415
P(H 0) (mm Hg )
2 345 337 345 129 96 90 61
Figure 10. Effect of the addition of butane upon the oxidation of the deposit.

4. B E N N E T T A N DPRICE Oxidation of a Pyrolysis Tube 75
Table I
Summary of c o n d i t i o n s of experiments f o r elements having e i t h e r no
e f f e c t or p o s s i b l y a s l i g h t i n f l u e n c e upon ESC deposit o x i d a t i o n
in 2 6 2 - 3 6 2 mm Hg water vapour p a r t i a l pressure a t 9 0 0 C
Probable - _
No. of atoms , Average
p
l c l etanical state o f P u \ reaction 0
Element Salt at canaencer "2 rate

ment of , _ range (a) , ,
., carbon site mg/gh (b)
oxidation
Boron boric acid oxide 354 No added 29
Magnesium acetate oxide 130 0.06-0.80 27
Aluminium nitrate
Phosphorus ammonium oxide 242 0.06-0.80 28
dihydrogen
phosphate
Calcium nitrate oxide 90 0.06-0.80 38
Vanadium ammonium oxide 49 0.06-0.80 24

vanadate
Chromium nitrate oxide 24 0.06-0.80 29
Manganese acetate oxide 39 0.06-0.80 46
Iron citrate oxide 72 0.06-0.80 32
Copper acetate metal 15 0.06-0.80 33
Zinc acetate oxide 69 0.06-0.80 16
Zirconium nitrate oxide 86 0.06-0.80 35
Molybdenum ammonium oxide 287 0.06-0.80 26

molybdate
Silver nitrate metal 187 0.06-0.80 23
Cadniun acetate metal 65 0.06-O.80 22
Tin nitrate metal 39 0.06-0.80 35
Lanthanum acetate oxide 61 0.06-0.80 36
Cerium nitrate oxide 86 No added 44
Bismuth nitrate metal 55 0.06-0.80 20
(a) Initially o x i d a t i o n was in PH2O =

^62^
& Subsequently, f o r
PH2/PH2O =
0.055, P H 2 0 = 3 5 3
^ H
S A N D
PH2 = 1 9 E
^ 1 1 1 1 1 1 H
8 >
while f o r /2 2
=
0 . 8 0 , pjÔ = 2 6 2 111111 H
S a n d
PH 2
= 2 0 9 111111 H g
*
(b) For comparison the average r e a c t i o n rates f o r seven separate

untreated samples of deposit o x i d i s e d over the same P H 2 O / P H 2 O
range, at 9 0 0 C , were 1 2 , 1 5 , 1 7 , 2 1 , 2 5 , 2 7 and 3 0 mg/gh
(Average = 2 1 mg/gh).

76 COKE FORMATION
in Table 2, while the o x i d a t i o n curves are shown in Figures 11-14.

A l l the a l k a l i metal oxides or carbonates were a c t i v e (Figure 11)
with t h e i r e f f e c t i v e n e s s decreasing with burn o f f . This has been
i n d i c a t e d in Table 2 by separating the i n i t i a l , high and the
subsequent, slower, r e a c t i o n r a t e s , which, in general, were s t i l l
greater than that of untreated d e p o s i t . On the assumption that the
e f f e c t i v e n e s s of these elements was d i r e c t l y p r o p o r t i o n a l to t h e i r
surface concentration then the order of i n c r e a s i n g a c t i v i t y of the
s a l t s of these elements was sodium comparable with potassium,
l i t h i u m , caesium and rubidium. The a l k a l i n e earth oxides a l s o
enhanced o x i d a t i o n , although to a smaller extent than the a l k a l i
metal carbonates or oxides. The r e s u l t s f o r calcium oxide have
been discussed already, while the e f f e c t s of barium and strontium
oxides are shown in Figure 12. Again the e f f e c t i v e n e s s of these
contaminants decreased with burn o f f but even a f t e r 50%
g a s i f i c a t i o n they enhance
and 4. Lead promoted deposite
i n t r o d u c t i o n of hydrogen to the gas phase such that P H O / P H ? 0
was 0.055 and i t would have been present in the m e t a l l i c s t a t e
(Figure 12). Iron, present as an oxide, had no i n f l u e n c e upon
d e p o s i t o x i d a t i o n (Figure 13). However, when the Pj^/PHoO
r a t i o was increased above that required (1.2) to ensure that the
element was in the m e t a l l i c s t a t e , i t was extremely c a t a l y t i c .
Other t r a n s i t i o n metals, n i c k e l and c o b a l t , also promoted
g a s i f i c a t i o n (Figure 14) with t h e i r a c t i v i t y being comparable to
that of i r o n . N i c k e l was e f f e c t i v e from the onset of the exposure
to water vapour, as the hydrogen released by the o x i d a t i o n was
s u f f i c i e n t to ensure that the element was completely reduced. In
c o n t r a s t , c o b a l t oxide, formed by decomposition of the acetate with
which the sample was t r e a t e d , was only reduced to the elemental
s t a t e on the a d d i t i o n of hydrogen to the gas phase such that
p
PH2/ H20 exceeded that (0.04) at which the oxide
was no longer thermodynamically s t a b l e .
Scanning E l e c t r o n Microscopy. The surface topography of

deposit samples o x i d i s e d at various temperatures and extents
of o x i d a t i o n were examined by scanning e l e c t r o n microscopy. To
provide a basis f o r subsequent comparison, i t was d e s i r a b l e to
e s t a b l i s h f i r s t the topography of the r e s i d u a l ash a f t e r complete
combustion. That formed at 1056C consisted of d i s c r e t e fragments
of v a r y i n g s i z e (Figure 15a) having a s k e l e t a l s t r u c t u r e . A f t e r
21% burn o f f at 862C the outer deposit surface ( i . e . nearest the
o r i g i n a l gas i n t e r f a c e ) was c r i s s - c r o s s e d with cracks ( F i g u r e 15b).
The surface between the cracks was smooth with l o c a l i s e d regions
covered with i r o n r i c h debris (Figure 15c) with the smaller
fragments being located p a r t i c u l a r l y along the crack edges.
Channelling had occurred at the sample edges, while the inner
s u r f a c e ( i . e . nearest to the o r i g i n a l tube i n t e r f a c e ) was covered
with inorganic debris remaining from the o x i d a t i o n of the inner
deposit l a y e r (Figure 15d). The s t r u c t u r a l features of the d e b r i s

Table II
Summary of the conditions for the experiments In which various elements enhanced
the deposit oxidation in 362 mm Hg partial pressure water vapour at 900C
Probable Burn off Burn off

No. of atoms Factor by Factor by
chemical Initial over Subsequent over
of element which which
state at reaction which reaction which
Element Salt per initial initial subsequent
commence rate initial rate subsequent
active rate was rate was
ment of mg/gh rate mg/gh rate
carbon site enhanced enhanced
oxidation applied applied
Lithium acetate oxide 145 440 0-10 21 30 25-30 1

Sodium carbonate carbonate 240 350 0-40 17 165 70-85 8
Sodium carbonate carbonate 215 435 0-40 21 185 60-75 9
Potassium carbonate carbonate 455 690 0-50 33 345 60-70 16
Rubidium carbonate carbonate 290 2830 0-20 135 65 75-85 3
Caesium carbonate carbonate 55 2700 0-10 130 55 45-55 2.5
Strontium nitrate oxide 65 100 0-20 5 40 40-50 2
Barium nitrate oxide 145 220 0-10 10 85 47-59 4
Lead acetate metal 20 125(A) 14-30 6
Iron citrate metal 35 230(B) 15-60 11
Cobalt acetate metal 25 440(A) 18-45 21 160 68-76 8
Nickel acetate metal 50 195 0-50 9 100 65-77 5

(A) Maximum rate in p 353 nm Hg, after = 19.4ranIfc added.
H
2 "2

(B) Rate in - 23.4 mm Ife, after = 35.1 nm Hg added.
78 COKE FORMATION
Figure 11. Effect of alkali metal salts upon the oxidation of the deposit in water
vapor at 900 C. For all curves P o = 362 mm H g except those after when
H2
P 19.4 mm H g was added to P o = 353 mm Hg.

H2 H2

Effect of barium and strontium oxides and lead upon the oxidation of the deposit in
water vapor at 900C.
Figure 12.

1
00

>


oo
S*
*
<x>
%
4^
i*
w
m

2
>

f
W
H
H

COKE FORMATION
Figure 15. Surface topography of oxidized ESC deposits.

appeared to be s i m i l a r to that of the ash. The underlying carbon

surface had a honeycomb topography and was traversed by channels,
while surface protrusions were often surmounted by small i r o n r i c h
p a r t i c l e s (Figure 15e). At 1056C attack of the outer surface at a
comparable burn o f f (18%) was c h a r a c t e r i s e d by p i t t i n g , in a d d i t i o n
to deeper c h a n n e l l i n g . A f t e r 60% burn o f f the topography of the
surfaces and edges were b a s i c a l l y s i m i l a r to that described, with a
coarsening of the main f e a t u r e s . The inorganic debris had s p a l l e d
from the inner surface but again was s t i l l present as d i s c r e t e
p a r t i c l e s surmounting deposit p r o t r u s i o n s .
The surface topography of the r e s p e c t i v e deposit surfaces
f o l l o w i n g o x i d a t i o n enhanced by the various a c t i v e contaminants was
e s s e n t i a l l y s i m i l a r to that described. The attack was
c h a r a c t e r i s e d by c h a n n e l l i n g and p i t t i n g , which r e s u l t e d in the
formation of deeper channel in th f th a l k a l i metal
oxides/carbonates, e.g
o f f i s shown in Figure 15f
Discussion
For the experimental conditions of temperature, water vapour

p a r t i a l pressure and gas flow rate examined the k i n e t i c s of
g a s i f i c a t i o n of the ESC d e p o s i t were c o n s i s t e n t with previous
observations f o r the carbon-water vapour r e a c t i o n (7,8). The
r e a c t i o n was chemically c o n t r o l l e d and the o x i d a t i o n rate was
l i n e a r l y dependent upon water vapour p a r t i a l pressure. The
1
measured a c t i v a t i o n energy (57 Kcal mole" ) was in the middle
of the p r e v i o u s l y reported values (13.5 ( l ) - 8 3 (9) K c a l mole" ) 1
for this reaction.

Many elements have been shown to c a t a l y s e carbon g a s i f i c a t i o n
by water vapour (2,3). The e f f e c t i v e n e s s of the majority of these
elements, as w e l l as others, in promoting the o x i d a t i o n of t h i s ESC
deposit were examined. In agreement with previous observations on
carbon, the three groups of elements which most a c t i v e l y catalysed
ESC deposit o x i d a t i o n were the t r a n s i t i o n metals (Fe, Co and N i ) ,
the a l k a l i metals (Na, K, L i , Rb and Cs) and the a l k a l i n e earths
(Ca, Ba and S r ) . The only apparent d i f f e r e n c e was that lead
promoted o x i d a t i o n of the ESC deposit but not g r a p h i t e .
I t seems to be widely accepted that oxygen t r a n s f e r mechanisms
are r e s p o n s i b l e p r i m a r i l y f o r the catalysed o x i d a t i o n of carbon.
These are based on the continuous c y c l i c v a r i a t i o n of the o x i d a t i o n
s t a t e of the c a t a l y s t as i t i s o x i d i s e d by chemisorbed oxygen, from
the d i s s o c i a t i o n of water vapour and then reduced by the underlying
carbon, which in turn becomes g a s i f i e d as carbon monoxide. The
l o c a l i s e d r e a c t i o n of the c a t a l y s t p a r t i c l e with the carbon
s u b s t r a t e r e s u l t s in p a r t i c l e motion and channelling of the
surface.
For i r o n , c o b a l t and n i c k e l the o x i d a t i o n - r e d u c t i o n c y c l e was
between metal and oxide, as g a s i f i c a t i o n of the ESC deposit was
c a t a l y s e d only when the element could be present in the m e t a l l i c

84 COKE FORMATION
state* The c r i t i c a l parameter in determining the e f f e c t i v e n e s s of

a t r a n s i t i o n metal would be i t s a f f i n i t y f o r oxygen. Metals, such
as copper and s i l v e r , having a lower r e a c t i v i t y f o r oxygen than
i r o n , n i c k e l and cobalt would form a l e s s stable oxide and as a
consequence could not have promoted the d i s s o c i a t i o n of water
vapour. In contrast other metals with a higher oxygen a f f i n i t y ,
such as chromium and manganese, formed a more s t a b l e oxide, which
could not be reduced by r e a c t i o n with the carbon substrate.
Confirmation that chromium and manganese, when present i n i t i a l l y in
a m e t a l l i c s t a t e , were not a c t i v e c a t a l y s t s was provided by the
1
o x i d a t i o n of deposit samples implanted with l O ^ of the
2
r e s p e c t i v e ions cm" , With t h i s surface treatment technique
the ions at concentration were incorporated i n t o the surface
to a maximum depth of 0.5 urn.
The observed c a t a l y t i e f f e c t f th a l k a l i metal carbonate
and oxides and the a l k a l i n
the ESC d e p o s i t in wate vapou agai probably
successive o x i d a t i o n and reduction processes. A possible cycle
carbonate-metal-hydroxide could be f e a s i b l e at t h i s temperature, at
l e a s t f o r sodium, potassium and l i t h i u m (_3) and conceivably a l s o
for cesium and rubidium. For barium and strontium the c y c l e could
be between a higher and a lower oxide. Calcium, in contrast to
barium and strontium, does not form a peroxide by o x i d a t i o n of
calcium oxide and in any case t h i s would not be stable above 200C,
which could e x p l a i n why calcium oxide was not an a c t i v e c a t a l y s t .
The ESC deposit contained appreciable l e v e l s of p o t e n t i a l
c a t a l y t i c elements. These appeared to have promoted g a s i f i c a t i o n ,
as the o x i d a t i o n of the ESC coke was nearly f i v e orders of
magnitude greater than that of e f f e c t i v e l y pure graphite (SP-1),
with an ash content of ^ 1 ppm (Table 3). Such a wide discrepancy
would be l e s s l i k e l y to be a t t r i b u t a b l e to s t r u c t u r a l or t e x t u r a l
d i f f e r e n c e s . A l s o , m e t a l l i c n i c k e l dispersed in the SP-1 graphite
at concentrations of 303 ppm and 1.4 wt.% increased i t s
2 2
g a s i f i c a t i o n rate by f a c t o r s of 10 and 4 10 r e s p e c t i v e l y .
The corresponding o x i d a t i o n rates of simulated carbonaceous
deposits formed from cyclohexane decomposition were a l s o
c o n s i d e r a b l y lower than that of the ESC coke (12). The f a c t o r of
3-4 higher g a s i f i c a t i o n rate of the deposit formed on a s t e e l
rather than a carbon or s i l i c a substrate could p o s s i b l y r e f l e c t the
i n c o r p o r a t i o n of p o t e n t i a l c a t a l y t i c m e t a l l i c c o n s t i t u e n t s during
i t s formation. The 580 graphite was believed to simulate ESC coke
(1) and in the event, i t s o x i d a t i o n behaviour was comparable to
that of the p a r t i c u l a r ESC coke examined. However, in view of the
c r u c i a l dependence of g a s i f i c a t i o n upon the extents and chemical
state of entrained inorganic i m p u r i t i e s and p o s s i b l y a l s o of the
carbon s t r u c t u r e , r e l i a b l e o x i d a t i o n data f o r plant deposits can be
obtained only on such m a t e r i a l . A c o r o l l a r y of t h i s conclusion
would be that there could be a s i g n i f i c a n t v a r i a t i o n between the
o x i d a t i o n behaviour of deposits from d i f f e r e n t plants and also of
those formed from d i f f e r e n t feedstocks.

Table I I I
2 1 1
S p e c i f i c o x i d a t i o n r a t e s (ug m" min" (mm HÔ)" a t 850C
-r (a) Oxidation _ _
Carbon Impurity content
J
^ Reference
* rate
SP-1 graphite
Modified SP-1 graphite 330 ppm Ni 15 (10, 11)
M o d i f i e d SP-1 graphite 1.4 wt.% N i 50 (10, 11)
1500 ppm Fe,

580 graphite
Ash content 1500 ppm 1000 (i)
Deposit on carbon (b) N.D. 35 (12)
Deposit on quartz (b) N.D. 44 (12)
Deposit on s t e e l (b) N.D. 156 (12)
ESC plant coke Outer layer - 200 ppm 880 This work
Fe, 50 ppm Ni
N.D. - not determined.
(a) T r a n s i t i o n metals and other elements known to c a t a l y s e

gasification.
(b) Deposit formed from cyclohexane and o x i d i s e d at 860C.

86 COKE FORMATION
The ESC coke examined consisted of two l a y e r s . Removal of the

t h i n n e r , inner, deposit layer and associated inorganic impurity
content d i d not appear to have any marked i n f l u e n c e on the
o x i d a t i o n behaviour. This would suggest that the o x i d a t i o n of the
main bulk of the deposit ( i . e . the outer pyrocarbon l a y e r ) was
catalysed by i m p u r i t i e s entrained w i t h i n the l a y e r . As f a r as
could be ascertained these i m p u r i t i e s were d i s t r i b u t e d randomly
( 5 ) . There was no evidence of a concentration gradient for any
element across t h i s l a y e r from the i n t e r f a c e with the inner deposit
layer.
Consistent with the dominant r o l e of entrained c a t a l y t i c
elements w i t h i n the ESC coke, hydrogen additions to the oxidant
promoted g a s i f i c a t i o n by a c t i v a t i n g c a t a l y s t formation. This
outweighed the expected r e t a r d a t i o n by hydrogen of the carbon-water
vapour r e a c t i o n , as a r e s u l t of i t being a product of both the
primary o x i d a t i o n (C + H
gas s h i f t (CO + H 0 f i = * C 0
2
decomposition products) a l s o enhanced the ESC coke g a s i f i c a t i o n ,

again most probably by a c t i v a t i n g p o t e n t i a l c a t a l y s t s . The extent
of the i n f l u e n c e of butane would seem to exceed that of hydrogen
and be continuous, whereas in some circumstances that of hydrogen
was t r a n s i t o r y .
Carbonaceous d e p o s i t i o n during steam cracking i s the net
r e s u l t of steady state formation and removal processes. I f the
measured o x i d a t i o n rates in water vapour did represent the removal
of the deposit in s i t u , then t h i s would be an extremely rapid
process over the temperature range at which d e p o s i t i o n on r a d i a n t l y
heated process tubes i s most s i g n i f i c a n t . Thus, 1 mm thickness of
deposit would be oxidised by 362 mm Hg water p a r t i a l pressure in
300 h at 800C, 33 h at 900C and 5 h at 1000C. I f a hydrocarbon,
or i t s decomposition products, enhanced the o x i d a t i o n rate these
times could be decreased. Coke removal by thermal o x i d a t i o n cannot
be ignored, t h e r e f o r e , although i t s extent would depend on s p e c i f i c
plant operating c o n d i t i o n s .
Conclusions
(1) Oxidation of an ESC p y r o l y s i s tube coke in water vapour, at

721-1056C, followed l i n e a r k i n e t i c s between 10-85% burn o f f .
The rate increased l i n e a r l y with water vapour p a r t i a l pressure
(38-362 mm Hg). The a c t i v a t i o n energy f o r o x i d a t i o n was 57
1 9
K c a l mole"* and the pre-exponential f a c t o r was 3.6 10
2 1
mg cm~ min"" .
(2) G a s i f i c a t i o n was catalysed by inorganic i m p u r i t i e s ,
p a r t i c u l a r l y i r o n and n i c k e l , entrained in the coke and was
promoted by butane and hydrogen.
(3) Contamination of the coke surface with Pb, Fe, Co and N i
( i n the m e t a l l i c s t a t e ) , Na, K, L i , Rb and Cs carbonates or
oxides and Ba and Sr oxides enhanced g a s i f i c a t i o n at 900C,

4. BENNETT A N D PRICE Oxidation of a Pyrolysis Tube 87
by up to a f a c t o r of 135. This c a t a l y s i s probably derived

from oxygen t r a n s f e r mechanisms. A further eighteen elements
(B, Mg, A l , P, Ca, V, Cr, Mn, Cu, Zn, Zr, Mo, Ag, Cd, Sn, La,
Ce and B i ) e i t h e r in the oxidised or elemental state had no
s i g n i f i c a n t influence.
Acknowledgements
This programme was sponsored by the Chemicals and M i n e r a l s

Requirements Board, Department o f Trade and Industry.
We are g r a t e f u l to Dr. L.C. Dick, Dr. B. Estruch, and R.D.
Smith (ICI L t d . ) f o r supplying the plant coke and also f o r the
opportunity f o r d e t a i l e d d i s c u s s i o n s with them and t h e i r
c o l l e a g u e s . Likewise we also acknowledge h e l p f u l d i s c u s s i o n s with
Dr. J.J. M c C a r r o l l and colleague f th BP Research Centre W
wish to thank Dr. J.E.
course of the programme
L i t e r a t u r e Cited
1. Reide, B.E.; Hanesian, D. Ind. Eng. Chem. Process. Des.

Develop. 1975, 14, 10.
2. McKee, D.W., "Chemistry and Physics of Carbon"; Walker Jr.,
P.L.,; Thower, P.A. Eds; M. Dekker New York, 1981, 16, 1.
3. McKee, D.W. Carbon 1979, 17 419.
4. Otto, K.; Bartosiewicz, L.; Shelef. M. Carbon 1979, 17, 351.
5. Bennett, M.J.; P r i c e , J.B. J. Mater. S c i . 1981, 16, 170.
6. Bennett, M.J.; P r i c e , J.B. Unpublished r e s u l t s .
7. Ergun, S; Menster, M. "Chemistry and Physics of Carbon";
Walker Jr., P.L. Ed.; M. Dekker: New York, 1965, 1, 203.
8. Thomas, J.M. Carbon 1970, 8, 413.
9. Long, F.J.; Sykes, K.W. J. Chim. Phys. 1950, 47, 361.
10. Otto, K.; Shelef, M. Carbon 1977, 15, 317.
11. Otto, K.; Shelef, M. S i x t h I n t . Congress on C a t a l y s i s ,
London, 12-16 J u l y 1976, P r e p r i n t B.47.
12, Lahaye, J.; Badie, P. Carbon 1979, 17, 181.

5
Effect of Hydrogen on the Iron- and Nickel-
Catalyzed Formation of Carbon from Benzene
A L B E R T O I. LACAVA, E . D A N I E L F E R N A N D E Z - R A O N E , L E S L I E L.
I S A A C S , and M A R I T Z A C A R A B A L L O
The City College of the City University of New York, Clean Fuels Institute,
Department of Chemical Engineering, New York, NY 10031
The kinetics o f c a r b o n d e p o s i t i o n from

benzene o v e r nickel d iron foils
s t u d i e d a t temperature
500 t o 650C in atmospheres o f hydrogen
and m i x t u r e s o f hydrogen and n i t r o g e n ,
using a microbalance t u b u l a r flow reac-
tor. Carbon d e p o s i t i o n proceeds a t a
c o n s t a n t r a t e o v e r both m e t a l s . The
dependence o f t h e r a t e on t h e partial
p r e s s u r e o f hydrogen c a n be a p p r o x i -
mated by a power law kinetics. I t is
a p p a r e n t l y third o r d e r o v e r nickel and
first order over i r o n . This behavior
c a n be e x p l a i n e d by a mechanism in which
the benzene adsorbed on t h e s u r f a c e is
hydrogenated t o produce i n t e r m e d i a t e s .
These i n t e r m e d i a t e s in t u r n decompose
t o form c a r b o n atoms which d i s s o l v e and
diffuse i n t o t h e m e t a l t o produce c a r -
bon f i l a m e n t s . Scanning E l e c t r o n M i c r o -
scope (S.E.M.) s t u d i e s o f t h e d e p o s i t s
showed the p r e s e n c e o f t h e s e c a r b o n fila-
ments on b o t h m e t a l s u r f a c e s .
The phenomenon o f c a r b o n f o r m a t i o n on t h e s u r f a c e
o f a c a t a l y t i c m a t e r i a l i s a reason f o r c a t a l y s t deac-
tivation. A l s o , c o k i n g on s u r f a c e s o f p r o c e s s e q u i p -
ment exposed t o streams o f gases c o n t a i n i n g h y d r o c a r b o n s
has been s t u d i e d s i n c e c a r b o n d e p o s i t s c a n reduce h e a t
t r a n s f e r e f f i c i e n c i e s , i n c r e a s e p r e s s u r e d r o p s , and
even produce p l u g g i n g in narrow tubes o r v a l v e s .
0097-6156/82/0202-0089$06.00/0

90 COKE FORMATION
B a s i c s t u d i e s have c o n c e n t r a t e d on the mechanism

o f c a r b o n f o r m a t i o n and the k i n e t i c s o f the p r o c e s s .
Two approaches have been used which complement each
other. M i c r o b a l a n c e t e c h n i q u e s (1# 2>.3) u s i n g pure
m e t a l f o i l s have s e r v e d t o e s t a b l i s h the o v e r a l l k i -
n e t i c s o f the p r o c e s s and the e f f e c t o f the o p e r a t i o n -
a l v a r i a b l e s on the k i n e t i c s . E l e c t r o n microscopy
s t u d i e s , e s p e c i a l l y experiments p e r f o r m e d under c o n -
t r o l l e d - a t m o s p h e r e c o n d i t i o n , have a l l o w e d an i n s i g h t
i n t o the m i c r o s c o p i c mechanism f o r the growth o f c a r -
bon d e p o s i t s (.4* 5/60
F o r b a s i c k i n e t i c s t u d i e s pure m e t a l f o i l s have
been p r e f e r r e d (.2/(5,2*8.) t o s u p p o r t e d c a t a l y s t s s i n c e
w i t h the f o i l s , m e t a l - s u p p o r
t r a n s f e r l i m i t a t i o n s and p o r e b l o c k a g e problems a r e
practically eliminated.
Among the d i f f e r e n t types o f carbonaceous d e p o s -
i t s on m e t a l s u r f a c e s , c a r b o n f i l a m e n t s have been
r e p o r t e d by many a u t h o r s . These f i l a m e n t o u s growths
c a n be e x p l a i n e d by the f o l l o w i n g mechanism: gaseous
h y d r o c a r b o n m o l e c u l e s a r e a d s o r b e d on the m e t a l s u r -
f a c e where a f t e r a s e r i e s o f r e a c t i o n s c a r b o n atoms
are p r o d u c e d . These c a r b o n atoms in t u r n d i s s o l v e in-
t o the b u l k m e t a l . M e t a l c r y s t a l s a r e pushed out o f
the s u r f a c e by the growing a c c u m u l a t i o n o f atomic c a r -
bon and are c a r r i e d w i t h o r w i t h i n the f i l a m e n t . This
a l l o w s f o r the s u r f a c e r e a c t i o n t o p r o p a g a t e , a l t h o u g h
the amount o f c a r b o n p r o d u c e d in t h i s way would be
more t h a n enough t o c o v e r a l l the a v a i l a b l e a c t i v e
sites. T h i s i s the commonly a c c e p t e d mechanism f o r
the p r o d u c t i o n o f c a r b o n f i l a m e n t s . What has y e t t o
be c l a r i f i e d i s how and where the m i g r a t i n g c a r b o n
atoms a r e formed, and what f a c t o r s are a f f e c t i n g t h i s
formation.
The q u e s t i o n o f where the c a r b o n atoms are formed
has t o be answered s e p a r a t e l y f o r each p a r t i c u l a r h y -
d r o c a r b o n - m e t a l r e a c t i o n because t h e a d s o r p t i o n mech-
anism i s s p e c i f i c t o the i n d i v i d u a l m e t a l . Once the
c a r b o n atoms are p r o d u c e d they d i s s o l v e in the m e t a l
and m i g r a t e t o p r e f e r e n t i a l r e g i o n s . These r e g i o n s
are thought t o be the g r a i n b o u n d a r i e s where the c a r -
bon atoms a r e t r a p p e d and accumulated d i s p l a c i n g m e t a l
c r y s t a l l i t e s from the g r a i n s u r f a c e s ( 9 , 1 0 ) . S i m i l a r -
i t y o f the c r y s t a l l i t e s i z e s o f t h e o r i g i n a l m e t a l f o i l s

5. LACAVA E T A L . Catalyzed Formation of Carbon 91
and c r y s t a l l i t e s c o n t a i n e d in the c a r b o n f i l a m e n t s s u p -
p o r t t h e s e c o n c l u s i o n s (11) .
The q u e s t i o n o f how coke p r e c u r s o r s are formed
has been a m a t t e r o f c o n t r o v e r s y , and a g e n e r a l mech-
anism e x p l a i n i n g the f o r m a t i o n has not y e t been d e v e l -
oped. T h i s i s due t o the many d i f f e r e n t ways in which
h y d r o c a r b o n s adsorb and r e a c t on m e t a l s u r f a c e s under
similar conditions. I n s p i t e o f t h i s , some common
f e a t u r e s do e x i s t . Among them i s the f a c t t h a t the
p r e s e n c e o f hydrogen a f f e c t s the c a r b o n d e p o s i t i o n .
Few s t u d i e s o f c a r b o n f o r m a t i o n from a r o m a t i c h y -
d r o c a r b o n s a r e r e p o r t e d in the l i t e r a t u r e (2, 1 2 ) .
Most o f the s t u d i e s have been p e r f o r m e d w i t h a c e t y l e n e ,
o l e f i n s and p a r a f f i n
o f the r e a c t i o n on hydrogen p a r t i a l p r e s s u r e i s not
unique.
P r e v i o u s r e s u l t s from s t u d i e s on the d e p o s i t i o n
from benzene (12) and o t h e r h y d r o c a r b o n s (13) in the
absence o f h y d r o g e n i n d i c a t e t h a t the r e a c t i o n t e r m i n -
a t e s a f t e r a f i x e d amount o f c a r b o n has been i n c o r p o -
r a t e d i n t o the m e t a l f o i l . Not s u r p r i s i n g l y , the
amount o f c a r b o n uptake by n i c k e l f o i l s c o r r e s p o n d s t o
the s o l u b i l i t y o f c a r b o n in n i c k e l .
I n t h i s paper i t i s shown t h a t the growth o f c a r -
bon d e p o s i t s c a n be m a i n t a i n e d f o r l o n g p e r i o d s o f
time in the p r e s e n c e o f h y d r o g e n . The e f f e c t o f h y d r o -
gen on the k i n e t i c s o f c a r b o n f o r m a t i o n from benzene
in hydrogen has been s t u d i e d in experiments u s i n g
n i c k e l and i r o n f o i l s . The r e s u l t s are p r e s e n t e d b e -
low.
Experimental
The p r i n c i p l e s o f f l o w m i c r o b a l a n c e r e a c t o r s were
d e s c r i b e d in a p r e v i o u s paper (_3) . The p r e s e n t e x p e r i -
ments were p e r f o r m e d in the equipment shown in F i g u r e
1.
The r e a c t o r was a q u a r t z t u b e , 4.25 cm i . d . and
80 cm l o n g , h e l d a t the d e s i r e d temperature w i t h i n a
tubular furnace. The sample f o i l was suspended by a
q u a r t z f i b e r from one o f the arms o f an A i n s w o r t h m i -
c r o b a l a n c e and the w e i g h t o f the f o i l s , as f u n c t i o n s o f
t i m e , was m o n i t o r e d w i t h a r e c o r d e r .

COKE FORMATION
Nitrogen-Microbalanc flush

Gas mixer
Figure 1. Schematic of flow microbalance reactor.

The m e t a l s h e e t s were o b t a i n e d from U n i t e d M i n e r a l

and C h e m i c a l Company w i t h s t a t e d p u r i t y o f 99.9%. The
m e t a l f o i l s were c u t i n t o 1 x 4 inch rectangular pieces
and gases u s e d were o f the h i g h e s t a v a i l a b l e p u r i t y
(Matheson). The morphology o f the d e p o s i t s were s t u d -
i e d w i t h an X - r a y D i f f r a c t o m e t e r and a Cambridge SH
Scanning E l e c t r o n M i c r o s c o p e .
Results
F i g u r e 2 shows the e f f e c t o f temperature and b e n -

zene c o n c e n t r a t i o n on the k i n e t i c s o f c a r b o n d e p o s i -
t i o n on a n i c k e l f o i l . The temperature b e h a v i o r f o l -
lows a p a t t e r n t h a
the c a t a l y t i c c a r b o n f o r m a t i o n from n o n - a r o m a t i c h y -
d r o c a r b o n s (1#.2). There are t h r e e r e g i o n s in the A r r h e -
nius p l o t . A t low t e m p e r a t u r e s , the r a t e i n c r e a s e s
w i t h i n c r e a s i n g temperature and, t h u s , a n e g a t i v e
s l o p e - l i n e i s o b t a i n e d in the A r r h e n i u s p l o t . This
low temperature r e g i o n i s denoted as R e g i o n I .
A t i n t e r m e d i a t e t e m p e r a t u r e s , R e g i o n I I , the d a t a
i n d i c a t e s an apparent n e g a t i v e a c t i v a t i o n e n e r g y , o r a
d e c r e a s e in the r a t e w i t h i n c r e a s i n g t e m p e r a t u r e . At
h i g h t e m p e r a t u r e s , the n o n - c a t a l y t i c c a r b o n f o r m a t i o n
mechanism s t a r t s t o be o f s i g n i f i c a n c e and t h e r e i s
another r e g i o n , Region I I I , o f apparent p o s i t i v e a c t i -
v a t i o n energy. In F i g u r e 2, the d o t t e d l i n e s r e p r e -
sent Region I I I . T h i s r e g i o n was o b t a i n e d from d a t a
o f c a r b o n d e p o s i t i o n from b e n z e n e - h y d r o g e n m i x t u r e s
under c o n d i t i o n s o f homogeneous r e a c t i o n ( 14). The tem-
p e r a t u r e dependence o f the r a t e o f c a r b o n d e p o s i t i o n
i s s i m i l a r t o t h a t r e p o r t e d by Lobo (15) f o r the d e p o s i -
t i o n from p r o p y l e n e - h y d r o g e n and 1 - b u t e n e - h y d r o g e n m i x -
tures. In a l l c a s e s , as temperature i s i n c r e a s e d , the
o v e r a l l r a t e o f c a r b o n d e p o s i t i o n s h i f t s from b e i n g
c a t a l y t i c a l l y c o n t r o l l e d t o b e i n g c o n t r o l l e d by the
homogeneous r e a c t i o n in the gas p h a s e . R e g i o n I shows
a d e f i n i t e v a r i a t i o n o f the r e a c t i o n r a t e w i t h benzene
concentration. The change c o r r e s p o n d s t o a f i r s t o r -
der e f f e c t .
F i g u r e 3 shows t h e e f f e c t o f temperature and b e n -
zene c o n c e n t r a t i o n o f the r a t e s o f c a r b o n f o r m a t i o n
over i r o n f o i l s . The o v e r a l l b e h a v i o r i s s i m i l a r t o
t h a t o f n i c k e l f o i l s , a l t h o u g h the changes w i t h tern-

1100 1000 900 800 700 600C 500 1100 1000 900 800 700 600 C 500

0.7 0.8 0.9 1.0 1.1 1.3
0.9 1.0 1.1
1
IOVHK" ) 3 _1
1 0 / T (K )

Figure 2. Arrhenius plot for the rate of carbon deposi
Figure 3. Arrhenius plot for the rate of carbon deposi
tion from benzene onto nickel foils (total pressure
atm a n d
tion from benzene onto iron foils (total pressure
1 atm). Key to F^nzene- y 032 > > 0-091
1 atm). Key is the same as in Figure 2.
atm.
5. LACAVA E T AL. Catalyzed Formation of Carbon 95
p e r a t u r e a r e l e s s marked in t h i s c a s e . A l l the r e
s u l t s shown in F i g u r e s 2 and 3 were o b t a i n e d u s i n g
m i x t u r e s o f h y d r o g e n and benzene w i t h o u t u s i n g an in
ert d i l u e n t gas. Thus, i t i s d i f f i c u l t t o observe the
e f f e c t o f hydrogen on the c a r b o n f o r m a t i o n r a t e . An
o t h e r s e t o f experiments was performed a d d i n g a d i l u e n t
g a s , n i t r o g e n , t o the gas s t r e a m . The t o t a l p r e s s u r e
o f benzene was k e p t c o n s t a n t , but the r e l a t i v e amounts
o f hydrogen and n i t r o g e n in the gas stream were v a r i e d .
The r e s u l t s a r e shown in F i g u r e 4 . The e f f e c t o f h y
drogen on the r a t e o f c a r b o n f o r m a t i o n on the n i c k e l
f o i l s i s v e r y marked, r e s u l t i n g in a r a t e i n c r e a s e o f
two o r d e r s o f m a g n i t u d e . The e f f e c t i s l e s s pronounced
w i t h i r o n f o i l s ; th
with hydrogen a d d i t i o n
F i g u r e 5 shows the r a t e o f c a r b o n f o r m a t i o n as a
f u n c t i o n o f the gas f l o w r a t e in the r e a c t o r as mea
s u r e d by the v o l u m e t r i c r e s i d e n c e t i m e . The r a t e o f
the c a t a l y t i c c a r b o n f o r m a t i o n , as e x p e c t e d , i s n e a r l y
independent o f the gas r e s i d e n c e time in the e x p e r i m e n
t a l range o f t h i s i n v e s t i g a t i o n .
S c a n n i n g E l e c t r o n M i c r o s c o p e o b s e r v a t i o n s o f the
d e p o s i t s t r u c t u r e showed s i m i l a r i t i e s in the morpho
l o g y b o t h f o r n i c k e l and i r o n f o i l s . F i g u r e 6 shows
the s t r u c t u r e on a n i c k e l f o i l . Carbon has been formed
in a f i l a m e n t - l i k e s t r u c t u r e , s i m i l a r t o what has been
o b s e r v e d p r e v i o u s l y in d e p o s i t s from o t h e r h y d r o c a r
bons ( 4 , 5 ) . The same t y p e o f s t r u c t u r e i s o b s e r v e d on
the i r o n f o i l s (see F i g u r e 7 ) .
In F i g u r e 8, the X - r a y D i f f r a c t i o n p a t t e r n s o f a
c a r b o n d e p o s i t o v e r n i c k e l and the pure n i c k e l s u b
s t r a t e are compared. A b r o a d , low i n t e n s i t y peak c o r
r e s p o n d i n g t o the g r a p h i t e p l a n e (002) appears in the
r e g i o n o f 2 6 (2) i n d i c a t i n g the p r e s e n c e o f a few
s m a l l g r a p h i t e c r y s t a l l i t e s , b u t the b u l k o f the depo
s i t appears t o be amorphous c a r b o n . A l l the l i n e s c o r
r e s p o n d i n g t o n i c k e l appear in the c a r b o n d e p o s i t p a t
t e r n , i n d i c a t i n g the p r e s e n c e o f n i c k e l c r y s t a l l i t e s
in the d e p o s i t . However, the r e l a t i v e i n t e n s i t i e s o f
the l i n e s i s d i f f e r e n t from the p a t t e r n o b t a i n e d w i t h
the pure s u b s t r a t e . T h i s may i n d i c a t e the p r e f e r e n
t i a l d e p o s i t i o n o f c a r b o n on d i f f e r e n t n i c k e l c r y s t a l -
lographic planes.

96 COKE FORMATION
I I I
10-2 h

Q.
10",-31 I I I I I
5 10 15 20 25 30
Gas phase residence time in the reactor (sec)
Figure 5. Effect of the gas residence time on the rate of carbon deposition at
650C.

Figure 6. SEM photograph of carbon deposited on a nickel foil showing filament

growth. Magnification is 9,35.
Figure 7. SEM photograph of carbon deposited on an iron foil showing filamentary

growth. Magnification is 9,350.

COKE FORMATION
Ni + Graphite
(311)
(220)
Graphite
(002) (111) (222) (400)
I I _L , il
(220)
(311)
(200)
(222) (400)
20 40 60 80 100 120
20
Figure 8. X-Ray diffraction patterns of carbon deposited on a nickel foil. Key:

top, after deposition; and bottom, before deposition (clean foil).

5. LACAVA ET AL. Catalyzed Formation of Carbon 99
Discussion
Carbon f o r m a t i o n from d i f f e r e n t h y d r o c a r b o n s o v e r
m e t a l s has been s t u d i e d by s e v e r a l w o r k e r s . The p r e s -
ence o f c a r b o n f i l a m e n t s on the s u r f a c e o f t h e m e t a l ,
c o n t a i n i n g m e t a l c r y s t a l s , has been r e p o r t e d under c o n -
d i t i o n s s i m i l a r to those o f these experiments.
Scanning E l e c t r o n M i c r o s c o p e ( S . E . M . ) s t u d i e s o f
the i r o n and n i c k e l f o i l s , a f t e r c a r b o n d e p o s i t i o n ,
showed the p r e s e n c e o f f i l a m e n t o u s growth o f c a r b o n on
b o t h m e t a l l i c s u r f a c e s , as was e x p e c t e d . T h i s i s in
agreement w i t h the s t e a d y - s t a t e r a t e o f c a r b o n depo-
s i t i o n o b s e r v e d f o r b o t h i r o n and n i c k e l f o i l s . If
filaments containin
formed, t h e r e a c t i o n would have to s t o p a t a c e r t a i n
p o i n t because o f d e a c t i v a t i o n and p o i s o n i n g o f the
m e t a l s u r f a c e by the d e p o s i t e d c a r b o n .
X - r a y d i f f r a c t i o n s t u d i e s suggest t h a t c a r b o n i s
formed on a l l f a c e s o f a n i c k e l c r y s t a l , b u t p r e f e r e n -
t i a l l y on the (111) p l a n e s . R e l a t i v e i n t e n s i t y o f the
d i f f r a c t i o n p a t t e r n s a s s o c i a t e d w i t h each p l a n e on the
s u r f a c e was measured b e f o r e and a f t e r r e a c t i o n . Lower
i n t e n s i t y would have t o be expected as the amount o f
n i c k e l d i f f r a c t i n g had been reduced t o those c r y s t a l -
l i t e s p r e s e n t in t h e c a r b o n d e p o s i t from the o r i g i n a l
nickel f o i l . I n t h i s c a s e s i m i l a r r e d u c t i o n in the
i n t e n s i t y o f the d i f f r a c t e d peaks s h o u l d be e x p e c t e d
f o r a l l p l a n e s d i f f r a c t i n g the X - r a y s . I t c a n be seen
from F i g u r e 8 t h a t the r e d u c t i o n in the (111) dif-
f r a c t e d peak i s above the a v e r a g e . Similar preferen-
t i a l s e g r e g a t i o n o f c a r b o n on n i c k e l (111) planes
( a r i s i n g from i n t e r n a l m i g r a t i o n ) has been o b s e r v e d
by Auger s p e c t r o s c o p y . T h i s seems t o c o r r e l a t e w i t h
the way in which benzene adsorbs on d i f f e r e n t p l a n e s
o f n i c k e l c r y s t a l s (16). The (111) p l a n e s have the
most f a v o r a b l e s t r u c t u r e f o r benzene c h e m i s o r p t i o n
because o f the s i m i l a r i t i e s between d i m e n s i o n and
shape o f benzene m o l e c u l e s and (111) p l a n e ( F i g u r e 9 ) .
Models have been p r o p o s e d in the l i t e r a t u r e t o
e x p l a i n the growth o f c a r b o n f i l a m e n t s . The models
p o s t u l a t e t h a t the p a r e n t h y d r o c a r b o n adsorbs on the
s u r f a c e o f a c r y s t a l l i t e and undergoes d e h y d r o g e n a t i o n
r e a c t i o n s t o form atomic c a r b o n . F i l a m e n t s grow on
the back o f the c r y s t a l l i t e s by the a d d i t i o n o f the
c a r b o n t h a t d i f f u s e s , as was e x p l a i n e d b e f o r e .

100 COKE FORMATION
The e f f e c t o f hydrogen on the r a t e o f f i l a m e n t

growth, and t h e r e f o r e c a r b o n d e p o s i t i o n , i s s t i l l open
to d i s c u s s i o n . I f c a r b o n d e p o s i t s are formed through
a d e h y d r o g e n a t i o n r e a c t i o n , the e f f e c t o f i n c r e a s i n g
hydrogen p a r t i a l p r e s s u r e s h o u l d be t o d e c r e a s e the
rate of carbon formation. The o p p o s i t e e f f e c t was o b
s e r v e d f o r t h e s e experiments s i n c e the r a t e o f c a r b o n
d e p o s i t i o n i n c r e a s e d w i t h the t h i r d power o f the h y d r o
gen p a r t i a l p r e s s u r e f o r n i c k e l f o i l s and w i t h the
f i r s t power o f hydrogen p a r t i a l p r e s s u r e f o r the i r o n
f o i l s (Figure 10). T h i s seems t o s u g g e s t t h a t even
though a d e h y d r o g e n a t i o n r e a c t i o n has t o be p r e s e n t in
o r d e r t o produce atomic c a r b o n , t h i s i s not the r a t e -
c o n t r o l l i n g step.
The p r o p o s e d k i n e t i c models d e s c r i b e d below t r y t o
take i n t o account t h i s p a r t i c u l a r e f f e c t o f hydrogen on
the o v e r a l l d e p o s i t i o n r a t e .
Mechanism o f Carbon F o r m a t i o n on N i c k e l
I n the c a s e o f n i c k e l f o i l s , i t i s assumed t h a t
benzene adsorbs r e v e r s i b l y on the m e t a l , f o l l o w e d by
h y d r o g e n o l y s i s o f the r i n g which l e a d s t o coke i n t e r
mediates. The i n t e r m e d i a t e s w i l l t h e n decompose r a p
i d l y to c a r b o n atoms which w i l l undergo the aforemen
t i o n e d d i s s o l u t i o n and d i f f u s i o n p r o c e s s e s through the
crystal:

+ S:^=B.S (1)
2 K
B.S + 3 H i I . S (2)
I.S CARBON + S + 6 H 2 (g) (3)
The s o l u t i o n o f the e q u a t i o n s o f the above model

gives the f o l l o w i n g r a t e e x p r e s s i o n :
k C
3 1 2 ,
r
c =
Vl.S
1 1 2 KL

Figure 9. Scheme of benzene chemisorbed on nickel (111). Key: O, Ni atoms;

, C atoms; %, H atoms; d = 2.49A; and d! = 1.48.
0.1 1.0
Hydrogen p a r t i a l pressure (aim )
Figure 10. Apparent reaction order with respect to hydrogen for carbon deposition
rate at constant temperature, constant pressure (1 atm), constant benzene partial
pressure on nickel foils (T = 650C, P = 0.132 atm) and iron foils (T =
B 625C,
= 0.132 atm). Key: , Ni foils; and Q Fe foils.

102 COKE FORMATION
The parameters o f t h e above model were e s t i m a t e d

u s i n g a n o n - l i n e a r r e g r e s s i o n computer program. The
parameters o b t a i n e d a r e :
K
1 B P + K
1 2 B H
K P P < K 1
(
^ 1 :
9 1 3
)
k
3 l 2T
K K = 1 , 2 X 1 0 X E X P
(- 3 1
' 2 0
/ R T
)
, -2 -1 ^ -4,
(mg cm s e c atm )
From e q u a t i o n ( 3 ) , t h e t o t a l a c t i v a t i o n o f energy
of the process should be:
E T = E 3 + ^ + = 31,200 c a l / g 2 mole (4)
The v a l u e o f t h e a c t i v a t i o n energy c a n be j u s t i
f i e d i f t h e i n d i v i d u a l a c t i v a t i o n e n e r g i e s and h e a t s o f
r e a c t i o n c a n be e s t i m a t e d o r known. For the reaction
o f a d s o r p t i o n o f benzene, l i t e r a t u r e v a l u e s range from
- 3 0 K c a l / m o l e (at z e r o c o v e r a g e ) ^ t o - 6 K c a l / g m o l e (18) .
A v a l u e c l o s e t o - 6 K c a l / g m o l e may be e x p e c t e d under
the e x p e r i m e n t a l c o n d i t i o n s r e p o r t e d h e r e , where c o v e r
age i s n o t z e r o .
R e a c t i o n 2 i s assumed t o be as f o l l o w s :
and t h e i n t e r m e d i a t e " I i s assumed t o be t h r e e a d

11
sorbed ethylene groups. The h e a t o f r e a c t i o n c a n be

e s t i m a t e d from t h e r m o c h e m i c a l d a t a , and i s found t o be
in the o r d e r o f - 1 0 K c a l / g m o l e .
I n r e a c t i o n ( 3 ) , t h e adsorbed e t h y l e n e groups r a p
i d l y decompose t o atomic c a r b o n through a s e r i e s o f
h y d r o g e n o l y s i s and d e h y d r o g e n a t i o n r e a c t i o n s t o y i e l d
i n d i v i d u a l c a r b o n atoms on t h e s u r f a c e . T h i s atomic
carbon d i f f u s e s through the metal c r y s t a l l i t e probably
d r i v e n by a temperature g r a d i e n t and forms a c a r b o n
d e p o s i t on t h e o p p o s i t e f a c e o f t h e c r y s t a l (15) .
Work p u b l i s h e d by Lobo e t a l . (15) r e p o r t s t h a t t h e
s t e p s o f r e a c t i o n (3) (carbon f o r m a t i o n from e t h y l e n e )
a r e c o n t r o l l e d by t h e d i f f u s i o n o f c a r b o n through t h e
metal c r y s t a l l i t e . T h i s p r o c e s s i s known t o have an
a c t i v a t i o n energy o f 35 K c a l / g m o l e .

5. LACAVA E T AL. Catalyzed Formation of Carbon 103
W i t h the above a s s u m p t i o n s , the t o t a l a c t i v a t i o n

energy c a l c u l a t e d from e q u a t i o n (4) s h o u l d be about 19
Kcal/jmole. The d i s c r e p a n c y c a n be a t t r i b u t e d t o i n a c -
c u r a c i e s in the e s t i m a t i o n o f the h e a t o f r e a c t i o n (1)
and (2). T h i s o r d e r o f magnitude a n a l y s i s i n d i c a t e s
t h a t the model c a n r o u g h l y account f o r the t h i r d o r d e r
dependence on h y d r o g e n p r e s s u r e and f i r s t o r d e r depen-
dence on benzene p r e s s u r e .
The f i t t i n g o f the model w i t h the parameters t o
the e x p e r i m e n t a l r e s u l t s i s shown in F i g u r e 11.
Mechanism o f Carbon F o r m a t i o n on I r o n
In the c a s e o
m o l e c u l e i s assumed t o be a t t a c k e d by h y d r o g e n in s t e p s
o f comparable r a t e t o produce the coke i n t e r m e d i a t e s .
As in the c a s e o f n i c k e l , i n t e r m e d i a t e s decompose t o
atomic c a r b o n which d i f f u s e s through the m e t a l c r y s t a l :
B + S^ZZTB.S (5)
K
2
B.S + . S (6)
I.S CARBON + 4 H 2 + S (7)
The r a t e e x p r e s s i o n o b t a i n e d from the above model

is:
k C
3 1 2 2

=
k
3 I e S =
1 + . + . ( 8 )
1 1 2 2
and the parameters o b t a i n e d by n o n - l i n e a r r e g r e s s i o n

are:
k
3 l 2T
K K = 2 , 9 X X E X P
(- 2 3
' 4 0
/ r t
)
+ K K 2 ^
1 (negligible)
For t h i s case also:
E
T =
^6
E +
^4 +
5^ = 2 3 , 4 0 0 CSil
/9ôle

104 COKE FORMATION
No i n f o r m a t i o n was a v a i l a b l e on the h e a t s o f a d -
s o r p t i o n o f benzene on i r o n , and no thermochemical
d a t a were found t o e s t i m a t e t h i s v a l u e .
R e a c t i o n (6) c a n be assumed t o p r o c e e d as f o l l o w s :
s i n c e a s i n g l e h y d r o g e n o l y s i s s t e p would e x p l a i n the
f i r s t o r d e r dependence o f the r a t e on the p r e s s u r e o f
hydrogen.
R e a c t i o n (7) i s assumed t o be a s e r i e s o f h y d r o -
g e n o l y s i s and d e h y d r o g e n a t i o n r e a c t i o n s t h a t would
y i e l d atomic c a r b o n in the s u r f a c e . T h i s atomic c a r -
bon would t h e n d i f f u s
c a r b o n on the o p p o s i t e f a c e o f the c r y s t a l l i t e . The
a c t i v a t i o n energy o f d i f f u s i o n o f c a r b o n on i r o n i s o f
the o r d e r o f 13 K c a l / g m o l e , b u t in t h i s c a s e t h e r e i s
no e v i d e n c e w i t h r e g a r d s t o which i s the l i m i t i n g mech-
anism. Any o f the s u r f a c e r e a c t i o n s t e p s i n v o l v e d in
r e a c t i o n (7) c o u l d be c o n t r o l l i n g f o r the k i n e t i c s o f
t h i s r e a c t i o n , and would y i e l d a h i g h e r a c t i v a t i o n
energy t h a n d i f f u s i o n .
Assuming h e a t s o f a d s o r p t i o n in the o r d e r 0 t o -6
Kcal/gmole, a heat of r e a c t i o n of -3.8 Kcal/gmole f o r
r e a c t i o n (6) ( e s t i m a t e d from bond e n e r g i e s ) and a c t i v a -
t i o n e n e r g i e s f o r r e a c t i o n (6) from 13 K c a l / g m o l e ( d i f -
f u s i o n c o n t r o l l i n g ) t o 40 K c a l / g m o l e ( t y p i c a l a c t i v a -
t i o n energy f o r a s u r f a c e r e a c t i o n ) , would y i e l d an
e s t i m a t e d t o t a l a c t i v a t i o n energy between 9 and 30
Kcal/gmole. The v a l u e o f 23,400 c a l / g m o l e i s w e l l
w i t h i n these expected l i m i t s .
These e s t i m a t e s t e n d t o i n d i c a t e t h a t the model
p r o p o s e d would y i e l d r o u g h l y the r i g h t a c t i v a t i o n
energy. I t a l s o e x p l a i n s the f i r s t o r d e r dependency
o f the r a t e on b o t h the p a r t i a l p r e s s u r e o f benzene
and h y d r o g e n .
F i g u r e 12 compares the m o d e l - p r e d i c t e d r a t e s w i t h
the e x p e r i m e n t a l r e s u l t s . As in the c a s e o f n i c k e l ,
the s t a n d a r d d e v i a t i o n between model and experiments
i s o f the same o r d e r o f magnitude as the s t a n d a r d d e -
v i a t i o n o f the e x p e r i m e n t s .

5. LACAVA E T AL. Fe & Ni Catalyzed Formation of Carbon 105
4 1
id
10 3
10'
r ( m 2
coicuiot*d 9 cm- sec- )
Figure 12. Comparison of carbon formation rates for iron foils from proposed
model and from experiments.

106 COKE FORMATION
Conclusions
We p r o p o s e mechanisms f o r c a r b o n f o r m a t i o n in the
p r e s e n c e o f h y d r o g e n on n i c k e l and i r o n s u r f a c e s . Ben-
zene i s assumed t o adsorb on the m e t a l s u r f a c e and t o
be h y d r o g e n a t e d t o i n t e r m e d i a t e s . These i n t e r m e d i a t e s
decompose t o form atomic c a r b o n which m i g r a t e s through
a m e t a l c r y s t a l l i t e t o form c a r b o n f i l a m e n t s .
The d i f f e r e n c e s between the r a t e s o f c a r b o n depo-
s i t i o n on n i c k e l and i r o n f o i l s c a n be e x p l a i n e d by the
p r o p o s e d mechanisms. I n the c a s e o f n i c k e l f o i l s , the
adsorbed benzene i s h y d r o g e n a t e d t o i n t e r m e d i a t e s t h a t
look l i k e adsorbed ethylene groups. The r a t e d e t e r m i n -
i n g s t e p i s the d e c o m p o s i t i o
t o c a r b o n and h y d r o g e n
h y d r o g n a t i o n o f the adsorbed benzene r i n g l e a d s t o a
d i f f e r e n t i n t e r m e d i a t e ( r e a c t i o n (7)) in which the o v e r -
a l l r a t e i s a g a i n c o n t r o l l e d by the d e c o m p o s i t i o n o f
the i n t e r m e d i a t e t o c a r b o n and h y d r o g e n .
Nomenclature
: Benzene m o l e c u l e
: P a r t i a l pressure o f i t h component (atm)
: Concentration of i t h species
: E q u i l i b r i u m constant for ith reaction
k : K i n e t i c constant o f the l i m i t i n g step
S : Active site
B.S : Benzene adsorbed on a c t i v e site
I.S : Intermediate species f o r coke f o r m a t i o n
Total concentration of active site
r Rate o f c a r b o n f o r m a t i o n (mg cm sec )

C

5. LACAVA ET AL. Catalyzed Formation of Carbon 107
Literature Cited
1. Bernardo, C.A.; Ph.D. Thesis, University of Lon

don (1977).
2. Lobo, L.S.; P h . D . T h e s i s , U n i v e r s i t y o f London,
1971.
3. LaCava, A.I.; Trimm, D.L.; T u r n e r , C.E.; Thermo-
c h i m i c a A c t a 1978, 24, 273.
4. Baker, R.T.K.; Waite, R.J., J. o f C a t . 1975, 37,
101.
5. B a k e r , R . ; B a r b e r , M . ; Harris, P . ; F e a t e s , F . ;
W a i t e , R . , J. o f C a t . 1972, 26, 51.
6. N i s h i y a m a , J ; Tamai, Y., J. o f C a t . 1976, 45, 1.
7. Tamai, Y.; N i s h i y a m a
1969, 7, 209.
8. Tamai, Y.; N i s h i y a m a , J.; T a k a h a s h i , . , Carbon
1968, 6, 593.
9. Figueredo, J.; Ph.D. Thesis, U n i v e r s i t y of Lon
don, 1975.
10. Kishimoto, S.; Sotani, N . ; Niirui, K , ; Urata, T.,
. o f the Chem. S o c . o f J a p a n , 1978, 51, 1887.
11. N i s h i y a m a , J.; Tamai, J., J. o f C a t . 1974,
33, 98.
12. T o m i t a , A,; Y o s h i d a , K.; N i s h i y a m a , Y.; Tamai, .,
Carbon 1972, 10, 601.
13. Trimm, D., Catal. Rev. - Sci. E n g . 1977, 16 (2),
155.
14. LaCava, A.I.; Fernandez-Raone, E.D.; Caraballo,
., A.C.S. Symposium S e r i e s 1981, New Y o r k .
15. Lobo, L.S.; Trimm, D.L., J. o f C a t . 1973, 29, 15.
16. Bertolini, J.C.; D a l m a u - I m e l i k , G.; Rousseau, J.,
S u r f . S c . 1977, 67, 478.
17. Y u , Y.F.; C h e s s i c k , J.J.; Zettlemoyer, . , J.
P h y s . Chem. 1959, 63, 1626.
18. Marangozis, J.K.; M a n t z o u r a n i s , B . G , ; Sophos, A .
. , I n d . E n g . Chem. P r o d . Res. Dev. 1979, 18, 61.

6
Mechanism of Surface Carbon Formation
During the Pyrolysis of Benzene in the Presence
of Hydrogen
ALBERTO I. LACAVA, E . D A N I E L FERNANDEZ-RAONE, and
MARITZA CARABALLO
The City College of the City University of New York, The Clean Fuels Institute,
Department of Chemical Engineering, New York, NY 10031
The mechanis
polycrystalline Cu foils was s t u d i e d
f o r the pyrolysis o f benzene in t h e
p r e s e n c e o f hydrogen. The s t u d y was
carried o u t on a m i c r o b a l a n c e t u b u l a r
f l o w r e a c t o r a t temperatures r a n g i n g
form 800 t o 1050C. The r a t e o f s u r -
f a c e c a r b o n d e p o s i t i o n was c o n s t a n t
after an initial p e r i o d d u r i n g which
no a p p r e c i a b l e d e p o s i t i o n was o b s e r v e d .
The dependence o f the r a t e on t h e p a r -
tial p r e s s u r e o f hydrogen seems t o
f o l l o w a n e g a t i v e o r d e r , w h i l e it is
linear w i t h r e s p e c t t o benzene initial
partial pressure. The temperature
dependence o f the r a t e was found t o fol-
low an A r r h e n i u s b e h a v i o r w i t h activa-
tion energy c l o s e t o 50 k c a l / m o l e .
These effects can be e x p l a i n e d by means
o f a mechanism p r o p o s e d in t h i s paper
w h i c h p o s t u l a t e s t h a t benzene m o l e c u l e s
decompose t o form f r e e radicals; the
f r e e radicals in t u r n r e a c t among them-
s e l v e s t o p r o d u c t macromolecules o r r e -
a c t w i t h hydrogen t o become inactive.
The macromolecules, a f t e r s a t u r a t i o n i s
r e a c h e d , will condense i n t o d r o p l e t s .
The d r o p l e t s will grow by f u r t h e r a d d i -
tion o f macromolecules and collide with
the metallic s u r f a c e where t h e y d e p o s i t .
0097-6156/82/0202-0109$06.00/0

110 COKE FORMATION
During the gas-phase thermal decomposition of

h y d r o c a r b o n s , a carbonaceous m a t e r i a l appears d e p o -
s i t e d o n the s u r f a c e t h a t e n c l o s e s the r e a c t i n g e n v i -
ronment. T h i s d e p o s i t can g i v e r i s e t o o p e r a t i o n a l
d i f f i c u l t i e s in h y d r o c a r b o n p r o c e s s i n g equipment, such
as i n c r e a s e d p r e s s u r e d r o p s , p l u g g i n g o f p i p e s and
v a l v e s and d e c r e a s i n g h e a t t r a n s f e r e f f i c i e n c i e s .
The mechanism under w h i c h t h i s s u r f a c e c a r b o n i s
formed on n o n - c a t a l y t i c a l s u r f a c e s i s n o t v e r y w e l l
understood y e t . S e v e r a l t h e o r i e s have been p r o p o s e d
from t h e o b s e r v a t i o n o f c a r b o n f o r m a t i o n on s u r f a c e s
and in t h e gas phase under d i f f e r e n t c o n d i t i o n s (1)
From t h i s s t u d y i t can be c o n c l u d e d t h a t a u n i q u e
mechanism t h a t e x p l a i n s the f o r m a t i o n o f c a r b o n d e p o -
s i t s on c a t a l y t i c a l l
exist. The anpwer has t o be l o o k e d f o r each p a r t i c u -
l a r c a s e as d i f f e r e n t o p e r a t i n g c o n d i t i o n s ( p r e s s u r e ,
t e m p e r a t u r e , r e a c t a n t s ) produce d i f f e r e n t , i f any,
carbon d e p o s i t s .
One o f the p r o p o s e d t h e o r i e s a p p l i e d s u c c e s s f u l l y
t o t h e f o r m a t i o n o f g a s - p h a s e c a r b o n from benzene i s
the d r o p l e t c o n d e n s a t i o n mechanism. This "condensa-
t i o n t h e o r y " , r e v i s e d r e c e n t l y by Lahaye e t a l . (2),
e x p l a i n s the f o r m a t i o n o f s o o t a e r o s o l s d u r i n g benzene
pyrolysis. The a u t h o r s o b t a i n e d an e x c e l l e n t a g r e e -
ment between the t h e o r y and e x p e r i m e n t a l r e s u l t s .
The t h e o r y assumes the f o l l o w i n g s t e p s in t h e
formation o f carbon d e p o s i t s :
a) F o r m a t i o n o f "macromolecules" ( l a r g e p o l y c y c -
l i c a r o m a t i c compounds) from b e n z e n e , t h r o u g h a s e t o f
polymerization reactions.
b) The macromolecules c o n c e n t r a t i o n i n c r e a s e s
a l o n g t h e r e a c t o r , u n t i l i t r e a c h e s the s a t u r a t i o n
point.
c) When t h e s a t u r a t i o n p o i n t i s r e a c h e d ( a f t e r a
r e s i d e n c e time t ) n u c l e a t i o n and f o r m a t i o n o f d r o p l e t s
occur.

6. LACAVA E T AL. Mechanism of Surface Carbon Formation 111
d) A f t e r n u c l e a t i o n , f u r t h e r macromolecules
formed c o n t r i b u t e t o the growth o f t h e d r o p l e t s .
T h i s t h e o r y i s shown h e r e t o be r e l e v a n t t o t h e
work d e s c r i b e d as t h e c o n d i t i o n s u s e d in (2) a r e c l o s e
t o t h o s e o f t h e e x p e r i m e n t s r e p o r t e d in t h i s p a p e r .
The p r e s e n t r e s e a r c h i s an attempt t o e l u c i d a t e t h e
mechanism o f s u r f a c e c a r b o n d e p o s i t i o n from benzene in
hydrogen a t a t m o s p h e r i c p r e s s u r e and in t h e tempera-
t u r e range 800 to 1 0 5 0 C .
Experimental
Cu f o i l s were s e l e c t e
e x p e r i m e n t s s i n c e t h e y do n o t p r e s e n t s i g n i f i c a n t c a t a -
l y t i c a c t i v i t y (3). The r a t e o f s u r f a c e carbon f o r m a -
t i o n on p u r e Cu p o l y c r y s t a l l i n e f o i l s was measured w i t h
the a i d of a microbalance t u b u l a r flow r e a c t o r . The
p r i n c i p l e s o f t h i s equipment were d e s c r i b e d in a p r e -
v i o u s paper (4).
The r e a c t o r was a q u a r t z t u b e , 4.25 cm i . d . and 80
cm l o n g , h e l d a t the d e s i r e d temperature w i t h i n a t u b u -
l a r furnace. The sample f o i l was suspended by q u a r t z
f i b e r s from one o f the arms o f an A i n s w o r t h RV m i c r o -
b a l a n c e and t h e w e i g h t o f the f o i l s , as f u n c t i o n o f
t i m e , was m o n i t o r e d w i t h a r e c o r d e r .
The m e t a l s h e e t s were o b t a i n e d from U n i t e d M i n e r a l
and C h e m i c a l Company w i t h 99.9% p u r i t y . M e t a l samples
were c u t i n t o 1 x 4 i n c h r e a c t a n g u l a r p i e c e s and gases
used were o f t h e h i g h e s t a v a i l a b l e p u r i t y (Matheson).
The Cu s h e e t s , a f t e r b e i n g washed in a c e t o n e ,
where r e d u c e d " i n s i t u " w i t h hydrogen a t the r e a c t i o n
temperature o f each r u n . The r a t e o f c a r b o n f o r m a t i o n
was measured as a f u n c t i o n o f t e m p e r a t u r e , benzene and
hydrogen p a r t i a l p r e s s u r e s , and gas phase r e a c t o r r e s i -
dence t i m e .
The morphology and n a t u r e o f the d e p o s i t s were
s t u d i e d w i t h a Cambridge SH S c a n n i n g E l e c t r o n M i c r o -
scope .
Results
F i g u r e 1 shows the e f f e c t o f temperature on the

r a t e o f c a r b o n d e p o s i t i o n . The r a t e was found t o

112 COKE FORMATION
T E M P E R A T U R E (C)
1100 1000 9 0 0 8 0 0 7 0 0 600
0.9 1.0
10 /T3
(~ )
Figure 1. Temperature effect on the carbon formation rate on copper foils. Key
to Pbenzene' Q , 0.132 atm; and , 0.043 atm.

6. LACAVA ET AL. Mechanism of Surface Carbon Formation 113
follow an apparent Arrhenius behavior in the range

800-1050C, with an a c t i v a t i o n energy close to 50
kcal/mole.
Figure 2 shows the dependence of the rate of car-
bon deposition with i n i t i a l hydrogen p a r t i a l pressure.
The rate depends on the hydrogen p a r t i a l pressure with
a negative order, i . e . , the rate of deposition de-
creases with increased hydrogen pressure. The depen-
dence of the rate on the i n i t i a l benzene p a r t i a l pres-
sure i s f i r s t order as revealed by the data on Figure
1. For f i x e d temperatures, benzene and hydrogen par-
t i a l pressures, there i s a c r i t i c a l gas phase r e s i -
dence time (t*) below which no appreciable deposition
occurs. Above the c r i t i c a
t i o n occurs and i t
residence time. This i s depicted in Figure 3.
Scanning E l e c t r o n Microscopy observations showed
the deposit to be an aggregate of p a r t i c l e s (Figure 4)
that tend to coalesce in larger "drops" that attach
to the surface of the f o i l (Figure 5). X-ray d i f f r a c -
t i o n shows the deposit i s amorphous in nature.
Discussion
Scanning E l e c t r o n Microscope observations of the

morphology of the deposit suggest the following me-
chanism f o r the "drop" formation:
a) Macromolecules are formed in the gas phase

as a consequence of homogeneous reactions. The macro-
molecules so formed condense into droplets or par-
t i c l e s by means of a p h y s i c a l or chemical process.
b) These p a r t i c l e s , in a p l a s t i c state, d i f f u s e
and c o l l i d e with the m e t a l l i c surface, depositing on
it.
The "condensation theory" presented by Lahaye et a l .

can account f o r part of the experimental f a c t s . The
model presented below i s an extension of that theory.
It also includes assumptions on how hydrogen p a r t i a l
pressure and gas phase reactor residence time a f f e c t
the rate of deposition.

114 COKE FORMATION
xlO" 3
UM -
<
0 1 1 1
0 0.2 0.4 0.6 0.8
HYDROGEN PARTIAL P R E S S U R E (ATM)
Figure 2. Effect of hydrogen partial pressure on the rate of carbon deposition on

copper foils. Conditions: T, 950C; P o, 0.132 atm; and t, 22 s.
B
Figure 3. Effect of the gas residence time on the rate of carbon deposition at
1000C. Conditions: P , 0.132 atm; and P , 0.868 atm.
B0 H

LACAVA E T A L . Mechanism of Surface Carbon Formation
Figure 4. SEM photograph of carbon deposited on Cu foil. Magnification is

9,350.
Figure 5. SEM photograph of carbon deposited on Cu foil. Magnification is

1,870.

116 COKE FORMATION
Model f o r Carbon D e p o s i t i o n in Droplets State
Gas Phase Reactions
(1) Radical generation (benzene decomposition)

k
l
R^ (1)
A t the h i g h temperatures of the experiments benzene is

a s s u m e d t o d e c o m p o s e i n t o f r e e r a d i c a l s a n d one o r
more h y d r o g e n a t o m s .
(2) Radicals capping with hydrogen
R
l +
2
H k ? , u
* R H + H e ( 2 )
The f r e e r a d i c a l s c a n r e a c t w i t h h y d r o g e n t o become
inactive o r r e a c t among t h e m s e l v e s t o g i v e r e a c t i o n 3.
(3) Formation of polymolecules or intermediates
R
l ^ - I (3)

free radicals react to give a polymolecule (macro-
molecule) .
Benzene Concentration Along the Reactor
The b e n z e n e c o n c e n t r a t i o n c h a n g e s a l o n g t h e r e
a c t o r as r a d i c a l s and m a c r o m o l e c u l e s a r e f o r m e d . In
o r d e r t o c a l c u l a t e t h i s change, the f o l l o w i n g a n a l y s i s
was p e r f o r m e d . A s s u m e a f t e r Hou a n d P a l m e r (_5) t h a t
b e n z e n e d e c o m p o s e s in t h e g a s p h a s e a s a f i r s t o r d e r
reaction:
d C
B
- = -k C (4)
dt 1
with initial condition C = C at t = 0.
Bo
By integration of (4)
C

= c Bo e"*!* (5)

6. LACAVA E T A L . Mechanism of Surface Carbon Formation
The hydrogen p a r t i a l p r e s s u r e i s assumed t o remain c o n

s t a n t a l o n g the r e a c t o r because o f the h i g h hydrogen to
benzene r a t i o and the low hydrogen p r o d u c t i o n .
Concentration of Intermediate A l o n g the Reactor
The i n t e r m e d i a t e c o n c e n t r a t i o n can be o b t a i n e d by
a p p l y i n g the s t a t i o n a r y s t a t e h y p o t h e s i s o f f r e e r a d i
c a l s to r e a c t i o n s (1), (2) and (3).
dl = BQ (6)
dt 1 + (k2A3)P
H
with i n i t i a l conditio
above e q u a t i o n g i v e s :
(l/n) Bp P
_ - k l t
+ (k A )P 2 3 H
L 1 ]
From (7), the time needed to r e a c h saturation (t*) can

be e a s i l y o b t a i n e d :
(1/n)
I * r e p r e s e n t s the minimum c o n c e n t r a t i o n o f i n t e r m e
d i a t e s n e c e s s a r y to b e g i n c o n d e n s a t i o n . When I* i s
r e a c h e d , n u c l e a t i o n and f o r m a t i o n o f d r o p l e t s o c c u r .
Any o t h e r macromolecule formed a f t e r t * w i l l c o n t r i
b u t e to the d r o p l e t s growth.
1
The d r o p l e t s ' c o n c e n
t r a t i o n a f t e r n u c l e a t i o n w i l l then b e :
[c] = (I - I*) ^ (9)
or (1/n) , -kit*. -k-Lt (10)

wl Bo (e e 1
) x
[c] -
l + (k A ) P 2 3 H
F o r s m a l l v a l u e s o f k ^ t the e x p o n e n t i a l s can be
l i n e a r i z e d to g i v e :
78 y t - t * ) P B O
1 + P
^ ^ 3 H

118 COKE FORMATION
Also
1 + ( AJP "
0
1 ( k
2 3
A
) P
H
Now, c a l l i n g k / k ^ = b
[ c ] = 78 k 1 (t-t*)P B o [l-bP ] R (12)
I t i s assumed a t t h i s p o i n t t h a t d r o p l e t s d e p o s i t on
the m e t a l l i c s u r f a c e b y Brownian m o t i o n ( i . e . , d i f f u -
sion) . T h i s assumption a l l o w s f o r the e v a l u a t i o n o f
the r a t e o f d e p o s i t i o n as f o l l o w s :
R
CD k
C
R
C D " 78 (t-t*) U-bPg) (13)
Temperature Dependence o f b and t *
The temperature dependence o f t h e term b can be

p r e d i c t e d i f v a l u e s f o r the a c t i v a t i o n e n e r g i e s o f r e
a c t i o n s (2) and (3) (E^ and E^) a r e known.
Capping o f hydrogen w i t h s i m i l a r f r e e r a d i c a l s
has an a c t i v a t i o n energy o f 2-8 k c a l / g m o l (_6) . A n
a c t i v a t i o n energy as low as 2 k c a l / g m o l can be e x
pected f o r r e a c t i o n (2). R e a c t i o n (3) has an a c t i v a
t i o n energy c l o s e t o 0 b e i n g t h a t i t i s a t e r m i n a t i o n
reaction. T h e r e f o r e , t h e dependence o f b w i t h tem
p e r a t u r e can be n e g l e c t e d under t h e p r e s e n t c o n d i t i o n s ,
The temperature dependence o f t * can be o b t a i n e d
by t h e f o l l o w i n g a n a l y s i s :
The p a r t i a l p r e s s u r e o f i n t e r m e d i a t e p o l y m o l e -
c u l e s r e q u i r e d t o condense a t e q u i l b r i u m i s g i v e n b y :
i . " C" ^ ) ,14)
Assume t h e s u p e r s a t u r a t i o n p r e s s u r e d i f f e r e n c e t o be
s m a l l , then
/-AH
I * 1* P (- ) U5>

6. LACAVA ET AL. Mechanism of Surface Carbon Formation 119
From (8), (15) and l i n e a r i z i n g t h e e x p o n e n t i a l for

small values of k.,t*
1 0
^ ~ R T ' ( 1 / n ) P
Bo ( 1 _ b P
H ) ( 1 6 )
has a v a l u e o f a p p r o x i m a t e l y 52 K c a l / g m o l (_5) .
can be e s t i m a t e d t o be around 25 k c a l / g m o l .
This
value corresponds to a b o i l i n g p o i n t temperature o f
macromolecules o f 1 2 0 0 K - 1 3 0 0 K .
t * w i l l t h e n d e c r e a s e w i t h temperature f o l l o w i n g
an e x p o n e n t i a l decay where (E^-AHy) i s p r e d i c t e d t o
be ~27 k c a l / g m o l .
The r a t e o f c a r b o n d e p o s i t i o n i s t h e n :
R_ = 78 k k , ( t - t * ) . P . ( 1 - b P )
n n (17)
CD C 1 B O
where t * i s o b t a i n e d from (16).

E q u a t i o n (17) r e p r e s e n t s v e r y c l o s e l y the e x p e r i
m e n t a l b e h a v i o r o f c a r b o n d e p o s i t i o n on C\l p o l y c r y s t a l -
l i n e f o i l s from m i x t u r e s o f benzene and hydrogen s i n c e :
(i) the r a t e o f d e p o s i t i o n decreases l i n e a r l y

w i t h hydrogen p a r t i a l p r e s s u r e ( F i g u r e 2 ) ;
(ii) t h e r a t e grows l i n e a r l y w i t h r e s i d e n c e time

s t a r t i n g from an i n i t i a l v a l u e o f t * ( F i g
u r e 3) ;
(iii) t h e r a t e f o l l o w s an A r r h e n i u s e x p r e s s i o n
w i t h temperature. The e f f e c t o f t e m p e r a t u r e
on t * and b i s masked b y t h e much s t r o n g e r
temperature of k j ^ ;
(iv) the r a t e i s p r o p o r t i o n a l to the i n i t i a l con

c e n t r a t i o n o f benzene.
The v a l u e o f the parameters in (12) was o b t a i n e d by a

n o n l i n e a r r e g r e s s i o n method u s i n g t h e Gauss-Newton
Algorithm. Those v a l u e s a r e :
78 k k = 0.5 10 7
e" 5 3
^ (cal/gmol)
c 1 RT

120 COKE FORMATION
0.87
0.22 10
- t & = 24,000 cal/gmol
Conclusions
A model based on the condensation theory was

developed to explain the dependence of the rate of
carbon deposition o
pressure, on the ga
temperature. The e f f e c t of hydrogen was explained
assuming that i t reacts with the free r a d i c a l s that
form the macromolecules of the condensation theory,
decreasing the rate of production of carbon-forming
intermediates.
The e f f e c t of i n i t i a l benzene p a r t i a l pressure
was accounted f o r , assuming benzene undergoes a f i r s t
order decomposition reaction to free r a d i c a l s at any
place in the reactor.
The dependence on the residence time was obtained
from the assumptions involved in the condensation
theory and by further l i n e a r i z a t i o n of the r e s u l t i n g
equation f o r short residence times. The model presents
a good agreement with the experimental r e s u l t s .
Nomenclature
: Benzene molecule
[c] : Concentration of droplets (mg C / ^ V o u m e )
C
B ' Molar concentration of benzene
C
BO : I n i t i a l molar concentration of benzene
H 2 : Hydrogen molecule
I* : Macromolecule concentration at saturation
k : Mass transfer c o e f f i c i e n t
c
k
i : K i n e t i c constant of i t h reaction (sec "S

6. LACAVA E T A L . Mechanism of Surface Carbon Formation 121
M^j : Molecular weight of intermediate (assumed

to be molecular weight of benzene,
i . e . , 78n).
: Number of free r a d i c a l s in a macro-
molecule
: P a r t i a l pressure of benzene
P B 0 : I n i t i a l benzene p a r t i a l pressure
P H : Hydrogen p a r t i a l pressure
R-p : Free r a d i c a l
t* : Time neede
Literature Cited
1. Palmer, H.; C u l l i s , C.F., "Chemistry and Physics
of Carton," Dekker, New York, 1965; p. 266.
2. Lahaye, J.; Prado, G.; Donnet, J.., Carbon 1974,
12, 27.
3. Lobo, L.S., Ph.D. Thesis, London U n i v e r s i t y ,
London, 1971.
4. LaCava, A.I.; Trimm, D.L.; Turner, C.E., Thermo-
chimica Acta 1978, 24, 273-280.
5. Hou, K.C.; Palmer, H., J. Phys. Chem. 1965, 69,
863.
6. LaCava, A.I., M.Sc. Thesis, London U n i v e r s i t y ,
London, 1973.

7
Formation and Removal of Coke Deposited on
Stainless Steel and Vycor Surfaces from
Acetylene and Ethylene
JAMES C. MAREK and LYLE F. A L B R I G H T
Purdue University, School of Chemical Engineering, West Lafayette, I N 47907
Small but s i g n i f i c a n t amounts of coke are unfor-

tunately always formed when hydrocarbons are pyrolyzed
to produce ethylene and other valuable by-products and
when 1,2-dichloroethan
duce v i n y l chloride
tubes i s always accompanied by the following d e l e t e r i -
ous e f f e c t s including reduced y i e l d s of desired pro-
ducts, down-time f o r decoking, increased resistance to
heat transfer, and reduced tube creep rupture strength
from c a r b u r i z a t i o n and the accompanying metal segrega-
tion. These e f f e c t s all contribute to increased
operating expenses, and s i g n i f i c a n t advantages would
r e s u l t if coking could be reduced or eliminated.
Albrights, McConnell and Welther (1) obtained
valuable new information by comparing the morphologies
of coke formed on s t a i n l e s s steels from acetylene,
ethylene, butadiene, and propylene. Acetylene i s a
highly r e a c t i v e precursor for the production of coke,
and i t i s present whenever large amounts of ethylene
are present in p y r o l y s i s units. Using a scanning
electron microscope equipped with EDAX to analyze f o r
metals, they concluded that coke formed on Incoloy 800
surfaces often contained highly dispersed metal p a r t i -
cles of nickel/ chromium/ and e s p e c i a l l y iron. These
metal p a r t i c l e s had apparently been extracted from the
Incoloy 800 surfaces in a manner s i m i l a r to a mechan-
ism postulated by Baker and associates (2/3/4) and
Trimm and associates (5/ 6/7) who used surfaces of pure
iron/ nickel/ etc. This mechanism explains the simul-
taneous formation of metal-catalyzed filamentous coke
and corrosion/ perhaps along with erosion/ of the
metal surface. P a r t i c u l a r l y noteworthy i s the finding
reported by Albright et a l . (I.)/ and Graff and
Albright (8)/ that f o r aluminized (or Alonized)
Incoloy 800 surfaces filamentous coke mas not observed
and iron/ nickel/ and chromium mere not detected in
the coke.
0097-6156/82/0202-0123$08.00/0

124 COKE FORMATION
Coke i s produced by both homogeneous gas-phase

reactions and heterogeneous metal-catalyzed reactions.
Similar mechanisms for coke production which incor
porate both homogeneous and heterogeneous coke forma
tion have been proposed by Lahaye et a l . (9), and
Graff and Albright (8). These mechanisms* while use
f u l , r a i s e more questions than they answer. Addi
tional information has been obtained in t h i s i n v e s t i
gation to c l a r i f y the interactions between coke pro
duced v i a homogeneous and heterogeneous reactions.
Information concerning coke formation on surfaces pre
viously subjected to one coking/decoking cycle i s also
presented. Other variables investigated include the
effect of temperature* p a r t i a l pressure of coke pre
cursor* and geometrical r e l a t i o n s h i p between the s o l i d
surface and the ga
aluminized Incoloy
EXPERIMENTAL DETAILS
The apparatus and operating procedures were s i m i

lar to those used by Albright* McConnell* and Welther
<i>. Metal a l l o y coupons (received from Alon Process
ing* Inc.* Tarentum* PA) were approximately 1.9 0.5
0. 2 cm. * the coupons were f i r s t rinsed with acetone*
then dried* and next weighed to +0.0001 g. using a
Mettler model H10 balance. These coupons were then
inserted into 2. 5 cm. lengths of 0. 64 cm. I. D. Vycor
glass tubing. The tubing containing the samples were
next placed inside a Vycor glass reactor tube (2. 2 cm.
I. D. and 85 cm. long) that was positioned h o r i z o n t a l l y
in an e l e c t r i c a l furnace which could be c o n t r o l l e d at
any desired temperature in the 500 to 900 C range.
For most experiments* Incoloy 800 and aluminized
Incoloy 800 coupons were postioned side by side at
identical process conditions near the furnace mid
point* several runs were also performed with coupons
upstream or downstream of the furnace midpoint. Ace
tylene* ethylene* helium* and oxygen flows were
metered as desired to the i n l e t of the Vycor reactor.
For decoking* some helium or helium-oxygen mixtures
were saturated with steam at any desired temperature
between 25 and 100C by bubbling the gases through a
heated flask containing water. Residence times of the
gases in the constant temperature section of the Vycor
reactor were from 7 to 16 seconds.
The coupons* a f t e r removal from the Vycor reac
tor* were cooled in an inert atmosphere and then
weighed. Coupon surfaces were analyzed using a Jeolco
JSM-U3 scanning electron microscope and photographs

7. MAREK A N D ALBRIGHT Formation and Removal of Coke Deposits 125
were taken at magnifications varying from 60 to

20#000. The metal content of the coupon surfaces or
bulk coke was determined using an EDAX model 9100
energy dispersive analyzer that c o l l e c t s data up to a
sample depth of approximately one micron.
RESULTS
Preliminaru Analyses of Metal Surfaces: As shown in

Figure lAz the untreated Incoloy 800 surfaces were
unpolished and exhibited numerous heterogeneities.
Iron-rich areas or p a r t i c l e s were scattered randomly
over about 5% of the surface. EDAX indicatd that the
approximate surface composition (in weight percent) of
51% iron/ 18% chromium/ and 31% nickel differed
s l i g h t l y from the bul
23% chromium, and 30
gen treatment at 900C resulted in some chromium-rich
spikes which protruded from a roughened Incoloy 800
surface (Figure 1C). After heating in helium for 3
hours, the surface analyzed 30% iron/ 55% chromium/
14% nickel* and 1% titanium/ indicating a s i g n i f i c a n t
enrichment in chromium and titanium. Graff and
Albright (8) had e a r l i e r reported similar findings.
Untreated aluminized (or Alonized) Incoloy 800
surfaces, as shown in Figure IB/ were smooth and exhi-
bited d i s t i n c t grain boundaries which appeared as a
network of i r r e g u l a r chicken wire. About 80-90% of
the aluminized surface was highly enriched in alumi-
num/ except for some heterogeneous areas which were
pitted and contained much less aluminum. Aluminum
chunks were observed both in these pitted areas and
scattered over the remainder of the surface. The
average surface composition was 45% aluminum, 28%
iron, 9% chromium, and 18% nickel. EDAX analyses for
cross sections of aluminized coupons indicated alumi-
num was diffused approximately 150-300 microns into
the Incoloy 800 base metal, r e l a t i v e aluminum weight
concentrations were s t i l l generally greater than 5% to
these depths. L i t t l e or no roughening or composition
change was observed f o r aluminized Incoloy 800 sur-
faces after heating at 900C. As shown in Figure ID,
however, the grain boundaries exhibited a smeared
appearance in comparison to those on an untreated
coupon.
Coking Results: Temperature, precursor type, precursor

partial pressure, and run duration a l l s i g n i f i c a n t l y
affected the amount of coke for Incoloy 800 and
aluminized Incoloy 800 coupons and Vycor glass. The

COKE FORMATION
Figure 1. Untreated and helium treated alloy coupons.

quantitative r e s u l t s obtained in eleven runs of t h i s

i n v e s t i g a t i o n confirm the e a r l i e r more q u a l i t a t i v e
findings of other i n v e s t i g a t o r s (4*8). The combined
rates of coke production and of c o l l e c t i o n on the sur
face are reported in the remainder of t h i s paper as
the rate of coke formation. This rate increased with
increasing temperature and p a r t i a l pressure (Table 1).
For i d e n t i c a l operating conditions* the amount of coke
formed from 0.05 atm. acetylene was in a l l cases
greater than or equal to the amount deposited from . 1
atm. ethylene (Table 1). Since the rate of coke forma
tion increases as confirmed in t h i s i n v e s t i g a t i o n with
increased p a r t i a l pressure of the hydrocarbon* more
coke i s formed from acetylene than from ethylene based
on s i m i l a r hydrocarbon concentrations. The net amount
of coke deposited
progressed* but th
with time for both Incoloy 800 and aluminized Incoloy
800 surfaces as w i l l be discussed later.
Several types of coke were noted during the
course of the present investigation. Filamentous
cokes (including needles* ribbons* c o i l e d filaments*
braided diameter filaments* and straight* constant
diameter filaments) were most predominant (but not
e x c l u s i v e l y present) on Incoloy 800 surfaces f o r runs
at low temperatures <500 to 700 C>, at low partial
pressures (0.05 and . 1 atm. )* and short durations (<
1 hour). For example* coke structures formed on
Incoloy 800 surfaces from 0.1 atm. ethylene ranged
from n e e d l e - l i k e filamentous deposits at 500C <Figure
2A>, and filaments at 700C <Figure 2C>, to aggregated
chunks of globular coke which also contained braided
diameter and c o i l e d filaments, ribbons, and c y l i n d r i
c a l coke at 800C <Figure 3B>, and stubby, c y l i n d r i c a l
coke imbedded in and protruding from a matrix of g l o
bular coke <Figures 4A,4C> at 900C. Raising the
ethylene p a r t i a l pressure to 0.5 atm. and increasing
the run time from 0.33 to 1.0 hours at 900 C r e s u l t e d
in a massive s p h e r i c a l - g l o b u l a r coke deposit <Figure
4E and Table 1>. S i m i l a r l y , at 700C a f a c t o r of ten
increase in the ethylene p a r t i a l pressure from 0. 1 to
1. atm. concomittant with a 25% increase in run
length led to a coke surface covered with globular
deposits (Figure 5A).
The orders of the rate of coke formation at 700
and 900 C were estimated from the measured buildup of
coke on the metal coupons r e l a t i v e to the inlet
ethylene p a r t i a l pressure by the folowing equation:
rate = k C O

TABLE I. Coking of Fresh Coupons
Hydrocarbon Time of Average Rate of Coking Furnace Tube

in Feed*, Run, 2 4 Posi tion-Remarks
Atm. T,C g coke/cm hr 10
Hours
INCOLOY 800 ALUMINIZED

ETHYLENE
0.1 500 16 0.12 0.02 Midstream
0.1 700 10 0.28 0.03 Midstream
1.0 700 2.34 0.14 Upstream
1.0 700 5.76 0.08 Downstream
0.1 800 3.14(G) 0.21(H) Midstream
0.1 800 3.61(E) 0.56(F) Midstream-repeatedly
withdrawn from tube
(see Figure 9)
0.1 900 0.33 3.40(C) 1.90(D) Midstream
0.5 900 1 48.9 (A) 39.7 (B) Midstream
ACETYLENE
0.05 500 0.14 0.04 Upstream
0.05 700 16 1.04 0.09 Midstream
0.05 800 8 3.30 Upstream, top of p a i r
0.05 800 8 2.53 Upstream, bottom of pair
0.05 800 8 3.73(1) 1.79(K) Midstream, s i n g l e s

0.05 800 8 4.03(J) Midstream, top of p a i r
0.05 800 8 3.20 Midstream,bottom of p a i r
0.05 800 8 3.79 Downstream,top of p a i r
0.05 800 8 3.07 Downstream, bot torn of p a i r

Helium comprises remainder of feedstream ( t o t a l pressure 1 atm.]
L e t t e r s a l l o w coupon's h i s t o r y to be t r a c e d .
MAREK AND ALBRIGHT Formation and Removal of Coke Deposits
Figure 2. 10% C H2 h at 500C and 700C.

COKE FORMATION
Figure 3. Coked and decoked Incoloy 800 surfaces.

7. MAREK AND ALBRIGHT Formation and Removal of Coke Deposits 131
Figure 4. 10% and 50% C H at 900C.

2 h Key: A and C, Incoloy 800, 10%
C H , 0.33 h; and D, alonized Incoloy 800, 10% C H , 0.33 h; E, Incoloy 800,
2 h 2 h
50% C H , 1 h; and F, alonized Incoloy 800, 50% C H , 1 h.

2 h 2 h

132 COKE FORMATION
Figure 5. 100% C H at 700C for 8 h. Key: A, Incoloy 800, panoramic view;

2 k
B, alonized Incoloy 800, panoramic view; C, round columns on Incoloy 800

surfaces; D, other columns on Incoloy 800 surfaces; E, face of round column; and
F, area of Incoloy 800 surface near base of round column.

where
k = constant of proportionality
C = i n l e t ethylene p a r t i a l pressure
= order of rate of coke formation
At 900C the order was s l i g h t l y less than 2 f o r

both aluminized and Incoloy 800 samples. At ?00C
the order estimated for Incoloy 800 coupons was
approximately 1.0, while aluminized samples exhibited
orders closer to 0. 5.
Comparison of Surfaces: The character of the surface

(i.e. material of construction) had major e f f e c t s on
both the amount and structure of the coke deposit/ as
indicated in Figures 2 through 8. Comparisons of the
coke deposited on aluminize
and Vycor glass surface
cess conditions support three findings. First, the
average rate of coking calculated from the weight gain
of the samples indicated that s i g n i f i c a n t l y more coke
(often by a factor of f i v e or greater) always formed
on the Incoloy 800 coupons. Coking data obtained f o r
samples subjected to 800C with a 0.1 atm. ethylene
feed and repeatedly withdrawn from the furnace tube
for weighing showed that differences in coking rates
for Incoloy 800 and aluminized Incoloy 800 samples on
a r e l a t i v e basis <i.e. r a t e . . /rate.. . . .>
y
were greatest at short run l e n g i R S The amoufiCs of
coke^, deposited on these coupons <reported as grams
cm. ^ 10 > are depicted in Figure 9 as a function of
time. The rate of coke formation for the Incoloy 800
coupon, determined as the slope of the top curve,
decreased with time up to at least 8 hours. The small
weight changes of the aluminized Incoloy 800 coupon
especially during the early stages of the run were
close to the observed precision of the balance, which
complicates the interpretation.
Less coke was formed or deposited on Vycor glass
in t h i s same run than on either type of metal coupon.
A s i l v e r or gray m i r r o r - l i k e coke generally covered
18-38 cm. of the Vycor furnace tube and the entire
lengths of the 2.5 cm. Vycor sample tubes containing
the metal coupons. Visual observations indicated that
more coke was present on the Incoloy 800 and alumin
ized Incoloy 800 coupons a f t e r 0.5 hours. A perhaps
more important finding i s that no coke whatsoever was
observed and no weight increase was detected a f t e r 0.5
hours when an empty Vycor sample tube was inserted in
the furnace tube. Based on weight measurements of the
empty sample tube a f t e r 8 hours operation, the rate of

134 COKE FORMATION
Figure 6. Coked and recoked alonized surfaces.

Figure 7. 5% C H2 2 at 500C and 700C.

136 COKE FORMATION
Figure 8. Coked and decoked Incoloy 800 and alonized Incoloy 800 surfaces.
Key: A and B, 5% C H 2 800C, 8 h; C and D, 10% O -50% H O 700C, 1 h;
2} 2 2 f
and and F, 5% C H , 800C, 8 h.

2 2

7. M A R E K AND ALBRIGHT Formation and Removal of Coke Deposits 137
30
T I M E , HR
Figure 9. Coke deposition vs. time (10% C H at 800C).

2 lt Key: O, Incoloy 800;
and , alonized Incoloy 800.

138 COKE FORMATION
formation on the Vycor glass surface was estimated to

be only 20/C of that on the aluminized Incoloy 800
coupon.
A second finding i s that the morphology of the
coke deposited on aluminized Incoloy 800 and Incoloy
800 surfaces often uias quite d i f f e r e n t . As depicted
in Figures 2B, 2D, 2F, 4D* 4F, 5B, 6B, and 8B, the
predominant structure of the coke observed on alumin-
ized surfaces tended to be either a f i l m of tar or a
globular coke deposit. Filamentous coke was found on
numerous Incoloy 800 samples (Figures 2A, 2C, 2E, 3B,
5C-5F, 7A, and 7C) whereas filamentous coke was
detected at most in only small amounts on the alumin-
ized surfaces of only three runs (Figures 2F# 7B, and
7D). Third/ EDAX analyses indicated appreciable
metal, generally mainl
formed on (or brushe
analyses of coke deposited on aluminized Incoloy 800
coupons in the same runs indicated trace amounts of
aluminum but no detectable iron, nickel, or chromium.
Surface heterogeneities described e a r l i e r often
were important r e l a t i v e to coke formed or deposited on
aluminized Incoloy 800 surfaces. Figures 5B, 6B# and
10B show globular and c y l i n d r i c a l coke which resulted
p r e f e r e n t i a l l y in the pitted areas of aluminized sur-
faces in several runs. Filamentous coke formed at
700 C on an aluminized Incoloy 800 coupon subjected to
a 0.05 atm. acetylene feed i s depicted in Figure 7D,
every filament observed was in or near a pitted area
but i n t e r e s t i n g l y not every pitted area contained
filaments.
Heterogeneities and edge phenomena s i g n i f i c a n t l y
a f f e c t e d the amount and type of coke formed at 700 C
on an Incoloy 800 coupon contacted with 1. 0 atm.
ethylene. Most of the surface exhibited c l u s t e r s of
large, aggregated globular coke (Figure 5A). Between
clusters, coiled filaments and smaller spherical-
globular deposits were observed at higher magnifica-
tions. One notable exception, however, occurred near
an edge of the coupon where the columns of coke dep-
icted in Figures 5C and 5D were formed. Based on
v i s u a l observations, t h i s region of the coupon was not
as heavily coked as the remainder of the coupon sur-
face. Filament coke was detected on the column faces
(Figure 5F). EDAX a n a l y s i s of columns indicated they
were formed in areas that were probably r i c h e r in iron
and titanium than the surrounding metal surface.
Geometrical E f f e c t s : For coke deposition on metal sam-

ples, the o r i e n t a t i o n of the coupon face r e l a t i v e to

Figure 10. Top-bottom geometrical effects. Key: A and B, 50% C^H^, 900C,
1 h; and C and D, 5% C H , 800C, 8 h.
2 2

140 COKE FORMATION
the gas flowing over i t had a s i g n i f i c a n t effect on

both the amount and structure of coke formed f o r runs
at 800C and 900C. Comparison of Figure 10A vs 4E
and Figure 10B vs 4F reveal major differences which
occurred in the morphology of coke deposited on the
top and bottom surfaces of both the Incoloy 800 and
aluminized coupons. A dense layer of s p h e r i c a l -
globular coke covered the top surfaces of both coupons
(4E and 4F>. The bottom surface of the Incoloy 800
coupon# on the other hand* exhibited numerous short
cylindrical or "spaghetti" coke* intermixed with
larger amorphous deposits (Figure 10A). The bottom
surface of the aluminized Incoloy 800 coupon exhibited
a thin layer of amorphous and globular coke deposits.
The grain boundaries of the aluminized surface were
c l e a r l y v i s i b l e throug
coke was present o
Numerous "weed patches consisting of c l u s t e r s of
c y l i n d r i c a l coke (Figure 10B) were scattered randomly
over the aluminized surface.
End e f f e c t s were l i k e l y important for Incoloy 800
coupons. Relatively coke-free surface metal* enriched
in both chromium and titanium* was v i s i b l e at the
upstream and/or downstream ends of several Incoloy 800
coupons subjected to 0.05 atm. acetylene at 800 C.
Numerous small craters* or holes* were observed on the
metal. A few isolated filaments protruded from the
surface* and sparse amounts of globular coke were also
detected at the ends. The bulk of the coke deposit*
which consisted of filaments intermixed with larger
amounts of globular coke (Figure 8A>* occurred near
the midsection of the coupon. A matrix of smooth and
rather s o l i d carbon was v i s i b l e at the metal to coke
t r a n s i t i o n region* the smooth matrix lay under the
globular coke.
To further c l a r i f y the r o l e of geometrical
effects* the following experiment was performed.
Three layered pairs of Incoloy 800 coupons* each pair
consisting of one coupon atop a second* were placed in
three separate 2. 5 cm. lengths of Vycor tubing. One
pair was positioned near the furnace midpoint* and the
other two pairs were positioned 5 cm. upstream and 3
cm. downstream of the midpoint, r e s p e c t i v e l y . Coke
was deposited from 0.05 atm. acetylene at 800 C. Upon
completion of the 8 hour run* a l l three coupon pairs
had to be pried apart to separate them. More coke
remained on the top coupons than on the bottom coupons
(Table 1) for each pair. The top surfaces of a l l
three top coupons exhibited s i m i l a r types of coke*
each was covered with a dense layer of s p h e r i c a l -

globular coke intermixed with r e l a t i v e l y few filaments

and amorphous chunks (Figure IOC). The bottom sur-
faces of a l l six coupons exhibited regions containing
thin needle-like filaments constant diameter f i l a -
ments* and only small amounts of globular coke. The
globular coke appeared to be entrapped by the f i l a -
ments. The top surfaces of the bottom coupons exhi-
bited both of these deposit c h a r a c t e r i s t i c s ; regions
that had not been covered by the coupon had deposits
similar to those on the top surfaces of the top
coupons. Other regions (Figure 10D) that had been
covered by the top coupons indicated coke coverage
similar to that of the bottom surfaces of the coupons.
In the region of the Vycor reactor tube where
m i r r o r - l i k e coke formed* more coke was observed on the
bottom of the tube
and 800 C employin
coke at the bottom of the tube was a l i g h t gray
powder. In addition* more coke was frequently
observed on the top exterior regions and the bottom
i n t e r i o r regions of the Vycor tubing used to hold the
coupons. For example* after a 1 hour run a dark*
powdery coke was detected on the top exterior of the
Vycor tubing* which elsewhere was lightly smoked in
appearance.
Results were also obtained at various a x i a l fur-
nace positions. Considerable more coke formed at 800 C
from 0.05 atm. acetylene on layered and paired Incoloy
800 coupons at the midstream and downstream positions
than at the upstream position. In a run employing
ethylene* Incoloy 800 and aluminized coupons were
positioned side by side in separate Vycor tubes both 4
cm. upstream and 4 cm. downstream of the furnace mid-
point. For the Incoloy 800 coupons* about twice as
much coke was formed at the dowstream position (see
Table 1). But* the reverse was true for the alumin-
ized coupons.
Removal of Coke Deposits: Decoking rates for Incoloy

800 coupons* as shown in Table II were approximately
1.3-4.0 times those of aluminized Incoloy 800 coupons
subjected to i d e n t i c a l conditions in both the i n i t i a l
coking and subsequent decoking runs. Caution must be
exercised* however* in comparing the decoking rates of
the two types of coupons since considerable less coke
was present on the aluminized samples and since the
decoking rates decreased s i g n i f i c a n t l y with increasing
extent of burn-off.
The rate of decoking was significantly greater
when oxygen was present in the oxidizing gas as

TABLE II. Decoking of Coupons a t 700C
Run Average
Coupon Type Feed* Duration, Decoking Rate % burn-off
%0 2 2
%H 0 Hours ^g coke removed\ at run end
2
REMOVAL OF COKE DEPOSITED FROM ETHYLENE AT 900C cm hr 10*
Incoloy 800, A 0 70 24 0,.77 38

Aluminized , 0 70 24 0,.59 36
A trace 100 105 2,.88 100
trace 100 105 2,.19 90
trace 100 3 0 .61 97

Incoloy, C 100 0 0.42 >5 .4 100
Aluminized, D 100 0 0.42 >3. .1 100
REMOVAL OF COKE DEPOSITED FROM ETHYLENE AT 800C

Incoloy, 10 50 1.75 14 .1 100
Aluminized, F 10 50 1 4 .81 100
Incoloy, G 0 50 2.25 1 .08 11
Aluminized, H 0 50 2.25 0 .3 <33
Incoloy, G 0 50 21.75 0 .22 33
REMOVAL OF COKE DEPOSITED FROM ACETYLENE AT 800C
Incoloy 800, I 10 50 1 29 .0 100

Incoloy 800, 10 50 0.60 53 .4 100
Aluminized, 10 50 1 14 .0 100

*Helium comprises remainder of feedstream ( t o t a l pressure 1 atm.)
L e t t e r s a l l o w coupon's h i s t o r y t o be t r a c e d .
i l l u s t r a t e d by decoking r e s u l t s f o r two Incoloy 800

coupons i n i t i a l l y coked at 800C with 0.1 atm.
ethylene. Decoking with a 50% He-50% steam mixture
for 24 hours removed only 30-40% of the coke deposit*
but a 10% 0-40% He-50% steam mixture r e s u l t e d in a
complete burn-off in 1.75 hours. The e f f e c t s of a
coking/decoking sequence on the morphology of the
resulting surfaces were s i g n i f i c a n t l y d i f f e r e n t for
Incoloy 800 and aluminized Incoloy 800 coupons. As
shown in both Figures 3C and 8C* the decoked Incoloy
800 surfaces were much rougher than the untreated
Incoloy 800 coupons shown in Figures 1A and 3A.
Iron-rich spikes and iron-enriched areas (formed
presumably v i a s p a l l i n g ) were frequently detected on
decoked Incoloy 800 surfaces. While the o v e r a l l sur-
face compositions wer
these iron-rich spike
segregation of the metals on Incoloy 800 surfaces. An
especially dramatic example of surface a l t e r a t i o n was
noted for an Incoloy 800 coupon decoked with a 10%
0^-40% He-50% steam mixture. Three d i s t i n c t regions
were v i s i b l e as seen by the naked eye - the upstream
exhibited an orange rust powder* the middle was dark
gray* and the downstream end was silver-gray in
appearance. EDAX a n a l y s i s of the top surface indi-
cated that both ends* and especially the upstream end*
were covered with flakes of iron oxide (see Figure
3C)* the middle region was* however* chromium r i c h and
contained some spikes r i c h e r in iron than the sur-
rounding metal surface. These a l t e r a t i o n s in surface
properties resulted in s i g n i f i c a n t changes in the cok-
ing phenomena upon recoking* as w i l l be discussed in
d e t a i l later.
A coking/decoking sequence for aluminized Incoloy
800 coupons had l i t t l e e f f e c t on the character of the
surface (Figures IB and 6A vs. Figures 6C and 8D).
The aluminized coupons* a f t e r decoking* typically
appeared to the naked eye as either a shiny s i l v e r or
blue tinted color. Alternating l i g h t and dark spots
were often detected on the aluminized Incoloy 800 sur-
faces under the SEM* in some cases these spots were so
numerous they gave the aluminized surface a leopard-
skin appearance (see Figure 6C). No differences in
metal composition could be detected between the light
and dark spots based on EDAX analyses. These spots
are thought to be the r e s u l t of varying degrees of
oxidation or perhaps d i f f e r e n t a l l o y spinels on the
aluminized surface.

144 COKE FORMATION
Coke Formation on Used Surfaces and After

Cok ino/Decok ino Sequences : Coke deposition at ?00C
from 0. 1 atm. ethylene was investigated using Incoloy
800 and aluminized Incoloy 800 coupons which were
first treated with oxygen at 700 C f o r 8 hours. As a
r e s u l t of the pretreatment/ apparently activated areas
of Incoloy 800 surface formed* patches of coke larger
in size and present in greater amounts than the coke
on the surrounding surface were detected on t h i s
Incoloy 800 coupon. These areas were scattered ran-
domly over the Incoloy 800 surface. As depicted in
Figure 2E* the filament and c y l i n d r i c a l coke in these
patches were more p l e n t i f u l and larger than the coke
r e s u l t i n g on an Incoloy 800 surface subjected to the
same coking condition
(Figure 2C>. Only a
filament coke were present on the aluminized Incoloy
800 surface as a r e s u i t of the oxygen p r i o r to coke
deposition (Figure 2F>* the predominant coke deposited
on the aluminized coupon was globular coke.
Incoloy 800 and aluminized Incoloy 800 coupons
were i n i t i a l l y coked at 800C with 0.1 atm. ethylene,
next decoked at 700C using a 10% 0^-40% He-50% steam
mixture, and were then recoked at fhe same conditions
as used for the i n i t i a l coking. The amounts of coke
formed in the recoking run were approximately 3.8 and
1. 5 times the amounts formed in the i n i t i a l coking run
on the Incoloy 800 and aluminized Incoloy 800 coupons*
respectively. For the Incoloy 800 coupon* more coke
was detected at the upstream and downstream ends of
the coupon* which were i r o n - r i c h after decoking as
explained earlier. The coke present at the ends con-
sisted of i r r e g u l a r l y shaped clumps of globular coke
which contained both constant diameter and coiled
filaments (Figure 3D). Iron was present in the fila-
ments. The middle area of t h i s coupon exhibited much
less coke* filament and globular coke as well as the
chromium-rich surface metal were a l l detected. For
the aluminized Incoloy 800 coupon* globular coke depo-
s i t s were predominant as indicated in Figure 6D.
Small amounts of filament coke were also intermixed
with the globular coke deposit. The amount of coke
formed on the surface was r e l a t i v e l y small* and the
discolored regions reported earlier could s t i l l be
seen to some extent.

In a second recoking run at 800C, used Incoloy

800 and aluminized Incoloy 800 surfaces were p o s i -
tioned side by side near the furnace midpoint and sub-
jected to 0.05 atm. acetylene. Two a d d i t i o n a l coupons
were included! a second used Incoloy 800 coupon was
placed beside a new Incoloy 800 coupon at a position
that was 5 cm. upstream of the furnace midpoint.
About 27% more coke formed on t h i s second used coupon
than on the new coupon beside i t * as indicated in
Table III. Analogously* the amount of coke deposited
on the aluminized Incoloy 800 coupon in the recoking
was 67% greater than the amount deposited in the i n i -
t i a l coking run. However* the amount of coke formed
on the used Incoloy 800 coupon near the midpoint was
17% less than the amount formed in th i n i t i a l cokin
run.
Several s i g n i f i c a n t differences were found for
coke structures formed on new and used coupons in the
runs employing acetylene. Profuse filament growth was
observed on both used Incoloy 800 coupons a f t e r recok-
ing* and as shown in Figure 8E* relatively smaller
amounts of globular coke were detected trapped in the
filaments. The coke deposited on the fresh Incoloy
800 coupon was s i m i l a r to that shown in Figure 8A.
Coke-free metal was observed on perhaps 20-30% of the
aluminized Incoloy 800 coupon a f t e r recoking. E l s e -
where on the aluminized surface* patches of globular
coke were predominant although some filament coke was
intermixed with the globular deposits (Figure 8F>.
The filament coke was not observed on the aluminized
surface a f t e r the i n i t i a l coking run (Figure 8B).
Observations near the edges of several recoked
Incoloy 800 coupons indicated that the structure of
the coke deposit varied considerably with depth as the
coke:metal interface was approached. The innermost
layer* i.e.* the layer in contact with the coupon sur-
face* was observed to be a matrix of smooth and rather
s o l i d carbon. The outermost layer* however* consisted
of the profuse filament growth which was described
earlier from two-dimensional observations. This
filamentous growth occurred in the region between the
carbon matrix and the reacting gas phase.
DISCUSSION
Considerable more information has been obtained

r e l a t i v e to coke formation and c o l l e c t i o n on s t a i n l e s s

TABLE III. Coking of Coupons w i t h Various Past H i s t o r i e s
>
, Time of Average Rate of Coking
Hydrocarbon
2 1 Remarks
in Feed*, Run, g coke/cm hr 10 *
Atm. T,C Hours
INCOLOY 800 ALUMINIZED
ETHYLENE
0.1 700 10 0.28 0.3 Fresh coupons
0.1 700 10 0.21 0.01 Coupons f i r s t
oxidized with 0 ?
8 hours
0.1 800 8 3.61(E) 0.56(F) Initial coking

0.1 800 8 13.8(E) 0.82(F) Recoki ng
ACETYLENE
0.05 800 8 3.73(1) 1.79(K) I n i t i a l coking,midstrean
4.03(J) Midstream, top of p a i r
0.05 800 8 3.09(1) 2.99(K) Recoking, midstream
4.61(J) Recoking, upstream

3.63 Fresh coupon, upstream

*Helium comprises remainder of feedstream ( t o t a l pressure 1 atm).
L e t t e r s a l l o w coupon's h i s t o r y to be t r a c e d .
steel surfaces and r e l a t i v e to decoking. Clearly some

coke i s formed c a t a l y t i c a l l y on the surfaces with the
subsequent corrosion of the surface as metal p a r t i c l e s
are extracted into the coke. Second* some coke or
coke precursors such as tar droplets are formed in the
gas phase and part of t h i s coke or precursors then
c o l l e c t at the surface whereas the remainder exhausts
with the main body of product gases. The c o l l e c t i o n
of the coke or precursors formed in the gas phase
obviously depends on several factors* but i t seems
obvious that filamentous coke and roughened surfaces
promote c o l l e c t i o n of the gas-phase coke on the sur-
face. The filamentous coke formed by c a t a l y t i c sur-
face reactions acts as a f i l t e r i n g medium for the tar
droplets for example
Surface corrosio
s t a i n l e s s s t e e l s during coking-decoking sequences
There i s f i r s t r e l a t i v e rapid d i f f u s i o n of at least
chromium and titanium to the surface. Second* cata-
l y t i c coke formation acts to remove iron and n i c k e l
from the surface* which w i l l be lost and l i k e l y
exhausted from the reactor c o i l during burnoff or when
portions of the filamentous coke are fragmented
because of a variety of reasons including the rapid
flow rates such as experienced in commerical p y r o l y s i s
coils. Third* carburization of the surface metals
leads to a breakup of the i n t e g r i t y of the surface.
Fourth* the surface oxidation or s u l f i d a t i o n of the
surface metals occurs frequently in most p y r o l y s i s
c o i l s because of the presence of steam* oxygen* hydro-
gen sulfide* or other sulfur-containing gases. The
metal oxides and s u l f i d e s are eventually destroyed*
the net r e s u l t is* however* i n i t i a l roughening of the
surface but with time there w i l l be a gradual s p a l l i n g
and loss of metal from the surface. Rougher surfaces
probably in general r e s u l t in increased formation of
surface- catalyzed cokes (such as filamentous coke)
and in more e f f e c t i v e c o l l e c t i o n of gas-phase cokes or
coke precursors on the surface.
The present r e s u l t s support the general conclu-
sion by Baker and Chludzinski (10) that c e r t a i n sur-
faces can minimize coke formation on the surface. In
the present case* aluminized s t a i n l e s s s t e e l s as
prepared by Alon Processing* Inc. retained their sur-
face characteristics over at least two coking
sequences. It i s known in addition that a tube
prepared by Alon Processing was used successfully in
an ethylene c o i l f o r at least a year and that appreci-
able aluminum was s t i l l present on the surface at the
American Chemical
Society Library
1155 16th St. N. W.
Washington,
ACS Symposium Series; D. C.Society:
American Chemical 20030Washington, DC, 1983.
148 COKE FORMATION
end of that time. Baker and Chludzinski (10) /how-

ever, reported that aluminum oxide fragmented and
rapidly spalled o f f t h e i r aluminum-coated stainless
steel, they did not report though t h e i r method of
treating the metal surface to get a coating.
Clearly geometrical factors r e l a t i v e to coke c o l -
lection on metal surfaces have an important e f f e c t on
coke formation. There i s obviously a need to obtain
more information r e l a t i v e to the flow patterns at or
near the surface and surface roughness (and
composition). Indirectly these factors would cer-
t a i n l y a f f e c t the w e t t a b i l i t y of the surface with coke
or coke precursors.
ACKNOWLEDGEMENT
Acknowledgment i s made to the donors of the

Petroleum Research Fund, administered by the American
Chemical Society, for p a r t i a l support of the research.
Alon Processing, Inc. of Tarentum, PA also provided
support.
LITERATURE CITED
1. A l b r i g h t , L.F.; McConnell, C.F.; Welther, K.,

"Thermal Hydrocarbon Chemistry"; Advances in
Chemistry Series No. 183, Chapter 10, A.G. Oblad,
H.G. Davis, and T.E. Eddinger, Ed., American
Chemical Society: Washington, D.C., 1979.
2. Baker, R.T.K.; Barber, M.A.; Harris, P.S.;
Feates, F.S.; Waite, R.J., J. C a t a l y s i s (1972),
26, 51-62.
3. Baker, R.T.K.; Harris, P.S., "Chemistry and Phy-
s i c s of Carbon", Vol. 14, Chapter 2, P.L. Walker
and P.A. Thrower, Ed., Marcel Dekker, Inc.: New
York, 1978.
4. Baker, R.T.K.; Harris, P.S.; Thomas, R.B.; Waite,
R.J., J. C a t a l y s i s (1973), 30, 86-95.
5. Lobo, L.S.; Trimm, D.L., J. C a t a l y s i s (1973), 29,
15-19.
6. Lobo, L.S.; Trimm, D.L.; Figueiredo, J.L., Proc.
5th Int. Cong. Cat. (1973), 1125-1137.

7. Trimm, D.L., Catal. Rev. - S c i . Eng. (1977),

16(2), 155-189
8. Graff, M.J.; Albright, L.F., Carbon (1982), in
press.
9. Lahaye, J.; Badie, P.; Ducret, J., Carbon (1977),
15, 87-93.
10. Baker, R.T.K.; Chludzinski, J.J., J. Catalysis
(1980), 64, 464-478.

8
Surface Phenomena During Pyrolysis:
The Effects of Treatments with Various
Inorganic Gases
JAMES C. MAREK and LYLE F . A L B R I G H T
Purdue University, School of Chemical Engineering, West Lafayette, IN 47907
Build-ups of cok
furnace and in the
shut-down of the unit for decoking purposes generally
every one to six months. Many factors a f f e c t the rates
of coke formation and c o l l e c t i o n on the surfaces of
the c o i l s and the transfer l i n e exchangers, including
the composition and roughness of the metal surfaces.
For example, significantly less coke r e s u l t s on
aluminized surfaces (1,2) and on s i l i c a - r i c h or
silicon-rich surfaces (3). Furthermore, more coke i s
normally formed on s t a i n l e s s s t e e l surfaces that have
been coked and decoked once as compared to new sur-
faces (2).
Metal oxides on the inner surfaces of s t a i n l e s s
steel c o i l s are known to a f f e c t the formation of coke
in p y r o l y s i s units. Such oxides are formed by reac-
tions with steam used as diluent in hydrocarbon
feedstocks and with steam-air mixtures used for decok-
ing the c o i l s . The amount of oxygen or steam that
reacts to produce metal oxides increases by a factor
of perhaps 4-5 during the first few oxidation-
-reduction sequences (4). When a reactor with an o x i -
dized surface i s contacted at p y r o l y s i s temperatures
with hydrogen s u l f i d e , the surface i s s u l f i d e d and
both water and sulfur dioxide are emitted as gaseous
products (4). Nickel s u l f i d e s are known to be l i q u i d s
at p y r o l y s i s temperatures, and may be separated from
the inner surfaces. Clearly oxidation, reduction, and
s u l f i d i n g of the surface roughens i t s i g n i f i c a n t l y .
Castle and Durbin (5) used x-ray photoelectron
spectroscopy (XPS) to investigate the surface composi-
t i o n o f 9% nickel and 12% chromium s t a i n l e s s s t e e l s
that were subjected t o o x i d i z i n g atmospheres at 500 C.
FeÔ. was predominant in the surface layer and a C r 0 ^ o
0097-6156/ 82/0202-0151 $06.00/0


152 COKE FORMATION
layer was present just beneath the base of the mag

netite film. B i t t n e r et al.<6>. investigated steam
oxidation of simulated Incoloy 800 surfaces at 600 C.
They found that the i n i t i a l iron oxide layer present
on the surface s p a l l s o f f leaving a f i l m r i c h in
chromium oxides that i s quite stable. Rather limited
information i s however a v a i l a b l e r e l a t i v e to coke f o r
mation on oxidized or vwduceu s t a i n l e s s steels. For
instance, a l l o y composition appears to be of consider
able importance in determining the amount ang s t r u c
ture of coke deposits formed at 500 or 700 C from
acetone-C0 mixtures <5,7>.
2
The objective of the present i n v e s t i g a t i o n was t o

investigate systematically the e f f e c t s of treating or
contacting Incoloy 800 d aluminized Incolo 800
s t e e l s with variou
how these treatments subsequently a f f e c t coking. In
addition, comparisons were made between the o r i g i n a l ,
unpolished metal surfaces and ones that were mechani
c a l l y polished and smoothed.
Experimental D e t a i l s
The apparatus was s i m i l a r to the one used by

Albright, McConnell, and Welther (8). The metal a l l o y
coupons (supplied by Alon Processing, Inc. , Tarentum,
PA) were approximately 1.9 0.5 0.2 cm. Some
coupons were conventional Incoloy 800 and others were
aluminized by t h e i r proprietary process. These l a t t e r
coupons are often referred to as alonized coupons.
Select coupons were polished using 200 through 600
g r i t s i l i c o n carbide, 5 diamond, and f i n a l l y 0.05
< alumina p o l i s h i n g wheels. Residue from the p o l i s h
ing operations was removed by immersing the coupons in
an u l t r a s o n i c cleaner. In every case, polished
coupons prepared in t h i s manner exhibited m i r r o r - l i k e
surfaces. Both polished and unpolished coupons were
rinsed in carbon t e t r a c h l o r i d e , dried, and weighed to
+0. 0001 g with a Mettler model H10 balance; they were
then inserted into separate 2.5 cm. lengths of 0.64
cm. I. D. Vycor glass tubing.
The tubing containing the coupon samples were
placed inside a Vycor glass tube (2.2 cm. I. D. and 85
cm.long> that was positioned h o r i z o n t a l l y in an
e l e c t r i c a l furnace c o n t r o l l e d at e i t h e r 700 or 900C.
For inorganic gas treatments, Incoloy 800 and polished
Incoloy 800 coupons were positioned side by side 4. 5
cm. upstream of the reactor midpoint; polished and
unpolished aluminized Incoloy 800 coupons were l i k e
wise positioned side by side except 2.0 cm. upstream

8. MAREK AND ALBRIGHT Surface Phenomena During Pyrolysis 153
of the midpoint. Helium, oxygen, and hydrogen s u l f i d e

flows were metered as desired to the i n l e t of the
Vycor glass tube. Steam treatments were performed by
saturating helium with steam; the gas was bubbled
through a flask of water heated to 87C to produce a
60% steam-40% helium mixture. For coking experiments,
Incoloy 800 and polished Incoloy 800 coupons were
positioned 3.8 cm. upstream of the reactor midpoint
while polished and unpolished aluminized Incoloy 800
coupons were positioned at the reactor midpoint. A 5%
mixture of acetylene in helium was then metered to the
i n l e t of the Vycor tube.
The coupons, a f t e r removal from the Vycor reac-
tor, were f i r s t cooled in an i n e r t atmosphere and then
weighed. Coupon surfaces were analyzed using a Jeolco
JSM-U3 scanning electro
300 A > and micrograph magnification
ranging in general from 1,000 to 10,000. The metal
content of the coupon surfaces was determined quanti-
tatively using an EDAX model 9100 energy dispersive
analyzer and EDAX supplied computer software.
Experimental Results
Surface Morphology q MeJfeaJL Cqupons: Surface
morphology changed significantly especially for Q
Incgloy 800 coupons a f t e r contacting them at 700 or

900 C with e i t h e r hlium. 60% steam in helium, oxygen,
or hydrogen s u l f i d e for four hours. In many cases
various portions of a coupon were changed to d i f f e r e n t
extents; the r e s u l t s are therefore an average of the
changes in surface morphology. Figures 1 through 4
show p i c t u r e s taken with the scanning e l e c t r o n micro-
scope before and a f t e r the four treatments at 700 C of
the Incoloy 800, polished Incoloy 800, aluminized (or
alonized) Incoloy 800, and polished aluminized Incoloy
800 coupons, respectively.
The r e l a t i v e e f f e c t of these treatments on mor-
phology was in the following order:
HS2 > 0 2 > H 0-He > He

2
Helium i s probably e s s e n t i a l l y inert although the

helium used did contain trace amounts of oxygen.
Changes in the morphology during helium treatments are
believed to be caused by the high temperatures. Fig-
ure IB shows an Incoloy 800 surface a f t e r helium
treatment at 700C; i t i s s l i g h t l y rougher than the
untreated Incoloy 800 surface shown in Figure 1A.
Helium treatment of polished Incoloy 800 resulted in
grains of metal outlined by a network of channels, as

COKE FORMATION
Figure 1. Gaseous treatments of Incoloy 800 at 700C for 4 h.

shown in Figure 2B. Roughness increased r e l a t i v e to

untreated polished Incoloy 800 (Figure 2A) but the
surface was c l e a r l y smoother than untreated or helium
treated unpolished Incoloy 800 surfaces.
Treatments of Incoloy 800 coupons with steam or
oxygen were at conditions which r e s u l t in the forma-
tion of metal oxides on the surface (4,6). As a
result, the surfaces were much rougher, as shown in
Figure 1; some areas had a fused p a r t i c l e appearance
(Figure ID) while other areas exhibited spikes. Less
pronounced v i s u a l changes occurred in a l l cases for
the polished Incoloy 800 coupons. As shown in Figures
2C and 2D, the surfaces were s t i l l generally smooth
except perhaps where scratches had not been completely
smoothed before treatment.
Treatments of
800 coupons with helium
general resulted in only rather small changes in
appearance, as shown in both Figures 3 and 4 for the
unpolished and the polished coupons, respectively.
The findings with the polished aluminized coupons must
however be considered less r e l i a b l e . The objective
had been to remove only the outer layer that in places
was almost pure aluminum and polish until the depth
was reached at which aluminum had alloyed with the
Incoloy 800. For some coupons, too much or perhaps
too l i t t l e metal was removed, such as for the rough
portion of the steam-treated coupon shown in Figure
4C.
Hydrogen s u l f i d e treatment had significant
e f f e c t s on the morphology of a l l coupons tested at
700 C . Exposure of Incoloy 800 to hydrogen s u l f i d e
resulted in a layer of s u l f i d e scale covered with den-
d r i t e s (or filaments) of metal s u l f i d e s , as shown in
Figure IE. The outer s u l f i d e scale flaked o f f the
base metal of the polished Incoloy 800 sample, r e s u l t -
ing in the rough surface depicted in Figure 2E. S u l -
fide dendrites were formed in small amounts on alumin-
ized Incoloy 800 and polished aluminized Incoloy 800
surfaces, as shown in Figures 3E and 4E. In general,
the morphology of the various coupons changed in the
following r e l a t i v e order with the various treatments:
Incoloy 800 > polished Incoloy 800 > aluminized
Incoloy 800 > polished aluminized Incoloy 800
Oxidizing treatments of Incoloy 800 and polished
Incoloy 800 coupons at 900C r e s u l t e d in larger
changes in surface morphology, as shown in Figure 5.
The surfaces were s u b s t a n t i a l l y rougher in Bppe<^r&nce
than a f t e r exposures t o steam or oxygen at 700 C; a
fused p a r t i c l e appearance was again observed. In some

COKE FORMATION
Figure 2. Gaseous treatments of polished Incoloy 800 at 700C for 4 h.

Figure 3. Gaseous treatments of alonized Incoloy 800 at 700C for 4 h.

158 COKE FORMATION
Figure 4. Gaseous treatments of polished alonized Incoloy 800 at 700C for 4 h.

MAREK AND ALBRIGHT Surface Phenomena During Pyrolysis
Figure 5. Gaseous treatments of Incoloy 800 surfaces at 900C for 4

160 COKE FORMATION
cases, structures resembling octahedrons or

tetrahedrons were observed at high magnifications.
Aluminized Incoloy 800 and polished aluminized
Incoloy 800 coupons were generally less affected than
Incoloy 800 coupons by treatments with oxygen or steam
Q
at 900 C, as shown in Figure 6. Rough, cracked, or

even spalled areas were formed to a small extent at
t h i s temperature on the aluminized Incoloy 800 and
polished aluminized Incoloy 800 surfaces. However,
major portions of the surfaces were r e l a t i v e l y
unchanged.
Surface Compositions of Metal Coupons: Surface

compositions of the Incoloy 800 and aluminized Incoloy
800 coupons a f t e r exposure to the inorganic gases f o r
four hours at 700
I and II. Analyses
coupons are included for comparison. Polishing of
both the Incoloy 800 and aluminized Incoloy 800
coupons resulted in major differences in the surface
composition. The a n a l y s i s reported in Table I for the
polished Incoloy 800 surface i s in excellent agreement
with the nominal composition (20.6% Cr, 46% Fe, and
31.97. Ni) reported for Incoloy 800 (9). Incoloy 800
coupons as received had more iron on the surface; par-
t i c l e s that were e s s e n t i a l l y almost pure iron were
noted on a l l unpolished coupons tested. Aluminized
Incoloy 800 coupons as received had regions of almost
pure aluminum (or alumina) on the surface. The pol-
ished aluminized coupons indicated almost 40% alumi-
num; on an aluminum-free basis the chromium content
was slightly lower compared to that for polished
Incoloy 800.
The compositions of Incoloy 800 and polished
Incoloy 800 surfaces a f t e r exposures to helium, steam,
and oxygen at 700 C were s l i g h t l y r i c h e r in chromium
and titanium and s l i g h t l y depleted in n i c k e l , r e l a t i v e
to untreated Incoloy 800. No s i g n i f i c a n t changes in
surface composition, within the l i m i t s of experimental
error, were detected at 700C f o r polished and unpol-
ished aluminized Incoloy 800 samples exposed to ident-
i c a l conditions (see Table II). A s l i g h t decrease in
aluminum from 39.6 wt% to approximately 35% was
observed for the polished aluminized Incoloy 800 sam-
ples. This difference may be, in part at least, a
result of v a r i a t i o n s in the thickness of the
aluminum-rich layer f o r polished samples.
In contrast to the f i n d i n g s at 700 C, major
differences in surface composition were found a f t e r
exposure of Incoloy 800 and polished Incoloy 800

Figure 6. Gaseous treatments of alonized Incoloy 800 surfaces at 900C for 4 h.

TABLE I: Compositions (wt.%) of Polished and Unpolished
Incoloy 800 Samples a f t e r 4-Hour Exposures
Treatment Incoloy 800 Polished Incoloy 800

%Ti %Cr % Fe %Ni %Cr %Fe Ni S
None - 18.0 49.0 33.0 - - 20.2 46.7 33.3 -
He, 700C - 24.1 46.4 29.5 - - 23.7 47.1 29.2 -
2
H 0, 700 C 0.4 20.8 49.5 29.3 - 1.0 22.6 47.1 29.2 -
2
0 , 700C - 37.7 43.4 18.9 - - 23.8 45.8 30.4 -
2
H S, 700C - 1.4, 45.7, 52.8, 29.5 0.8, 2.3, 60.0, 36.9, 28
2
H 0, 900C 2.5 54.9 28.1 14.5 - 3.0 66.9 19.2 10.9 -
2
0 , 900C 2.0 62.8 26.5 8.8 - 3.2 69.9 16.8 10.0 -
,Sulfur-free basis

TABLE II: Compositions (wt.%) of Polished and Unpolished
Aluminized Incoloy 800 Samples a f t e r 4-Hour Exposures
Treatment Aluminized Incoloy 800 Polished Aluminized Incoloy 800
%A1 %Ti %Cr %Fe % Ni %S %A1 %Ti %Cr %Fe % Ni % S

None 45.1 - 9.2 27.5 18.1 39.6 9.3 29.1 22.0 -
- -
He, 700C 45.3 0.3 6.6 29.1 18.7 - 35.3 0.4 10.0 32.2 22.0 -
2
H 0 , 700C 42.3 0.2 8.7 29.7 19.2 - 34.6 0.3 8.9 34.1 22.0 -
o 2 , 700C 45.7 0.2 8.0 28.0 18.1 - 35.6 0.4 9.7 33.5 20.8 -
H S,2 700C 45.5, - 9.2, 27.5, 17.7, 22.7 41.8, - 9.6, 29.1, 19.5, 19.7
2
H 0 , 900C 52.4 0.4 7.3 24.3 15.6 - 52.5 0.6 7.0 23.8 16.2 -
o 2 , 900C 56.8 0.2 7.2 22.0 13.9 - 54.1 0.3 7.7 22.8 15.2 -

,Sulfur-free basis

164 COKE FORMATION
samples to steam or oxygen at 900 C e.g. the chromium

and titanium content increased from about 18-20 and 0
wt.% to 55-70 and 2.5-3.0 wt.%, respectively. Expo
sure of aluminized samples to oxygen or steam at 900 C
resulted in a detectable increase in the aluminum con
tent with a f i n a l value of about 52-57 wt. X for both
unpolished and polished coupons. This increase in the
aluminum content was primarily at the expense of iron
and nickel.
An appreciable amount of s u l f u r (probably as
metal sulfides> was incorporated in the surface of a l l
coupons exposed to hydrogen s u l f i d e at 700 C, as shown
in Tables I and II. For Incoloy 800 coupons, there
was a very large decrease in the chromium content at
the surface. On a s u l f u r - f r e e basis the iron content
increased greatly fo
n i c k e l content increase
coupon. For aluminized Incoloy 800 coupons, there was
little change in the metal content on a s u l f u r - f r e e
basis as a r e s u l t of hydrogen s u l f i d e treatments, as
shown in Table II.
The metal coupons increased in weight as a r e s u l t
of the treatments with inorganic gases. With oxygen
and steam, metal oxides were formed on the surfaces.
The r a t e of w e i g h t y increase with oxygen was in the
range of 0.3-0.6 10~ g/cm /hr and with steam was
perhaps s l i g h t l y less; the p r e c i s i o n of the data are
not s u f f i c i e n t , however, to d i f f e r e n t i a t e between the
weight increases at 700 or 900C f o r Incoloy 800 or
aluminized Incoloy 800, or for unpolished or polished
surfaces. Weight gains of aluminized and polished
aluminized Incoloy 800 coupons because of treatment
with hydrogen s u l f i d e were s i m i l a r to those with oxy
gen. The rate of weight increase with hydrogen s u l ^
f i d e ^ was much greater <approximately 31 10
g/cm /hr> in the case of Incoloy 800 and polished
Incoloy 800 coupons. The metal s u l f i d e s spalled o f f
the polished Incoloy 800 coupon quite readily; part of
the s u l f i d e s and metal surface were lost when the
coupon was removed from the balance a f t e r weighing.
Coke Deposits on Coupons: The amount and charac

t e r i s t i c s of the coke formed on coupons contacted with
a mixture of 5% acetylene and 95% helium at 900 C
varied s i g n i f i c a n t l y depending on the pretreatment of
the coupons, as indicated by Table III and Figures 7
through 10. Although the coke deposits were generally
rather rough and over r e l a t i v e l y short distances were
quite heterogeneous in appearance, panoramic views at
magnifications of about 1000 often indicated s i m i l a r

TABLE III: Rates of Coking f o r Pretreated Surfaces
Exposed to 5% Acetylene a t 900C f o r 1 hour
2
Pretreatment Coking Rate 10", grams/cm /hr
f o r 4 hours Incoloy 800 A l o n i z e d Incoloy 800
Regular Polished Regular Polished
None 6.4 2.7 3.1 2.2
2
H 0, 700C 7.0 3.9 2.7 2.3
2
H 0, 900C 11.8 1.6, 2.9 2.5
2
0 , 700C 19.1 12.6
2
0 , 900C 9.8 19.7 2.4 2.4
2
H S, 700C (Sulfided surface) 14.8 7.5
Coked, 900C; flaked (No evidence of s u l f i d e flaking)
Decoked, 700C
2 2
with 0 - H 0 - H e 15.4 19.0
Coked, 900C;
Decoked, 700C
2 2
with 0 - H 0 - H e ; 45.1 95.0
2
H S, 700C, 2 hrs.

,Based on SEM observations t h i s s u r f a c e was more uniformly covered than e i t h e r the r e g u l a r or
p o l i s h e d a l o n i z e d Incoloy 800 s u r f a c e s . There were apparently uncovered areas on the l a t t e r

two s u r f a c e s .
166 COKE FORMATION
Figure 7. Coke deposited on various Incoloy 800 surfaces. Conditions: 5%

C H ;900Cforl
2 2 h.

c h a r a c t e r i s t i c s and what appeared to be rather uniform

coke thickness. The polished Incoloy 800 coupon pre-
treated with oxygen at 900C was a d e f i n i t e exception
however; on t h i s coupon, coke deposits appeared espe-
c i a l l y thick near the edges of coupon, but less coke
seemed to be present in the central regions of both
the top and bottom f l a t surfaces. The reasons f o r
such v a r i a t i o n s in coke thickness are not known.
The rates of coke formation on the d i f f e r e n t
coupons, as reported in Table III, were calculated
using the weight increase of the coupon while i t was
contacted with the acetylene-helium mixture. The
basic assumption made was that the weight of coke
deposited on each coupon was equal to the weight
increase. The coupons had to be handled c a r e f u l l y so
that no coke or
dling. The small weigh
by the formation of metal oxides or metal s u l f i d e s on
the surface because of the pretreatments was ignored;
i t was assumed that the oxides and s u l f i d e s were
reduced back to metals while the coke formed. The
rates of coking, as l i s t e d in Table III, are obviously
average rates averages for the one hour runs and
averages r e l a t i v e to the entire surface of the coupon.
Figure 7 shows the coke formed on the various
unpolished Incoloy 800 coupons. In a l l cases mixtures
of filament and globular coke resulted on the Incoloy
800 surfaces; certain areas exhibited r e l a t i v e l y large
c l u s t e r s of globular coke from which filament coke
protruded.
For polished Incoloy 800 coupons (see Figure 8),
a mixture of filament and globular coke formed on the
oxygen-treated surfaces. Filament coke was, however,
not detected on e i t h e r untreated or steam treated
coupons. The coupon treated with steam at 700 C was
covered rather uniformly with globular coke. The
coupon treated with steam at 900 C exhibited a r i p p l e d
layer of coalesced globular coke.
Four of the f i v e comparisons made with Incoloy
800 coupons that were either untreated, steam treated,
or oxygen treated indicated that more coke formed on
unpolished coupons as compared to polished coupons
(see Table III). The single exception was the coupon
on which most of the coke formed on the edges whereas
the f l a t and polished surfaces were r e l a t i v e l y free of
coke. It seems safe to conclude therefore that less
coke formed in a l l cases on the polished f l a t surfaces
as compared to the unpolished surfaces.
In an e f f o r t to minimize the problem of s p a l l i n g
of metal s u l f i d e s from Incoloy 800 surfaces contacted

168 COKE FORMATION
Figure 8. Coke deposited on various polished Incoloy 800 surfaces. Conditions:

5% C H ; 900C for 1 h.
2 2

with hydrogen s u l f i d e , the following procedure was

employed to compare polished and unpolished Incoloy
800 coupons. Two polished and two unpolished Incoloy
800 coupons were f i r s t contacted with 5% acetylene f o r
one hour at 900 C; each coupon was then decoked with a
mixture of 10% oxygen, 50% steam, and the remainder
helium. Next, one polished and one unpolished coupon
were contacted with hydrogen s u l f i d e f o r two hours at
700 C; f i n a l l y , a l l four coupons were then contacted
with a 5% acetylene stream at 900C f o r one hour.
S u l f i d i n g of the coupons resulted in a major increase
(by a factor of 3 to 5) in the rate of coking. On the
polished and unpolished coupons that had been s u l -
fided, the filament coke formed was of r e l a t i v e l y
large diameter and contained iron and nickel
In what i s considere
investigation, significan
formed on the surface of the Vycor tubes holding the
s u l f i d e d coupons. This coke was found to contain both
iron and n i c k e l which had obviously been transferred
from the Incoloy 800 coupons. Possibly the iron and
n i c k e l s u l f i d e s o r i g i n a l l y present on the coupons were
liquefied or even v o l a t i l i z e d and then transported to
the Vycor surfaces where they catalyzed the growth of
coke filaments.
For aluminized Incoloy 800 coupons that had been
untreated, steam treated, or oxygen treated, the
amount, metal content, and general appearance of the
coke deposited on each coupon were s i m i l a r , as i n d i -
cated by SEM pictures in Figures 9 and 10, by EDAX
analyses, and by the rates of coking. Coking rates
l i s t e d in Table III indicated that polishing the
aluminized coupons perhaps s l i g h t l y decreased the
amount of coke. In a l l cases, globular coke was
present on a layer of amorphous coke. As shown in
Figures 9 and 10, a few coke filaments were scattered
on some of the surfaces. In the case of the untreated
aluminized Incoloy 800 coupon, the filaments were
clustered at or near pitted areas on the surface; less
aluminum was detected by EDAX in these pitted areas.
For steam-treated and oxygen-treated coupons which had
not been polished, globular coke was collected to some
extent in the pitted areas. Polishing the coupons
usually tended to remove s u f f i c i e n t surface so that
the pitted areas were no longer detectable, as shown
in Figure 10.
Much more coke formed on aluminized surfaces that
had been s u l f i d e d than on any other aluminized surface
(see Table III). An appreciable number of coke fila-
ments formed on both the polished and unpolished

170 COKE FORMATION
Figure 9. Coke deposited on various alonized Incoloy 800 surfaces. Conditions:

5% C H ;900Cjorlh.
2 2

Figure 10. Coke deposited on various polished alonized Incoloy 800 surfaces.
Conditions: 5% C H ; 900C for 1 h.
2 2

172 COKE FORMATION
coupons, as sown in Figures 9E and 10E. These fila-

ments probably contain iron and nickel; EDAX analyses
were inconclusive because dense growths of filaments
were not detected. The polished aluminized coupon had
a s i g n i f i c a n t l y lower rate of coking than the unpol-
ished coupon.
For unpolished coupons, a l l comparisons shown in
Table III indicate that less coke formed on aluminized
Incoloy 800 coupons as compared to Incoloy 800
coupons. Some caution must be exercised in i n t e r p r e t -
ing the r e s u l t s since the Incoloy 800 coupons were
positioned about 2.5 cm. upstream of the aluminized
coupons in the flow path of the gases. Small differ-
ences in coking rates have been shown to r e s u l t when
coupons of the same a l l o y composition are positioned
about 4 cm. apar
comparisons betwee
800 coupons found here are s i m i l a r to those reported
e a r l i e r (1/8). For polished coupons, three of the
four comparisons indicate that less coke formed on the
aluminized coupons as compared to the Incoloy 800
coupons. The lowest rate of coking apparently
occurred, however, on the polished Incoloy 800 coupon
that had been steam treated at 900C. The coke on t h i s
coupon appeared to rather uniformly cover the surface,
although the thickness of the coke layer was not
determined. The comparably treated aluminized coupon
appeared under the SEM to have areas that were coke
free. No explanation can currently be given for these
perhaps s i g n i f i c a n t findings.
Discussion of Results
The r e s u l t s of t h i s investigation greatly c l a r i f y

several f a c t o r s that a f f e c t coking in p y r o l y s i s c o i l s
and transfer l i n e exchangers. In p a r t i c u l a r , the r o l e
of the surface i s better defined since s i g n i f i c a n t
differences in r e s u l t s were obtained when d i r e c t l y
comparing Incoloy 800 versus aluminized Incoloy 800
and polished versus unpolished surfaces.
Increased roughness and major changes in surface
roughness have been known for a considerable time to
occur as a p y r o l y s i s c o i l i s used. The present
results clearly indicate that s i g n i f i c a n t changes
occur within just four hours because of surface reac-
t i o n s with steam, oxygen, or e s p e c i a l l y hydrogen s u l -
f i d e in the 700 to 900 C range. Even heating f o r four
hours at 900 C caused major changes in the surface
morphology of Incoloy 800. Although not specifically
investigated, repeated oxidation-reduction sequences

8. MARE AND ALBRIGHT Surface Phenomena During Pyrolysis 173
such as occur during p y r o l y s i s would severely roughen

the surfaces. Such sequences occur as steam or oxygen
(during burnoffs) oxidize the surfaces or as hydrocar
bons react with the metal oxides to form carbon
oxides, steam, and reduced metals (4). In units in
which sulfur-containing gases are in the feedstream,
s u l f i d i n g - d e s u l f i d i n g sequences also occur r e s u l t i n g
in severe roughening of the metal surfaces. As i n d i
cated here, major differences occur in the a b i l i t y of
the surfaces to r e s i s t t h i s roughening depending on
t h e i r surface composition and roughness.
The present r e s u l t s also c l a r i f y some of the
methods by which chromium, n i c k e l , and iron are lost
from the surface. For chromium, d i f f u s i o n to the sur
face was c l e a r l y shown to be r a p i d at temperatures of
900 C or higher <as
and the chromium a
with either steam or oxygen. A variety of surface
reactions such as reduction, sulfiding, or coking
would act to eventually s p a l l o f f the chromia or other
chromium compounds. In commercial units, the r a p i d l y
flowing gases would f l u i d i z e and move many of these
compounds along the c o i l length.
Nickel and iron are c e r t a i n l y removed from the
surface by at least three mechanisms. F i r s t , both
elements are incorporated in c e r t a i n cokes by cata
lytic reactions (10.); filamentous coke i s one such
coke. The filaments are probably broken to some
extent by the high v e l o c i t y gases in commercial pyro
lysis coils. Furthermore, oxidation reactions with
steam (during p y r o l y s i s runs or during burnouts) or
with oxygen (during burnouts) act to free p a r t i c l e s of
finely divided iron and n i c k e l oxides or other com
pounds. Second, s p e l l i n g of the iron and n i c k e l
oxides or s u l f i d e s from the roughened surface cer
t a i n l y accounts for some losses. Third, some n i c k e l
and iron compounds (probably s u l f i d e s ) are entrained
in the gas stream or vaporized at temperatures of
900 C or higher. This l a t t e r means of t r a n s f e r may be
of considerable importance for transport of both
n i c k e l and iron to the transfer l i n e exchanger where
they are imbedded in the coke that c o l l e c t s there.
The r e s u l t s of t h i s i n v e s t i g a t i o n help clarify
why machining i s b e n e f i c i a l r e l a t i v e to coke forma
tion, rough areas on the surface act as excellent c o l
l e c t i o n s i t e s for coke or tar droplets formed in the
gas phase. Such tar droplets eventually become globu
lar coke. Smoother surfaces hence minimize such c o l
l e c t i o n or surface deposits. In addition, smoothing
or polishing of both Incoloy 800 and aluminized

174 COKE FORMATION
Incoloy 800 surfaces acts to produce surfaces with

more desirable compositions; these new surfaces are
more r e s i s t a n t to oxidizing, s u l f i d i n g , or surface
coking reactions. Of interest, Gregg and Leach (11)
had found that less coke was formed on electropolished
nickel surfaces as compared to unpolished n i c k e l sur-
faces. In the case of the aluminized Incoloy 800,
care must be taken not to remove too much of the sur-
face since the aluminum has penetrated only short d i s -
tances into the surface. The r e s u l t s of the present
i n v e s t i g a t i o n imply that the method or degree of p o l -
ishing i s important. It i s not clear why polished
coupons in some cases c o l l e c t e d considerable coke near
the corners of the coupons.
Another advantage of aluminized Incoloy 800 sur-
faces i s that d i f f u s i o
the surface i s d r a s t i c a l l
stopped. It seems clear that d i f f u s i o n of aluminum in
such a l l o y s i s however f a i r l y rapid, as indicated by
the present r e s u l t s . One would expect in commercial
units however that a l l aluminum reaching the surface
would quickly react with steam or oxygen to produce
alumina.
The r e s u l t s of the present i n v e s t i g a t i o n strongly
suggest that c e r t a i n oxidized surfaces are highly
b e n e f i c i a l on e s p e c i a l l y polished Incoloy 800 sur-
faces. For example, oxidation of the polished Incoloy
800 coupons with steam at 900C r e s u l t e d in a coupon
that c o l l e c t e d only a small amount of coke. Earlier
Brown and Albright <i> also found that some highly
oxidized surfaces were c a t a l y t i c a l l y inert. It i s
thought that these desirable surfaces are r i c h in
chromia and are probably quite impervious to d i f f u s i o n
of oxygen, steam, or hydrocarbons. There i s c l e a r l y a
need to obtain a d d i t i o n a l information c l a r i f y i n g the
c h a r a c t e r i s t i c s of t h i s ummived layer of surface
oxides.
Farther investigations now in progress w i l l c l a r -
ify further the key factors that a f f e c t the formation
of catalytical1y-formed coke and the c o l l e c t i o n or
deposition of gas-phase coke or t a r droplets on s o l i d
surfaces.
Acknowledgment
Alon Processing, Inc. provided financial support

to the present investigation.

Literature Cited
1. Graff, M.J.; Albright, L.F., Carbon (1982), in

press.
2. Marek, J.C.; Albright, L.F., 182nd American Chem
i c a l Society National Meeting, New York, August,
1981; (Chapter 7, t h i s book).
3. Baker, R.T.K.; Chludzinski, J.J., J. Catalysis
(1980), 64, 464-478.
4. Tsai, C.H.; Albright, L.F., " I n d u s t r i a l and
Laboratory Pyrolyses"; ACS Symposium Series No.
32, Chapter 16, L.F. Albright and B.L. Crynes,
Ed., American Chemical Society: Washington, D.C.,
1976.
5. Castle, J.E.; Durbin M.J. Carbon (1975) 13
23-31.
6. Bittner, H.F. .
trochem. Soc. (1980), 127, 902-906.
7. Durbin, M.J.; Castle, J.., Carbon (1976), 14,
27-33.
8. Albright, L.F.; McConnell, C.F.; Welther, .,
"Thermal Hydrocarbon Chemistry"; Advances in
Chemistry Series No. 183, Chapter 10, A.G.
Oblad, H.G. Davis, and T.E. Eddinger, Ed., Ameri
can Chemical Society: Washington, D.C., 1979.
9. Perry, R.H.; Chilton, C.H., Ed.; Chemical
Engineers' Handbook", McGraw-Hill, Inc.: New
York, 1973.
10. Baker, R.T.K.; Harris, P.S.; Thomas, R.B.; Waite,
R.J., J. Catalysis (1973), 30, 86-95.
11. Gregg, S.J.; Leach, H.F., J. Catalysis (1966), 6,
308-313.
12. Brown, S.M.; Albright, L.F., " I n d u s t r i a l and
Laboratory Pyrolyses"; ACS Symposium Series No.
32, Chapter 17, L.F. Albright and B.L. Crynes,
Ed., American Chemical Society: Washington, D.C.,
1976.

9
Growth and Initiation Mechanism of Filamentous
Coke
1
A L B E R T SACCO, JR., and JOHN C. CAULMARE
Worcester Polytechnic Institute, Department of Chemical Engineering,
Worcester, M A 01609
Decomposition of carbo g gase

often results in the formation of filamentous materials ("carbon
fibers"). These carbon fibers are uniform i n width, usually
between 500-1000, come in the shape of f l a t ribbons, solid or
hollow tubes, and some are even twisted. The formation of these
filaments results in corrosion of the metallic phase.
An investigation was performed to try to ascertain the i n i -
tiation and growth mechanism for fiber formation in a five com-
ponent gas mixture (CO, CO , CH , H , H O) over iron. Phase
2 4 2 2
diagrams were used to try to control the solid phase composition

during reaction. An electrobalance was used to continuously
monitor weight gain, and electron optics were used to examine the
bulk metal and fiber structure(s). Preliminary results indicate
that fiber formation only occurs when a carbide i s thermodynamic-
ally favored. Also, the rate plotted as change i n fractional
weight gain per unit time goes through a maximum and then levels
out at a constant rate. Possible reasons for this will be pro-
posed and a mechanism hypothesized.
T r a n s i t i o n metals exposed t o carbon bearing gases a t e l e v a t e d

temperatures o f t e n c a t a l y z e the formation o f carbonaceous d e p o s i t s .
One of the more i n t e r e s t i n g carbon morphologies observed is fre-
quently called " f i l a m e n t o u s " carbon. This form o f carbon c o n s i s t s
of f i l a m e n t s o r fibers. These f i l a m e n t s a r e g e n e r a l l y cylindrical
i n shape and l e s s than 1000 in diameter. Both solid (Hofer
et al., (1)) and hollow ( O b e r l i n e t al., (2)) fibers have been
observed as w e l l as t w i s t e d or braided f i l a m e n t s (Boehm (3).
Most f i l a m e n t s have a small piece o f m e t a l , u s u a l l y about the same
diameter as the f i l a m e n t , embedded a t some p o i n t along its l e n g t h .
1
Current address: EXXON Research and Engineering Company, Florhan Park, NJ 07932.
0097-6156/82/0202-0177$06.00/0

178 COKE FORMATION
This metal c r y s t a l i s b e l i e v e d to be the growth c e n t e r (Baker

et a l . , ( 4 ) ) . The recent r e s u l t s of Baker and Chludzinski (5j)
f u r t h e r support t h i s c o n t e n t i o n . The penchant of t h i s form of
carbon f o r removing metal from the s u r f a c e of a large piece of
metal, or from a support m a t e r i a l i s the most i n t e r e s t i n g as well
as damaging aspect of t h i s type of d e p o s i t . E v e n t u a l l y , i t s form
a t i o n r e s u l t s in the d e s t r u c t i o n of the parent metal m a t r i x , or
the removal of c a t a l y t i c m a t e r i a l from i t s support.
Many i n v e s t i g a t i o n s have been performed to t r y to a s c e r t a i n
the growth mechanism of t h i s form of carbon. An e x c e l l e n t review
on work in t h i s area i s presented by Baker and H a r r i s (6). How
ever, none has r e s u l t e d in a completely c o n s i s t e n t mechanism that
can e x p l a i n the v a r i e d reported r e s u l t s . S u r p r i s i n g l y few in
v e s t i g a t i o n s have attempted to study the i n i t i a t i o n s t e p , the way
the growth c r y s t a l i s e x t r a c t e
or support i n i t i a l l y . Als
no attempt has been made to c o n t r o l the s u r f a c e phase(s) during
reaction. This i s of importance s i n c e phase(s) ( e . g . , c a r b i d e s )
can form during heating and c o o l i n g sequences. The o b j e c t i v e of
the present i n v e s t i g a t i o n i s to t r y to understand the i n i t i a t i o n
step in f i b e r growth, and a l s o to e s t a b l i s h what i r o n metal phases
c a t a l y z e f i l a m e n t growth.
Experimental
A l l experiments were performed on high purity(>99.99%) p o l y -

c r y s t a l l i n e iron f o i l s . Carbon was deposited from multicomponent
mixtures of H , H 0 , CH^, CO, and C0 at 900 and 1 bar pressure.
2 2 2
These r e a c t a n t gases were d e l i v e r e d to the r e a c t o r a t 20 c c / s (STP).

The weight changes observed were a t t r i b u t e d to carbon d e p o s i t i o n
or o x i d a t i o n and monitored throughout the course of an experiment
using an e l e c t r o b a l a n c e - r e c o r d e r u n i t . Figure 1 i s a schematic of
the experimental apparatus. Reactant gases were i n d i v i d u a l l y
metered through Brook mass flow r e g u l a t o r s . Their precise flow-
rates were determined by measurement of t h e i r pressure drops through
p r e c i s i o n bore c a p i l l a r y tubes. They were then mixed by passage
through a drying tube and fed dry or saturated with water to a
fused quartz p r e h e a t e r - r e a c t o r . S a t u r a t i o n of the feed gas was
accomplished by flow through a s e r i e s of bubblers submerged in a
t h e r m o s t a t i c a l l y c o n t r o l l e d water bath. P a r t i a l pressures of
water from 0 to 0.34 bar were e a s i l y obtained. A l l feed and e x i t
l i n e s were wrapped with heating tapes and maintained at temperatures
in excess of 363 K.
The r e a c t o r assembly c o n s i s t e d to two 38 mm diameter t u b u l a r
s e c t i o n s : the r e a c t o r - p r e h e a t e r tube and the r e a c t o r - e l e c t r o b a l a n c e
interface section. The r e a c t o r - p r e h e a t e r tube i s 0.66 m in length
and i s c o n s t r u c t e d of fused q u a r t z . The lower p o r t i o n of t h i s
tube i s packed with fused quartz r i n g s and i s used as a feed gas
preheater. A thermocouple i s l o c a t e d in the r e a c t o r d i r e c t l y be
low the metal f o i l and a gas sampling port i s p o s i t i o n e d immediately

M A S S FLOW R E G U L A T O R
MANOMETER
J 1 1 J A 1 rc 1 rA / r 1
PRECISION
BORE C A P I L L A R Y
/ TUBE
If if If
I
L__.T L.J
ELECTROBALANCE
ORYING TUBE
WT. RECORDER WATER
3ATURATOR
EFFLUENT GAS
- REACTOR TUBE

1 INDICATING T.C.
GAS CHROMATOGRAPH I
SAMPLE VALVE PREHEATER

TEMP FURNACE
CONT.
Figure 1. Experimental apparatus.

180 COKE FORMATION
above the sample. The r e a c t o r e f f l u e n t and the i n e r t gas (helium),

which i s fed through the e l e c t r o b a l a n c e to p r o t e c t i t s mechanism,
e x i t through l i n e s l o c a t e d in the i n t e r f a c e s e c t i o n . The r e a c t o r -
preheater tube i s housed w i t h i n a tube furnace powered and c o n
t r o l l e d by a West SCR s t e p l e s s p r o p o r t i o n a l temperature c o n t r o l l e r .
This system was capable of maintaining a 1 cm isothermal zone up
to 1200 K. The e n t i r e r e a c t o r assembly and e l e c t r o b a l a n c e were
f i x e d on a s p e c i a l l y designed frame (Figure 2). The frame allowed
the e l e c t r o b a l a n c e to perform at n e a r l y maximum s e n s i t i v i t y .
Weight changes were monitored continuously using a Cahn 2000
electrobalance. A s e n s i t i v i t y of 1 0 " grams was t y p i c a l f o r the
6
f l o w - r e a c t o r e l e c t r o b a l a n c e system used in t h i s i n v e s t i g a t i o n .
I n l e t and e f f l u e n t gas streams were analyzed p e r i o d i c a l l y using
an o n - l i n e Sigma I (Perkin Elmer) gas chromatograph.
Method of Analysis
To determine which s o l i d phases c a t a l y z e the formation of

carbon f i l a m e n t s , phase diagrams were used. The usefulness of
phase diagrams f o r t h i s system has been demonstrated in the work of
Sacco and Reid (7_) ; and thus, only a b r i e f d i s c r i p t i o n of t h e i r use
w i l l be given here. A phase diagram f o r the gas components of
i n t e r e s t and the s o l i d phases of i n t e r e s t i s generated using a v a i l
able G i b b s - f r e e energy d a t a . Figure 3 represents the
F e C - F e 0 - C g - g a s ( H , H 0 , ChU, CO, C0 ) phase diagram at 900 and
3 x 2 2 2
1 bar pressure. The apexes of the e q u i l a t e r i a l t r i a n g l e represent

atomic carbon, hydrogen and oxygen. Thus, any gas mixture com
posed of these elements can be p l o t t e d on t h i s t r i a n g u l a r s u r f a c e .
As examples, the l o c a t i o n s of pure CO, C 0 , H 0 , and CtU are shown
2 2
in Figure 3. The curve which i s concave downward represents the

e q u i l i b r i a between alpha i r o n - w u s t i t e ( F e 0 ) and gas.
x Any p o i n t
located on t h i s curve represents a gas mixture in e q u i l i b r i u m with
alpha iron and w u s t i t e . As p l o t t e d i f one i s below t h i s c u r v e ,
such as in the region i n d i c a t e d by point X, i r o n oxide i s the
s t a b l e iron phase. That i s , in t h i s phase f i e l d the chemical
p o t e n t i a l d r i v i n g f o r c e i s such that reduced i r o n can not form.
If one i s above t h i s c u r v e , the i r o n - i r o n oxide-gas e q u i l i b r i a
p r e d i c t s reduced i r o n . However, when the alpha i r o n - c e m e n t i t e
(Fe C)-gas e q u i l i b r i a i s imposed on t h i s system (dotted l i n e ) i t
3
i s seen that any reduced i r o n formed w i l l r e a c t with the gas phase

to produce c a r b i d e (Fe C) in t h i s r e g i o n .
3 F i n a l l y , the g r a p h i t e -
gas e q u i l i b r i a i s superimposed on t h i s diagram ( s o l i d l i n e concave
upwards). This curve represents the l o c i of p o s s i b l e gas mixtures
in e q u i l i b r i u m with s o l i d graphite at 900 and under 1 bar
pressure. If a gas mixture l i e s above t h i s c u r v e , then the chem
i c a l p o t e n t i a l d r i v i n g f o r c e i s such that s o l i d carbon should form.
A gas mixture below t h i s boundary w i l l r e s u l t in a d r i v i n g f o r c e
that favors s o l i d carbon o x i d a t i o n . T h i s assumes that the s o l i d
surface present during r e a c t i o n i s a c a t a l y s t f o r carbon d e p o s i t i o n
or o x i d a t i o n . For example, i f we c a r e f u l l y carbide the s u r f a c e

SACCO AND CAULMARE Filamentous Coke
\<Support Rails - H
Vibration Isolators
Figure 2. Reactor support assembly.

GO
8
to

>
H

9. SACCO AND CAULMARE Filamentous Coke 183
and then feed a gas mixture represented by point M carbon should

form i f cementite (Fe C) i s a c a t a l y s t f o r carbon d e p o s i t i o n .
3 If
Fe C i s not a c a t a l y s t f o r carbon d e p o s i t i o n , then there w i l l not
3
be a n o t i c e a b l e weight g a i n . In t h i s manner one can c o n t r o l the

s u r f a c e phase and determine i f i t c a t a l y z e s f i b e r growth.
Procedures
In t h i s work, a d i f f e r e n t i a l r e a c t o r was used to i n s u r e that

the gas composition remains e s s e n t i a l l y unchanged and thus o p e r a t -
ion during an experiment remained in the phase f i e l d of i n t e r e s t .
A computer program was used to c a l c u l a t e the gas phase compositions
to be used f o r an experiment. T y p i c a l l y , a preweighted p o l y -
c r y s t a l l i n e f o i l was placed in the r e a c t o r heated in hydrogen to
the d e s i r e d r e a c t i o n temperature
passed c o n t i n u o u s l y ove
taken and analyzed every twenty minutes to i n s u r e that the gas
composition remained constant. The mass of the f o i l was r e -
corded throughout the run from s t a r t - u p through the c o o l i n g
sequence.
At the c o n c l u s i o n of an experiment, the r e a c t i o n gases were
vented and the r e a c t o r was allowed to cool down to room temp-
erature w i t h i n a flowing stream of helium. The time of c o o l i n g
was not c r i t i c a l s i n c e experiments were only made a t temperatures
below the E u t e c t o i d temperature (996 K), samples were held at
r e a c t i o n temperature f o r times in excess of 25 minutes, and
c o o l i n g was slow (3-4 h r s ) . The E u t e c t o i d temperature i s the
temperature at which a s i n g l e s o l i d phase begins to decompose i n t o
two other phases on c o o l i n g . The samples were removed from the
r e a c t o r assembly and stored in a helium atmosphere to prevent
oxidation. The samples were then examined using both an o p t i c a l
and scanning e l e c t r o n microscope.
Results and Discussion
I n i t i a l l y , a s e r i e s of experiments were performed with a gas

phase composition that maintained the s o l i d s u r f a c e in the r e -
duced c o n d i t i o n , w h i l e a l s o maintaining a chemical p o t e n t i a l
d r i v i n g f o r c e f o r carbon d e p o s i t i o n . These experiments are i d e n -
t i f i e d by the open t r i a n g l e s on the C/H = 0.13 l i n e in Figure 4.
In Figure 4 an open t r i a n g l e means that during the course of the
experiment n e i t h e r weight l o s s nor weight gain was d e t e c t e d . In
these i n i t i a l experiments, no weight change was detected up to as
long as 140 minutes. A f t e r a s u f f i c i e n t l y long period of n e i t h e r
weight gain or l o s s , u s u a l l y between 30-60 minutes, the r e a c t a n t
gases were bypassed around the s a t u r a t o r .
This r e s u l t e d in a dry gas stream at the same flow r a t e
e n t e r i n g the r e a c t o r . In a l l cases a weight gain was observed
immediately. These data are shown as the two darkened t r i a n g l e s


00
>

2

on the C/H l i n e of 0.13. These dry gaseous mixtures are in the

region where an i r o n c a r b i d e (Fe C) w i l l form and suggests that
3
carbon d e p o s i t i o n may only occur when a c a r b i d e i s present. To

t r y to f u r t h e r s u b s t a n t i a t e t h i s h y p o t h e s i s , as well as to d e t e r
mine i f water has an i n f l u e n c e on the observed behavior, a s e r i e s
of experiments were performed at a C/H r a t i o of 0.40 in the c a r b i d e
region. As i n d i c a t e d in Figure 4, weight gain was observed. The
gas phase composition f o r these i n t i a l runs are presented in
Table I. A l s o included in Figure 4 are data taken by Sacco and
Reid (7_) over a s t e e l wool c a t a l y s t . Although more h e a v i l y
a l l o y e d (<99% i r o n ) and porous in n a t u r e , the behaviour i s the
same; that i s , carbon d e p o s i t i o n only occurs in the region where
a c a r b i d e (Fe C) i s f a v o r e d .
3
Using a JSM-U3 scanning e l e c t r o n microscope, the f o i l s on

which a weight gain wa d examined Th s u r f a c
found to be covered wit
f i b e r s were c y l i n d r i c a shap approximately y
diameter. A l l these f i b e r s appeared to have a m e t a l l i c c r y s t a l
at t h e i r t i p . However, the r e s o l u t i o n was not f i n e enough to
determine i f the filaments were hollow or not. The f o i l s were
then p o l i s h e d and etched with 2-3% n i t a l s o l u t i o n ( n i t a l i s an
etch c o n s i s t i n g of n i t r i c a c i d in methanol). The s t r u c t u r e was
p e a r l i t i c in nature, showing large c a r b i d e formations along g r a i n
boundaries.
The f a c t that the formation of cementite i s apparently
necessary before carbon w i l l d e p o s i t ( i . e . , f i l a m e n t s w i l l grow)
i s in agreement with the work of Tsao (8). Tsao ran pure carbon
monoxide over reduced i r o n d i s k s at 903 K. He then used Mossbauer
spectroscopy to generate that data presented in Figure 5. As
i l l u s t r a t e d , i r o n carbide forms r a p i d l y while f r e e carbon appears
to form only a f t e r s u f f i c i e n t q u a n t i t i e s of c a r b i d e are present.
These d a t a , in agreement with the r e s u l t s i l l u s t r a t e d in Figure 4,
suggest that cementite ( F e C ) , not - i r o n , i s the c a t a l y s t f o r
3
carbon d e p o s i t i o n and t h e r e f o r e f i b e r growth.

Figure 6 i s a p l o t of a f r a c t i o n a l weight gain versus time f o r
f i v e d i f f e r e n t experiments run in the c a r b i d e r e g i o n . As expected,
the f r a c t i o n a l weight gain increases at a given time as the CO
concentration increases. A l s o , there appears to be an i n d u c t i o n
period followed by a period of constant weight g a i n . The slope
of these curves were taken and p l o t t e d versus time in Figure 7.
As i n d i c a t e d by the data in Figure 7, the rate of f r a c t i o n a l
weight gain appears to i n c r e a s e r a p i d l y reaching a maximum then
decreases s l i g h t l y to a steady s t a t e v a l u e . This type of behavior
was found f o r a l l experiments run in the c a r b i d e r e g i o n .
It i s tempting to suggest a k i n e t i c mechanism f o r carbon
d e p o s i t i o n due to the apparent CO dependency; however, i t must be
remembered that the s u r f a c e area i s changing c o n t i n u o u s l y in a l l
these experiments. This i s best i l l u s t r a t e d in Figure 8. Under
i n d e n t i c a l c o n d i t i o n s f o r three separate experiments, the f r a c t
i o n a l weight gain as a f u n c t i o n of time i s shown to d e v i a t e from

COKE FORMATION
Table I. Composition of A l l P r e l i m i n a r y Experiments
Mole P e r c e n t
CO CH, co 2 H 0
2 C/H 0/H
H
2 4
Run No.
1 62.1
2 61.3 7.6 16,.4 2. 3 12.4 0..12 0.12
3 63.8 8.0 17,.6 3. 4 7.2 0,.14 0.10
4 62.7 6.8 20,.9 0. 9 8.7 0,.13 0.08
5 69.6 8.9 19 .0 2. 5 0.0 0,.14 0.07
6 69.9 8.9 19,.1 2. 1 0.0 0,.14 0.06
7 68.2 7.4 22,.9 1. 5 0.0 0,.14 0.05
8 62.2 1.0 34,.7 0. 1 2.0 0..13 0.01
9 19.9 37.6 39,.7 1. 7 1.1 0,.39 0.21
10 19.9 37.6 40,.0 1. 8 0.7 0.,40 0.21
11 19.6 37.6 40 .0 1. 9 0.9 0..40 0.21
,12 65.0 2.7 30 .2 0. 2 1.9 0,.13 0.02
,13 66.2 2.8 30,.8 0. 2 0.0 0,.13 0.01
, Composition s e t u s i n g f l o w system not

c o n f i r m e d by gas chromatograph

SACCO AND CAULMARE Filamentous Coke
L
10 20 30 40 50
TIME (minutes)
Figure 5. Carbon analysis of the disks reacted at 903 K (G 0.3 L (STP)/min).

Key: , iron carbide; and free carbon. (Reproduced, with permission, from
Ref. 8).

00
00
W
h-*
>


1
s
00
8
Ci
S
3
>
>

COKE FORMATION
(|6!/\ |BU!U|/96uegQ 6) UIBQ iu,6!9M leuoipej j

each other a f t e r 6-10 minutes. This behavior i s due t o the f a c t

t h a t i n i t i a l l y the s u r f a c e areas f o r the three f o i l s are very
nearly e q u a l . A f t e r carbides form ( f i r s t 6-10 minutes), f i b e r s
begin t o form and the e f f e c t i v e surface area i n c r e a s e s . This
increase i s r e l a t e d t o the number of f i b e r s and the number o f
l o c a t i o n s where f i b e r s begin t o grow. This behavior makes i t very
d i f f i c u l t t o t e s t any proposed k i n e t i c mechanism.
Conclusions
These p r e l i m i n a r y r e s u l t s suggest t h a t cementite i s probably

a c a t a l y s t f o r carbon d e p o s i t i o n and thereby f i l a m e n t growth.
A l s o , the p e a r l i t i c s t r u c t u r e found a f t e r the f o i l s were etched
i n d i c a t e s t h a t carbon from the gas phase d i f f u s e s i n t o the s u r
face l a y e r (no p e a r l i t i
to r e a c t i o n ) . Based o
Tsao ( 8 ) , i t i s f e l t that the shape o f the curves i n Figure 7 can
be i n t e r p r e t e d as cementite formation f o l l o w e d by an i n c r e a s i n g
carbon d e p o s i t i o n rate as more and more c a r b i d e i s formed. Car
bides such as cementite w i l l form a t the more energy f a v o r a b l e
d i s l o c a t i o n s such as g r a i n boundaries and other areas o f s t r u c
t u r a l i r r e g u l a r i t i e s . These formations on s u r f a c e i r r e g u l a r i t i e s
( e . g . , s c r a t c h e s , edges, g r a i n boundaries) r e s u l t s i n large growth
areas which then break i n t o s m a l l e r c r y s t a l s which form the growth
t i p s f o r f i l a m e n t s . The formation of these c a r b i d e growth c r y s t a l s
(with t h e i r concomitant area increase) i s r e f l e c t e d i n the r a p i d
increase i n r a t e of f r a c t i o n a l weight g a i n . The steady s t a t e
(constant r a t e ) p o r t i o n i s b e l i e v e d t o be due t o f i b e r growth w i t h
a r e l a t i v e l y f i x e d number o f f i b e r s .
Acknowledgement
The authors g r a t e f u l l y acknowledge the support and encourage

ment o f the National Science Foundation through the Research
I n i t i a t i o n Grant Program, Grant No. ENG 78-05579.
Literature Cited
1. Hofer, L.J.E.; Sterling, E.; and McCartney, J.T. "Structure

of the Carbon Deposited from Carbon Monoxide on Iron, Cobalt,
and Nickel"; J. Phys. Chem. 1955, 59, 1153.
2. Oberlin, .; Endo, M.; and Koyama, T. "Filamentous Growth of
Carbon through Benzene Decomposition"; J. Crystal Growth 1976,
32, 335.
3. Boehm, H.P. "Carbon from Carbon Monoxide Disproportionation
on Nickel and Iron Catalysts: Morphological Studies and
Possible Growth Mechanisms"; Carbon 1973,11,583.

192 COKE FORMATION
4. Baker, R.T.K.; Harris, R.S.; Thomas, R.E.; and Waite, R.J.

"Formation of Filamentous Carbon from Iron, Cobalt and
Chromium Catalyzed Decomposition of Acetylene"; J. Catalysis
1973, 30, 86.
5. Baker, R.T.K.; Chludzinski, J r . , J.J. "Filamentous Carbon
Growth on Nickel-Iron Surfaces: The Effect of Various Oxide
Additives"; J. Catalysis 1980, 64, 464.
6. Baker, R.T.K; Harris, R.S. "The Formation of Filamentous
Carbon"; Chem. Physics Carbon 1978, 14, 83.
7. Sacco, J r . , .; Reid, R.C. "Water Limitations in the C-H-O
System over Iron"; AIChE J. 1979, 25, 839.
8. Tsao, T. "Kinetics of Dissociation of Carbon Monoxide on
-Fe"; Carnegie-Mellon University, Ph.D. 1974.
RECEIVED June 28, 1982

10
The Characterization of Carbon Deposit
Morphologies Using In Situ Scanning Electron
Microscopy
A. M . BROWN and M . P. HILL
Central Electricity Research Laboratories, Surrey, United Kingdom
Carbon deposits have been grown on heated poly-

crystalline iro
a scanning electro
of deposits formed from methane at temperatures
between 620C and 850C have been surveyed, from the
f i r s t appearance of solid carbon on the surface to
the f i n a l structural breakdown of the metal. Four
characteristic morphologies have been identified.
There are indications that solution-precipitation
processes are involved i n the growth mechanisms i n
each case.
The importance of structural disorder i n the
metal is considered and the behaviour of well
annealed material i s compared to structurally less
stable but clean metal surfaces. The processes that
occur i n the development of particulate deposits have
been followed. Auger analysis of individual
morphologies has highlighted particular problems i n
the analysis of carbon deposits after ion etching.
The implications of these observations to
deposition on less well-defined metal surfaces and
gases containing trace impurities i s discussed.
The f o r m a t i o n o f c a r b o n d e p o s i t s i s a n u n d e s i r a b l e f e a t u r e o f
a number o f i n d u s t r i a l p r o c e s s e s , f o r e x a m p l e o n t h e f u e l p i n s i n
n u c l e a r r e a c t o r s , on t h e c a t a l y s t s and s t r u c t u r a l m a t e r i a l s o f
r e a c t o r s i n p e t r o c h e m i c a l p l a n t , and on f u r n a c e w a l l l i n i n g s . A
g r e a t e r u n d e r s t a n d i n g o f t h e mechanism o f d e p o s i t i o n i s r e q u i r e d
i n o r d e r t o d e v e l o p i m p r o v e d methods o f c o n t r o l . M e t a l - c a r b o n
i n t e r a c t i o n s a r e a l s o important i n the c a t a l y s i s o f carbon g a s i -
f i c a t i o n f o r the manufacture o f s y n t h e t i c f u e l s .
The d e p o s i t s f o r m e d o n t r a n s i t i o n m e t a l s f r o m h y d r o c a r b o n s o r
carbon monoxide e x h i b i t a v a r i e t y o f m o r p h o l o g i e s i n c l u d i n g
g r a p h i t i c l a m i n a r f i l m s , mound ( m o n t i c u l a r ) g r o w t h s , c o l u m n a r ,
p a r t i c u l a t e , a n d numerous f i l a m e n t a r y t y p e s o f c a r b o n , (1-4). The
0097-6156/82/0202-0193$08.50/0

194 COKE FORMATION
o b s e r v a t i o n s suggest t h a t s e v e r a l d i f f e r e n t c h e m i c a l and/or
p h y s i c a l p r o c e s s e s o c c u r b o t h s i m u l t a n e o u s l y and s e q u e n t i a l l y
during the r e a c t i o n . A l t h o u g h one p a r t i c u l a r m o r p h o l o g y may have
b e e n i d e n t i f i e d as a p r o d u c t o f s e v e r a l h y d r o c a r b o n - m e t a l
r e a c t i o n s , t h e r e have b e e n few s y s t e m a t i c s t u d i e s o f t h e g r o w t h
mechanisms. However, c o n s i d e r a b l e p r o g r e s s has b e e n made in
u n d e r s t a n d i n g the growth of f i l a m e n t a r y carbon ( 4 ) , u s i n g con-
t r o l l e d a t m o s p h e r e t r a n s m i s s i o n e l e c t r o n m i c r o s c o p y w h i c h has
demonstrated the v a l u e of in-situ observations (5). Transmission
e l e c t r o n m i c r o s c o p y has t h e b e n e f i t s o f h i g h r e s o l u t i o n and t h e
a v a i l a b i l i t y of e l e c t r o n d i f f r a c t i o n , but i s l i m i t e d t o the
e x a m i n a t i o n o f s m a l l p a r t i c l e s , t h i n f o i l s , and p r o d u c t s formed a t
the edges o f s p e c i m e n s t o o t h i c k f o r t r a n s m i s s i o n o f t h e e l e c t r o n
beam. I n o r d e r t o s t u d y c a r b o n d e p o s i t i o n on b u l k m e t a l s in-situ
s c a n n i n g e l e c t r o n m i c r o s c o p y i s more s u i t a b l e o f f e r i n g the
f a c i l i t i e s of r e s o l u t i o
stereoscopic viewing o
a n a l y t i c a l techniques.
The m e t a l most a c t i v e in s u p p o r t i n g c a r b o n d e p o s i t i o n i s i r o n ,
c l o s e l y f o l l o w e d by n i c k e l , and i s t h e one s e l e c t e d f o r t h i s w o r k .
The i r o n - c a r b o n s y s t e m i s c o m p l e x b e c a u s e b o t h g r a p h i t e and i r o n
c a r b i d e s a r e p o s s i b l e r e a c t i o n p r o d u c t s . B e l o w t h e Fe-C e u t e c t o i d
t e m p e r a t u r e (721C o r 738C) a d d i t i o n a l s o l i d - s t a t e t r a n s f o r m a t i o n s
are known l e a d i n g t o t h e s t r u c t u r e s f o u n d in f e r r i t i c s t e e l s , i . e .
p e a r l i t e , m a r t e n s i t e and b a i n i t e e t c . C o n s e q u e n t l y , c a r e must be
t a k e n o v e r t h e t e m p e r a t u r e c y c l i n g e x p e r i e n c e d by t h e s p e c i m e n t o
avoid introducing a d d i t i o n a l complications. In p a r t i c u l a r , cooling
a specimen t o ambient temperature f o r e x a m i n a t i o n i n c r e a s e s con-
s i d e r a b l y the r i s k of m o d i f y i n g e x i s t i n g s t r u c t u r e s or i n t r o d u c i n g
new p r e c i p i t a t i o n p r o d u c t s . A m b i g u i t i e s a r i s i n g f r o m t h e s e s o u r c e s
are l a r g e l y a v o i d e d by use o f t h e in-situ SEM t e c h n i q u e .
S e v e r a l mechanisms o f c a r b o n d e p o s i t i o n have b e e n p r o p o s e d
(4, 6-8) i n c l u d i n g :
(i) carbon d i s s o l u t i o n , d i f f u s i o n to s u i t a b l e s i t e s ,
f o l l o w e d by p r e c i p i t a t i o n ,
(ii) f o r m a t i o n o f m e t a l c a r b i d e on t h e s u r f a c e f o l l o w e d
by t h e r m a l d e c o m p o s i t i o n ,
(iii) s u r f a c e d i f f u s i o n o f c a r b o n atoms o r a C/H/metal
o r g a n o - m e t a l l i c type complex s p e c i e s ,
(iv) b u l k carbon d i f f u s i o n .
Under d i f f e r e n t e x p e r i m e n t a l c o n d i t i o n s one o r o t h e r o f t h e s e
mechanisms may p r e d o m i n a t e . However, a t t h e p r e s e n t t i m e t h e
growth mechanism f o r t h e m a j o r i t y o f c a r b o n s t r u c t u r e s i s u n c e r t a i n .
I n c a r b o n d e p o s i t i o n on a b u l k m e t a l s p e c i m e n , t h e c a r b o n
u p t a k e f o l l o w s a s i g m o i d a l c u r v e as a f u n c t i o n o f t i m e t y p i c a l o f
an a u t o c a t a l y t i c r e a c t i o n . I n i t i a l l y c a r b o n d i s s o l v e s in t h e
m e t a l u n t i l t h e s a t u r a t i o n s o l u b i l i t y has b e e n e x c e e d e d . This step
i s o b s e r v e d as an i n c u b a t i o n p e r i o d . The i n i t i a l s o l i d p r o d u c t
formed c a u s e s no d i s r u p t i o n o f t h e m e t a l s u r f a c e and t h e g r o w t h
r a t e remains low. I t s t a r t s t o r i s e r a p i d l y as p a r t i c u l a t e

10. BROWN AND HILL Carbon Deposit Morphologies 195
m a t e r i a l i s e x t r a c t e d f r o m t h e m e t a l and becomes i n c o r p o r a t e d in
the d e p o s i t , l e a d i n g e v e n t u a l l y t o complete breakdown o f t h e m e t a l
structure. Most o f t h e c a r b o n d e p o s i t i s formed d u r i n g t h i s
p e r i o d as i n c r e a s i n g amounts o f a c t i v e c a t a l y s t become a v a i l a b l e ,
and t h e g r e a t e s t v a r i e t y o f d e p o s i t m o r p h o l o g i e s a r e o b s e r v e d .
The r e a c t i o n e v e n t u a l l y s l o w s down e i t h e r b y f o r m a t i o n o f i n e r t
p r o d u c t s , e . g . Fe + CO ( 9 ) o r b y e n c a p s u l a t i o n o f a c t i v e m e t a l
p a r t i c l e s in c a r b o n Q 0) .
I n t h e w o r k r e p o r t e d in t h i s p a p e r , t h e in-situ h o t s t a g e SEM
t e c h n i q u e h a s b e e n u s e d t o e x a m i n e t h e c a r b o n d e p o s i t s f o r m e d in
the i r o n - m e t h a n e r e a c t i o n , w i t h t h e o b j e c t i v e o f s e p a r a t i n g t h e
d i f f e r e n t stages by i d e n t i f y i n g t h e c h a r a c t e r i s t i c morphologies.
I t i s p r e s e n t e d as a s u r v e y o f t h e r a n g e o f p r o d u c t m o r p h o l o g i e s
s t a r t i n g w i t h t h e c a r b o n d i s s o l u t i o n s t a g e and e n d i n g w i t h t h e
complete s t r u c t u r a l breakdown o f t h e e x p e r i m e n t a l f o i l
Experimental
The SEM u s e d f o r t h e w o r k i s a s p e c i a l l y a d a p t e d u l t r a - h i g h
vacuum f i e l d e m i s s i o n s o u r c e i n s t r u m e n t (V.G. M i c r o s c o p e s L t d . ) .
I t has a gas r e a c t i o n c e l l w h i c h s u r r o u n d s t h e specimen w h i l s t
p e r m i t t i n g most m i c r o s c o p e s t a g e movements. R e a c t i o n s c a n be
c a r r i e d o u t a t p r e s s u r e s up t o ^50 T o r r , b u t above ^0.2 T o r r t h e
e l e c t r o n gun chamber must be i s o l a t e d and s o c o n t i n u o u s s p e c i m e n
observation i snot p o s s i b l e . I n t h e n o r m a l m i c r o s c o p e mode t h e
r e s o l u t i o n i s b e t t e r t h a n 50 8. a t s p e c i m e n t e m p e r a t u r e s up t o
800C, b u t i s r e d u c e d t o ^250 8. in t h e r e a c t i o n c e l l b e c a u s e o f a
requirement t o i n c r e a s e t h e probe c u r r e n t t o a c h i e v e s u f f i c i e n t
signal(11). The m i c r o s c o p e i s e q u i p p e d w i t h a n e n e r g y d i s p e r s i v e
X - r a y a n a l y s e r , a c y l i n d r i c a l m i r r o r A u g e r a n a l y s e r s (CMA) and a n
a r g o n i o n gun. As i n d i c a t e d in F i g u r e 1, t h e r e a c t i o n c e l l must
be opened t o p e r m i t m i c r o a n a l y s i s and i o n e t c h i n g . Full operation
o f t h e m i c r o s c o p e i s a v a i l a b l e o n t h e h e a t e d s p e c i m e n s and a l l t h e
m i c r o g r a p h s and a n a l y t i c a l d a t a p r e s e n t e d were t a k e n w i t h t h e
specimens a t t h e a p p r o p r i a t e r e a c t i o n t e m p e r a t u r e .
The s p e c i m e n i s in t h e f o r m o f a 25 um t h i c k f o i l . Three
m o u n t i n g s y s t e m s have b e e n u s e d :
(i) an e l e c t r i c a l l y heated p l a t e ,
(ii) direct resistive heating,
(iii) i n d i r e c t e l e c t r i c a l h e a t i n g in w h i c h t h e f o i l i s
s p o t - w e l d e d t o two D.C. h e a t e d c o n d u c t i n g w i r e s ( 1 1 ) .
f
Methods ( i ) and ( i i i ) g i v e u n i f o r m t e m p e r a t u r e s , b u t t h e h o t
1
plate i s more s u s c e p t i b l e t o t r a n s f e r o f i m p u r i t i e s . Method ( i i )
i n t r o d u c e s s t e e p t e m p e r a t u r e g r a d i e n t s b e t w e e n t h e c e n t r e and ends
of t h e f o i l , b u t p e r m i t s b o t h c a r b o n d i s s o l u t i o n ( i n t h e c e n t r e )
and c a r b o n p r e c i p i t a t i o n ( i n t h e c o o l e r r e g i o n s ) t o t a k e p l a c e
simultaneously. The c a r b o n d e p o s i t s t r u c t u r e i s i n d e p e n d e n t o f
t h e method u s e d .
Q u a n t i f i c a t i o n o f Auger d a t a c a n p r e s e n t problems on rough
s u r f a c e s , f o r example, a f t e r i o n e t c h i n g . To m i n i m i s e r o u g h n e s s

COKE FORMATION
AUGER DETECTOR IN
ANALYSIS POSITION
BEAM 5 1 0 " 10
- 5xlO" A 8
AUGER DETECTOR WITHDRAWN
GUNON<?' 2 T o
" 4 GUN OFF
Figure 1. Modes of operation of the cerl field emission source SEM with environ
mental cell. Key: top, scanning electron microscopy, Auger electron spectroscopy,
and argon ion etching; and bottom, gas reaction cell configuration.

e f f e c t s , areas are chosen f o r a n a l y s i s that are favourably o r i e n t e d

to the CMA. Ion etching introduces f u r t h e r d i f f i c u l t i e s .
Sputtered m a t e r i a l can be spread over the s u r f a c e , and s e l e c t i v e
e t c h i n g e f f e c t s can i n f l u e n c e the measured compositions. These
e f f e c t s w i l l be discussed f u r t h e r in the r e s u l t s s e c t i o n .
Estimates of the depth of m a t e r i a l removed from the surface by i o n
e t c h i n g are based on measurements of the height r e d u c t i o n of r e a l
features and are regarded as more accurate than values c a l c u l a t e d
from published sputter r a t e s .
The experimental procedure can be understood by reference to
the Fe-C phase diagram, Figure 2. The specimen i s reacted with
methane at temperatures of 750-850C. Carbon d i s s o l v e s in the
metal u n t i l the s a t u r a t i o n s o l u b i l i t y has been exceeded at the
gamma-Fe/Fe3C phase boundary, or a l t e r n a t i v e l y the specimen i s
cooled to a temperature belo th iron-carbo e u t e c t o i d (721C
738C). The s o l i d and dotte
a l t e r n a t i v e iron-Fe3C an
respectively. E i t h e r method produces s i m i l a r r e a c t i o n products but
the isothermal experiment i s p r e f e r e a b l y c a r r i e d out at higher
pressures, e.g. 50 T o r r , to minimise run times.
P o l y c r y s t a l l i n e i r o n f o i l (99.999% quoted p u r i t y ,
ex-Johnson-Matthey) was used so that any s p e c i f i c a c t i v i t y of the
g r a i n boundary i n t e r s e c t i o n s at the surface would be apparent. The
gas was B.O.C. L t d . research grade, used without f u r t h e r
purification.
Results
Surface P r e p a r a t i o n . In the "as r e c e i v e d " c o n d i t i o n the metal

f o i l i s covered with an oxide l a y e r and has extensive surface
damage from the r o l l i n g process, Figure 3a. Ion e t c h i n g i s
r e q u i r e d to remove the cold-worked l a y e r and the oxide, and i t
introduces c h a r a c t e r i s t i c etch s t r u c t u r e s dependent on i o n beam
incidence angle, c r y s t a l o r i e n t a t i o n and r e l a t i v e s p u t t e r y i e l d s
of contaminants. The cone type features in the foreground of
Figure 3b are o f t e n regarded as the p r i n c i p a l i o n etch s t r u c t u r e s ,
but our experience suggests that the stepped s t r u c t u r e s shown are
e q u a l l y probable. In Figure 3b a treatment of 10^ uA-mins has
removed ^2 urn of the s u r f a c e . I t i s necessary to thermally anneal
to remove the i o n etch damage, Figure 3c and 3d. Several i o n
etching-thermal annealing c y c l e s may be needed to remove i m p u r i t i e s
that segregate to the s u r f a c e from the bulk metal, e.g. sulphur.
Annealing at 850C f o r at l e a s t 15 hours i s r e q u i r e d to produce
a c l e a n surface that would be thermally s t a b l e at the r e a c t i o n
temperature f o r long periods in the absence of r e a c t i o n .
A f t e r the p r e p a r a t i v e treatment, the metal has r e c r y s t a l l i s e d
i n t o a few l a r g e g r a i n s , but i s r i p p l e d from the remains of former
g r a i n boundaries, Figure 4a. The g r a i n boundary i n t e r s e c t i o n s at
the surface are thermally grooved and e x h i b i t a c h a r a c t e r i s t i c
rounded p r o f i l e , Figure 4b( 12). The p r o f i l e and step d e n s i t i e s of

198 COKE FORMATION
0-5 1-0
CARBON,WT %
Figure 2. The iron-carbon phase diagram (part), with the dissolution and precipi-
tation regions used in this work. Key: , Fe-cementite; and , Fe-graphite.

Figure 3. Surface preparation of the poly crystalline iron foil as received, with
damage from cold work (a), ion etched, to remove ~2 / of metal (b) after anneal
ing for 2 hat 500C to remove etch structure (c), and development of step structure
after further annealing for 3 hat 600 C (d).

200 COKE FORMATION
Figure 4. Structure of as prepared iron foil. Key: a, grain structure after high
temperature annealing at 850 C; b, typical step structure at a thermal groove; and
c, terrace structure developed at sites away from grain boundaries.

t h e g r o o v e s change o n e x p o s u r e t o m e t h a n e , b e f o r e a n y c a r b o n i s
deposited(13). Elsewhere on the s u r f a c e t e r r a c e s t r u c t u r e s develop
d u r i n g a n n e a l i n g , a t l o w t e m p e r a t u r e s , F i g u r e 3d and a f t e r t h e f i n a l
h e a t t r e a t m e n t ( F i g u r e 4 c ) w i t h t y p i c a l s t e p h e i g h t s o f ^0.2 um
and t e r r a c e w i d t h s o f ^0.4 um in t h e l a t t e r c a s e .
Carbon P r e c i p i t a t i o n and R e - s o l u t i o n . I f carbon i s d i s s o l v e d

in t h e i r o n f o i l a t 750C and t h e n p r e c i p i t a t e d b y c o o l i n g t o
620C, i t f o r m s r a p i d l y o n some g r a i n s w h i l s t o t h e r s r e m a i n
u n a f f e c t e d , F i g u r e 5 a . The s t e p p e d s t r u c t u r e i s smoothed in t h e
a r e a s o f h e a v i e s t p r e c i p i t a t i o n ( A r e a A, F i g u r e 5 a ) l e a v i n g a
1 f
laminar carbon l a y e r w i t h a p o l y g o n i s e d r i d g e s t r u c t u r e t h a t has
b e e n n o t e d p r e v i o u s l y in t h i s and o t h e r d e p o s i t i o n s y s t e m s
( 1 , 2, 14, 1 5 ) . Some i n t e r m e d i a t e z o n e s a r e e v i d e n t where t h e
t e r r a c e w i d t h and s t e p h e i g h t s have i n c r e a s e d ; A r e a F i g u r e 5 a
S t e p h e i g h t s in t h e c a r b o
and 500-1500 % in t h e i n t e r m e d i a t
The s c a n n i n g A u g e r map f o r c a r b o n , F i g u r e 5 c , c o n f i r m s t h e
a b s e n c e o f p r e c i p i t a t i o n in t h e f a c e t t e d r e g i o n s o f F i g u r e 5 b .
Changes in t h e s t e p s t r u c t u r e o c c u r r i n g b e f o r e a l a m i n a r c a r b o n
f i l m a p p e a r s ( l o w e r l e f t in F i g u r e 5 b ) a r e shown in t h e A u g e r map
t o be a s s o c i a t e d w i t h c a r b o n . Extended areas covered w i t h t h e
l a m i n a r c a r b o n f i l m , F i g u r e 5 a , a r e common b u t a r e n o t t h e o n l y
form o f carbon p r e c i p i t a t e . I n some a r e a s , m o u n d - l i k e g r o w t h s
d e v e l o p , F i g u r e 6. S t r u c t u r a l changes c o n t i n u e f o r s e v e r a l h o u r s
a f t e r a p r e c i p i t a t e has appeared. Carbon covered zones spread
l a t e r a l l y i n t o c a r b o n f r e e a r e a s , F i g u r e 7. P r e v i o u s measurements
showed t h a t t h e l a t e r a l g r o w t h f o l l o w e d a t i power l a w , w h i c h f o r
p r o c e s s e s s u c h as t h e r m a l g r o o v i n g i s i n d i c a t i v e o f mass t r a n s p o r t
r a t e c o n t r o l by s u r f a c e d i f f u s i o n Q 3 ) .
I f t h e carbon p r e c i p i t a t e s are r e - d i s s o l v e d by i n c r e a s i n g t h e
t e m p e r a t u r e above t h e Fe-C e u t e c t o i d , t h e n r e c r y s t a l l i z a t i o n t o
f o r m a new g r a i n s t r u c t u r e o c c u r s , a c c o m p a n i e d b y f a c e t t i n g in
most a r e a s , F i g u r e 8 a , b , c . A f t e r a n o t h e r c o o l i n g i n d u c e d
p r e c i p i t a t i o n a t 620C, t h e same f i e l d o f v i e w now h a s i s o l a t e d
mound t y p e p r e c i p i t a t e s f o r m i n g , F i g u r e 8 d , e , as i n d i c a t e d b y t h e
arrows. The o r i g i n a l g r a i n s t r u c t u r e , as in F i g u r e 8 a , i s n o t
re-established. The o v e r a l l t e n d e n c y f r o m r e p e a t e d d i s s o l u t i o n
and p r e c i p i t a t i o n c y c l e s i s t o d i s o r d e r t h e s u r f a c e and p r o d u c e
p a r t i c u l a t e m a t e r i a l (1 3 ) .
C a r b o n Mound G r o w t h s . The d i s s o l u t i o n - p r e c i p i t a t i o n c y c l i n g
- e x p e r i m e n t s above s u g g e s t t h a t t h e c a r b o n mounds a r e a s s o c i a t e d
w i t h s t r u c t u r a l changes in t h e u n d e r l y i n g m e t a l . I f these deposits
a r e f o r m e d c o n t i n u o u s l y in t h e d e p o s i t i o n r e a c t i o n , f o r e x a m p l e
u s i n g t h e t h e r m a l m i g r a t i o n method d e s c r i b e d in S e c t i o n 2, c o n
s i d e r a b l e areas o f the s u r f a c e a r e covered w i t h the p r e c i p i t a t e
b u t a l i m i t t o g r o w t h i s r e a c h e d w i t h some o f t h e m e t a l s u r f a c e
s t i l l exposed. I n F i g u r e 9, t h e p r o j e c t e d a r e a o f c a r b o n mounds
on t h e s u r f a c e does n o t c h a n g e w i t h i n c r e a s e d methane e x p o s u r e ,

202 COKE FORMATION
Figure 5. Iron foil after carbon precipitation at 620C. Key: a, laminar carbon
film, region A, and carbon free regions C; b, carbon precipitated regions, facetted
carbon free regions, and intermediate stepped zone; and c, carbon Auger map of
area in b, (KLL 271 eV).

BROWN AND HILL Carbon Deposit Morphologies 203
Figure 6. Mound-type carbon growths formed by precipitation at 620C after

prior methane exposure of 12 torr h at 750C. Key: a, surface after 10 min; and
b, same view after 1 h.

204 COKE FORMATION
Figure 7. Lateral spreading of carbon precipitate zone into adjacent carbon-free

area. Key to time after cooling to 600C: a, 18 h; b, 44 h; and c, 136 h.

Figure 8. Carbon dissolution and reprecipitation. Key: a, as precipitated at

620C; b, same site as (a) after dissolution at 750C for 15 min; c, further dissolu-
tion 20 min at 750C; d, same site after cooling for 15 min at 620C; and e,
precipitation product after 47 min at 620C.

206 COKE FORMATION
Figure 9. Typical mound carbon deposits formed at 720C. Key: a, initial island
areas of mounds; and b, same area after further methane exposure for 170 torr h
with carbon dissolved at 800C.

although the height o f the mound features increases due to

processes o c c u r r i n g in the s u b s t r a t e . The growth k i n e t i c s f o l l o w
a d i r e c t l o g a r i t h m i c r a t e law
AW = k log(t + t ) - k log(t. + t )
O 1 0
where AW = carbon uptake, t = i n d u c t i o n p e r i o d to d e p o s i t i o n , t Q
i s an a r b i t r a r y constant, and k i s the r a t e constant. Such

k i n e t i c s can be derived on the b a s i s of a f i x e d number of surface
s i t e s or a c t i v e area a v a i l a b l e f o r d e p o s i t i o n , which decreases
e x p o n e n t i a l l y during the course of the r e a c t i o n . The r a t e at any
time t depends on the amount of a c t i v e area remaining(16).
Under the argon i o n beam (4 KeV), carbon etches more slowly
than the surrounding metal, as expected from the r e l a t i v e s p u t t e r
y i e l d s (17). The ridge
more r a p i d l y than the surroundin
channels in the s u r f a c e , p o s s i b l y because they present a more
favourable o r i e n t a t i o n to the i o n beam. Heavier e t c h i n g
(12325 uAmins) exposes the i n t e r f a c e between the carbon cap and
the s u b s t r a t e , Figure 10b. Auger spot and l i n e scan analyses have
been made on the substrate and s i d e o f the mound as exposed by i o n
e t c h i n g , and on the mound top, Figure 11. The micrograph in
Figure 11b i s s l i g h t l y defocussed to provide s u f f i c i e n t Auger
s i g n a l ( 1 1 ) . The l i g h t band in the middle of Figure 11b shows
m a t e r i a l in the s i d e of the mound. There i s no i n d i c a t i o n of a
compositional d i s c o n t i n u i t y at the boundary between the carbon cap
and i t s s u b s t r a t e . The carbon content i s low (<10 At%) in the
surrounding metal, but r i s e s continuously in the substrate of the
mound. At the i n t e r f a c e the concentrations are Fe = 72 A t % ,
C = 23 At%, which approximates to the cementite-Fe3C composition.
This apparent c o r r e l a t i o n should be t r e a t e d with c a u t i o n because
there i s no microscopic evidence o f a separate phase immediately
below the carbon zone and there i s a continuous compositional
v a r i a t i o n both above and below the i n t e r f a c e . The surface of an
unetched mound has t y p i c a l i r o n concentrations of 0-3 At%. In the
mound of Figure 11, a f t e r removal of ^0.25 um of carbon, the i r o n
content i s ^28 At%. This value could be s p u r i o u s l y high i f i r o n
from the surrounding areas has contaminated the s u r f a c e during i o n
etching. Iron contamination i s more l i k e l y i f bare metal i s
exposed between the carbon mounds by e t c h i n g as in t h i s case.
P a r t i c u l a t e Development: C r y s t a l l i n e P a r t i c l e s . P a r t i c u l a t e
m a t e r i a l i s f i r s t detected in areas between the carbon mounds
a f t e r l a t e r a l growth of the mounds has ceased, Figure 9b. Two
types of p a r t i c u l a t e e v e n t u a l l y develop, v i z
( i ) c r y s t a l l i n e deposits between the mounds, and
(ii) agglomerates of smaller p a r t i c l e s , p o s s i b l y
amorphous m a t e r i a l , formed at i s o l a t e d s i t e s
on the carbon l a y e r , Figure 12.
The c r y s t a l l i n e deposits have p a r t i c l e s i z e s t y p i c a l l y in the s i z e

208 COKE FORMATION
Figure 10. Structure of carbon mounds after ion etching. Conditions: a, 1,325
min; b, 12,325 min. White markers show position of interface.

10. BROWN A N D HILL Carbon Deposit Morphologies 209

210 COKE FORMATION
Figure 12. Initial development of particulates between the mound growths.

Methane exposure 406 torr h at 800C.

r a n g e 1 um t o 4 um. M o s t have some a n g u l a r f a c e t s , F i g u r e 1 3 a ,

and a f e w a p p r o a c h a n e q u i l i b r i u m s h a p e , F i g u r e 13b. A number o f
d i f f e r e n t c r y s t a l h a b i t s have b e e n o b s e r v e d i n c l u d i n g o c t a h e d r a l
and c u b i c s t r u c t u r e s . I n some a r e a s t h e p a r t i c l e s a r e o b s e r v e d t o
have p e n e t r a t e d t h e l a m i n a r c a r b o n l a y e r , F i g u r e 1 3 c .
Auger a n a l y s i s o f t h e c r y s t a l l i n e p a r t i c l e s , a f t e r i o n
e t c h i n g t o r e v e a l s t r u c t u r e , i s g i v e n in F i g u r e 14. I n i t i a l l y a l l
a r e a s r e v e a l h i g h c a r b o n c o n c e n t r a t i o n s , e . g . >85%, b u t a f t e r
l i g h t e t c h i n g g r e a t l y i n c r e a s e d i r o n l e v e l s (^50 A t % ) a r e d e t e c t e d
on c r y s t a l A, F i g u r e 14. W i t h c o n t i n u e d e t c h i n g t h e c a r b o n c o n
centration increases again suggesting that the carbide i s
decomposed u n d e r t h e i o n beam and t h e i r o n component i s s e l e c t i v e l y
removed. R e g i o n C, F i g u r e 14, d i s p l a y s a h i g h c a r b o n c o n t e n t
b e c a u s e i t h a s b e e n p r o t e c t e d f r o m t h e i o n beam b y t h e o v e r l y i n g
m a t e r i a l in r e g i o n B. Th c o m p o s i t i o f c r y s t a l A correspond t
a s t o i c h i o m e t r y o f FeC
later. The c o m p o s i t i o n
F i g u r e 1 2 , shows t h e i r o n c o n t e n t i n c r e a s i n g w i t h t h e amount o f
ion etching. The a n a l y t i c a l e r r o r ^ q u o t e d in F i g u r e 14 r e f e r s t o
r e p r o d u c i b i l i t y , and does n o t i n d i c a t e t h e m a g n i t u d e o f t h e
p o s s i b l e i o n beam e f f e c t s d i s c u s s e d a b o v e . When t h e c r y s t a l l i n e
m a t e r i a l i s grown i s o t h e r m a l l y , r a t h e r t h a n p r e c i p i t a t e d b y
c o o l i n g , considerable m o b i l i t y o f the surface l a y e r s i s observed
d u r i n g t h e in-cell e x p e r i m e n t s a t methane e x p o s u r e s in t h e r a n g e
600-2000 T o r r . h a t 750-800C. The m o b i l e m a t e r i a l c a n d e v e l o p
i n t o e x t e n d e d n e t w o r k s o f d e p o s i t , F i g u r e 15. However, t h e o v e r a l l
t r e n d in t h e r e a c t i o n i s t o w a r d s t h e f o r m a t i o n o f t h e i s o l a t e d
c r y s t a l l i n e t y p e o f p a r t i c u l a t e d e p o s i t , F i g u r e s 13 and 14.
Energy d i s p e r s i v e X-ray a n a l y s i s confirms t h a t both types o f
p a r t i c u l a t e m a t e r i a l c o n t a i n i r o n , F i g u r e 16. The a b s e n c e o f a n
Fe s i g n a l f r o m t h e s u r r o u n d i n g l a m i n a r c a r b o n i n d i c a t e s t h a t
i t s l a y e r t h i c k n e s s in t h i s r e g i o n i s M t o 2 urn, in agreement w i t h
t h e v a l u e e s t i m a t e d f r o m t h e e t c h e d mounds.
1 1 1
P a r t i c u l a t e Development: ' C o r e and S h e l l Type P a r t i c l e s
and F i l a m e n t a r y D e p o s i t s . These p a r t i c l e s a r e i d e n t i f i e d by
1 1 1
the s t r o n g l y e l e c t r o n e m i t t i n g ' c o r e surrounded by a s h e l l o f
l o w e r e m i s s i o n , F i g u r e 17a,b. The Fe X - r a y map, F i g u r e 1 7 c ,
1
c l e a r l y shows t h e ' c o r e m a t e r i a l t o c o n t a i n i r o n . Auger a n a l y s i s
of unetched c l u s t e r s o f t h e p a r t i c l e s gives carbon contents f o r
t h e s h e l l s o f 91 t o 96 A t % , w h i c h i s c o m p a r a b l e t o t h e l a m i n a r
carbon f i l m s . T y p i c a l o v e r a l l d i a m e t e r s a r e in t h e r a n g e 0.3 urn
1
t o 0.6 um. 'Shell t h i c k n e s s e s a r e e s t i m a t e d t o be ^0.1 um.
As d e p o s i t i o n c o n t i n u e s , t h e l a m i n a r c a r b o n f i l m o n t h e mounds
becomes c o v e r e d w i t h p a r t i c u l a t e s and a t t h e s t a g e where t h e m e t a l
s t r u c t u r e b r e a k s down c o m p l e t e l y , t h e mounds a r e u n d e t e c t a b l e .
Heavy d e p o s i t i o n i n v o l v e s o n l y t h e f o r m a t i o n o f p a r t i c u l a t e s ,
F i g u r e 1 8 a . The s u r f a c e s o f t h e p a r t i c l e s a p p e a r t o have a c t i v e
s i t e s f o r t h e development o f f u r t h e r p a r t i c u l a t e m a t e r i a l .

212 COKE FORMATION
Figure 13. Typical particulate deposits. Key: a, larger crystalline particles, and
agglomerations of smaller particles after 10,120 torr h methane; b, development of
stable crystal habit; and c, particulate material breaking through laminar carbon
film.

REGION MEAN COMPOSITIONS

%C %Fe
A
( 0.2 m removed) 58 42
A
( 0.5 m removed)
48 52
63 37
C 71 29
ADJACENT MOUND
(not shown)
0.02 m removed

93 7
0.2 M m removed 89 11
all analyses 1 2 % AUGER ANALYSIS
Figure 14. Ion etched Fe/C crystals with Auger analysis of selected areas. Methane
exposure 406 torr h at 800C.

214 COKE FORMATION
Figure 15. Coalescence of Fe/C crystals to form extended networks of deposit

between the carbon mound growths. Methane exposure 900 torr h at 780C.
Figure 16. Two types of particulate deposit surrounded by a laminar carbon

layer (left) and iron K X-ray map (primary beam energy = 10 KeV) (right).
a

Figure 17. Core/shell type particles. Methane exposure 10,120 torr h at 780C.
Key: a, cluster of particles at a growth site; b, individual particle cores in a cluster;
and c, iron K X-ray map of area in b (primary beam energy 10 KeV).
a

216 COKE FORMATION
Figure 18. Particulate structure developed when the iron foil is reacted to the
stage of structural breakdown (a), filaments and two types of Fe/C particulate
material (A and B) (b), and filaments composed of small particles (c). Methane expo-
sure 10,120 torr h at 780C.

O n l y a l i m i t e d amount o f f i l a m e n t a r y m a t e r i a l i s f o r m e d ,
F i g u r e 18b and c. The f i l a m e n t s shown in F i g u r e 18b a r e s i m i l a r
t o those r e p o r t e d f o r o t h e r systems, e.g. N 1 / C 2 H 2 , h a v i n g s i n g l e
m e t a l p a r t i c l e s c o n t a i n e d in t h e h e a d ( 4 ) . However, t h e m a j o r i t y
o f f i l a m e n t s w e r e composed e n t i r e l y o f p a r t i c u l a t e m a t e r i a l
( F i g u r e 18c) w i t h i r o n d i s t r i b u t e d t h r o u g h o u t t h e s t r u c t u r e ,
Figure 19. I n n e i t h e r c a s e was i t p o s s i b l e t o a s s o c i a t e t h e
f i l a m e n t growth s i t e w i t h a s p e c i f i c type o f p a r t i c l e .
Discussion
The I n f l u e n c e s o f M e t a l S t r u c t u r e . The f o r m a t i o n o f a
continuous laminar carbon f i l m over extended areas o f t h e surface
a p p e a r s t o be a c h a r a c t e r i s t i c o f p r e c i p i t a t i o n o n a w e l l - a n n e a l e d
metal. Structural disorde b introduced b successiv
dissolution-precipitatio
zone o n n o n - a n n e a l e d m a t e r i a l
o f t h e mound-type o f d e p o s i t i s e x p e c t e d , w h i c h h a s a c a r b o n o v e r -
l a y e r i d e n t i c a l t o the continuous laminar carbon l a y e r .
Changes in t h e m e t a l s t r u c t u r e o c c u r d u r i n g a c o o l i n g i n d u c e d
p r e c i p i t a t i o n b e c a u s e t h e m e t a l t r a n s f o r m s f r o m t h e -(face
c e n t r e d c u b i c ) t o t h e a-(body c e n t r e d c u b i c ) i r o n l a t t i c e .
P r e c i p i t a t i o n a t 620C, F i g u r e s 5 t o 7, t a k e s p l a c e a t t h e o n s e t
t e m p e r a t u r e f o r r e c r y s t a l l i z a t i o n , i . e . 0.4 x Tm (Tm = m e l t i n g
point). I t i s n o t s u r p r i s i n g , t h e r e f o r e , t h a t t h e m e t a l undergoes
a r a d i c a l change in g r a i n s t r u c t u r e . U s i n g t h e r e s i s t i v e h e a t i n g
t e c h n i q u e s (method ( i i ) , S e c t i o n 2 ) , t h e m e t a l u n d e r g o e s a n -
t r a n s f o r m a t i o n in t h e h o t z o n e as c a r b o n d i s s o l v e s and t h e c o n
c e n t r a t i o n r i s e s above t h e -phase b o u n d a r y , F i g u r e 2. Initially
p r e c i p i t a t i o n in t h e c o l d zone t a k e s p l a c e in -Fe, b u t i t i s
l i k e l y t h a t t h e h i g h e m i s s i v i t y o f t h e d e p o s i t p r o d u c e s some
l o c a l i s e d c o o l i n g , w h i c h w o u l d move t h e p r e c i p i t a t i o n zone t o w a r d s
the h o t t e r c e n t r a l r e g i o n o f t h e specimen as t h e r e a c t i o n p r o c e e d s .
S u b s e q u e n t p r e c i p i t a t i o n c o u l d be t a k i n g p l a c e in a z o n e t h a t h a s
u n d e r g o n e a n > > c h a n g e , and t h e c o n s e q u e n t d i s o r d e r in t h e
m e t a l w o u l d c o n t r i b u t e s i g n i f i c a n t l y t o f o r m i n g t h e mound-type
d e p o s i t s , F i g u r e s 9 and 12. A s i m i l a r t y p e o f d e p o s i t was
r e p o r t e d p r e v i o u s l y , a l t h o u g h u n d e r c o n d i t i o n s in w h i c h t h e
s p e c i m e n was c o o l e d t o a m b i e n t t e m p e r a t u r e p r i o r t o SEM
e x a m i n a t i o n , w h i c h may have i n t r o d u c e d s t r u c t u r a l c h a n g e s a f t e r
t h e d e p o s i t i o n e x p e r i m e n t had f i n i s h e d ( 1 8 ) .
The s l o w e r changes o b s e r v e d as a s p r e a d i n g o f t h e i s l a n d
c a r b o n z o n e s may a r i s e b e c a u s e t h e t r a n s f o r m a t i o n does n o t
go t o c o m p l e t i o n in a l l a r e a s . The l a t e r a l s p r e a d i n g ( F i g u r e 7)
c o u l d be a s s o c i a t e d w i t h r e t a i n e d -Fe b e i n g s l o w l y i n c o r p o r a t e d
in t h e a d j a c e n t -matrix w i t h t h e r e j e c t i o n o f more c a r b o n t o t h e
surface.

218 COKE FORMATION
Figure 19. Filament composed of Fe/C particles (a), and iron K X-ray map
(primary beam energy 20 KeV)(b).

The D e v e l o p m e n t o f Mound G r o w t h s . The mound c a r b o n e n c a p

s u l a t e s t h e m e t a l and p r e v e n t s i t f r o m t a k i n g p a r t in t h e r e a c t i o n
u n t i l p a r t i c u l a t e growth has caused s u b s t a n t i a l break-up o f t h e
bulk metal. S i m i l a r t y p e s o f d e p o s i t h a v e b e e n r e p o r t e d in t h e
N 1 / C 2 H 2 r e a c t i o n a t 990C and F e / C H 4 s y s t e m a t 1100C(j_9). A
r e d u c t i o n in r e a c t i v i t y c a u s e d b y e n c a p s u l a t i o n was r e p o r t e d f o r
the F e / C 3 H 5 d e p o s i t i o n r e a c t i o n ( 2 0 )
The r e a s o n s f o r t h e l i m i t a t i o n o n t h e g r o w t h o f mound
deposits i s not y e t c l e a r . The amount o f c a r b o n f o r m e d depends o n
t h e amount i n i t i a l l y in s o l u t i o n in t h e m e t a l ( 1 6 ) . Precipitation
can proceed a c c o r d i n g t o t h e s t a b l e i r o n - g r a p h i t e o r t h e meta-
s t a b l e i r o n - i r o n c a r b i d e p h a s e d i a g r a m s ( b o t h a r e s u p e r i m p o s e d in
Figure 2). I t i s proposed t h a t t h e c a r b o n f i l m i s n o t formed over
the e n t i r e s u r f a c e because c a r b i d e p r e c i p i t a t e s a r e n u c l e a t i n g
w i t h i n t h e m e t a l in som competin in
solution. Growth o f t h
during this carbide nucleatio stage Eventually, crysta
g r o w t h becomes s u f f i c i e n t l y r a p i d f r o m t h e a v a i l a b l e c a r b o n in
s o l u t i o n t h a t t h e r a t e o f growth o f t h e laminar carbon on t h e
mounds d e c r e a s e s .
A number o f q u e s t i o n s o n t h e c o m p o s i t i o n o f t h e c a r b o n mounds
remain unanswered. I t i s n o t c l e a r w h e t h e r t h e c a r b o n cap c o n t a i n s
i r o n w i t h t h e c o n c e n t r a t i o n i n c r e a s i n g w i t h depth from the s u r f a c e ,
o r w h e t h e r t h e i r o n p r e s e n t ( F i g u r e 11) h a s b e e n d e p o s i t e d b y t h e
sputtering process. The o u t e r s u r f a c e o f t h e u n e t c h e d d e p o s i t
u s u a l l y c o n s i s t s o f 98-100 A t % c a r b o n . The c o m p o s i t i o n o f t h e
m a t e r i a l u n d e r t h e cap i s a l s o u n c e r t a i n ; t h e v a l i d i t y o f t h e
observed carbon p r o f i l e r e q u i r e s c o n f i r m a t i o n .
The c a r b o n l a y e r c o m p o s i n g t h e c a p i s s t r o n g l y a d h e r e n t .
T h e r e i s no e v i d e n c e o f s p a l l a t i o n d u r i n g i o n e t c h i n g a s w o u l d be
p o s s i b l e i f t h e r e was a n a b r u p t c o m p o s i t i o n a l change a t t h e
interface.
P a r t i c u l a t e and F i l a m e n t a r y G r o w t h . I t i s i m p l i c i t in t h e
m e c h a n i s m p r o p o s e d above f o r c a r b o n mound g r o w t h , t h a t t h e c r y s t a l
l i n e p a r t i c u l a t e s are nucleated at a c t i v e s i t e s w i t h i n the metal.
The e v i d e n c e t h a t f u r t h e r g r o w t h c a u s e s t h e p a r t i c l e s t o be
e j e c t e d t h r o u g h l a m i n a r c a r b o n o v e r l a y e r i s g i v e n in F i g u r e 1 3 c .
The m e c h a n i s t i c s t e p s r e q u i r e d f o r c a r b i d e p a r t i c l e g r o w t h a r e
solution

diffusion to active sites
\
nucleation
\
precipitation
r a t h e r than a d i r e c t gas-phase a t t a c k a t t h e m e t a l s u r f a c e .
Auger a n a l y s i s o f t h e c r y s t a l l i n e d e p o s i t , F i g u r e 14, s u g g e s t s

220 COKE FORMATION
t h a t i t i s a c a r b i d e w i t h t h e f o r m u l a FeC. A carbide with this

c o m p o s i t i o n was r e p o r t e d t o be f o r m e d in F i s h c h e r - T r o p s c h h y d r o -
carbon s y n t h e s i s ( 2 1 ) , but l a t e r work c l a i m e d t h a t the t r u e
s t o i c h i o m e t r y was FeyC3 ( 2 2 ) . F i r m c o n c l u s i o n s on t h e c o m p o s i t i o n
w i l l n o t be p o s s i b l e u n t i l t h e p r o b l e m s s u r r o u n d i n g A u g e r m e a s u r e -
ments on i o n e t c h e d s u r f a c e s have b e e n r e s o l v e d .
1 1
The ' c o r e and ' s h e l l t y p e o f p a r t i c u l a t e s a r e s i m i l a r t o one
o f t h e d e p o s i t m o r p h o l o g i e s f o r m e d on an F e - N i a l l o y f r o m CO a t
t e m p e r a t u r e s above 500C where t h e ' c o r e ' c o n s i s t e d o f a m e t a l
p a r t i c l e in t h e s i z e r a n g e 0.09 t o 0.2 um, w i t h a ' s h e l l ' t h i c k n e s s
t y p i c a l l y o f 0.04 um(_23). The s t r u c t u r e o f t h e p a r t i c l e s , i . e . a
c a r b o n l a y e r on m e t a l , i s c o m p a r a b l e t o t h e l a m i n a r f i l m on t h e
m e t a l , s u g g e s t i n g t h a t t h e c a r b o n in t h e s h e l l has b e e n
precipitated. F r e e m e t a l p a r t i c l e s have n o t b e e n o b s e r v e d on t h e
i r o n f o i l s t h a t c o u l d s e r v e as a c t i v e c e n t r e s f o r g r o w t h d i r e c t l y
f r o m t h e gas p h a s e . T h e r e f o r e
s o l u t i o n - p r e c i p i t a t i o n proces
f i n a l morphology of the ' c o r e ' / ' s h e l l ' p a r t i c l e s , but f u r t h e r
d e t a i l s o f t h e m e c h a n i s m o f g r o w t h c a n n o t be e s t a b l i s h e d a t
present.
The i n i t i a l p a r t i c u l a t e d e p o s i t s c a n a c t as a s u b s t r a t e f o r
the development o f f u r t h e r p a r t i c u l a t e m a t e r i a l . I n s p i t e o f t h i s
h i g h a c t i v i t y , t h e f a c t t h a t many p a r t i c l e s a r e o f a s u i t a b l e s i z e
f o r i n c o r p o r a t i o n i n t o f i l a m e n t s , i . e . 0.01-1 uni, and t h e l a r g e
q u a n t i t y and h i g h a r e a o f p a r t i c l e s , v e r y l i t t l e f i l a m e n t a r y
c a r b o n i s f o r m e d . P r e v i o u s r e p o r t s have i n d i c a t e d t h a t t h e r e i s
d i f f i c u l t y in f o r m i n g f i l a m e n t s f r o m m e t h a n e ( 2 4 ) . I t has b e e n
suggested t h a t f i l a m e n t s are formed o n l y from h i g h e r h y d r o c a r b o n
i m p u r i t i e s in t h e m e t h a n e ( 2 5 ) . Trace q u a n t i t i e s of higher hydro-
c a r b o n s c o u l d be f o r m e d by a F i s c h e r - T r o p s c h r e a c t i o n u s i n g i r o n
c a r b i d e in t h e d e p o s i t as a c a t a l y s t and h y d r o g e n r e l e a s e d f r o m t h e
CH4 d i s s o c i a t i o n d u r i n g d e p o s i t i o n . F a c t o r s s u c h as temperature,
p r e s s u r e , and r e s i d e n c e t i m e o f methane o v e r t h e d e p o s i t w o u l d be
i m p o r t a n t in d e t e r m i n i n g t h e q u a n t i t i e s o f h y d r o c a r b o n s f o r m e d .
The f a i l u r e o f p u r e methane t o f o r m f i l a m e n t s has b e e n a t t r i b u t e d
to the d e c o m p o s i t i o n b e i n g endothermic. I n a d d i t i o n to thermo-
d y n a m i c r e a s o n s , k i n e t i c f a c t o r s may f a v o u r t h e e n c a p s u l a t i o n o f
a c t i v e p a r t i c l e s , p a r t i c u l a r l y as in t h e s e e x p e r i m e n t s t h e c o n -
d i t i o n s a p p e a r t o be s u i t a b l e f o r t h e f o r m a t i o n o f a c a r b o n ' s h e l l ' .
The f a c t t h a t some f i l a m e n t s c o n s i s t o f an a g g l o m e r a t i o n o f
p a r t i c l e s i m p l i e s c o n s i d e r a b l e m o b i l i t y o f Fe/C s p e c i e s . Some
e v i d e n c e f o r m o b i l i t y i s shown in F i g u r e 15, where t h e c r y s t a l l i n e
d e p o s i t s have c o a l e s c e d i n t o e x t e n d e d n e t w o r k s .
A p p l i c a t i o n t o L e s s W e l l - d e f i n e d S u r f a c e s and R e a c t i o n
Conditions. I n a l l p r a c t i c a l s i t u a t i o n s where c a r b o n
d e p o s i t i o n p r e s e n t s p r o b l e m s , t h e a l l o y s u r f a c e i s n o t in a c o n -
d i t i o n comparable to t h a t prepared f o r these experiments. A
h e a v i l y c o l d - w o r k l a y e r w i l l be p r e s e n t c o v e r e d by an o x i d e f i l m ,
w h i c h i t s e l f may have a c o m p l e x c o m p o s i t i o n and s t r u c t u r e . The

m a i n p h y s i c a l e f f e c t o n d e p o s i t i o n i s t o p r o v i d e a more d i s o r d e r e d
s u r f a c e w h i c h w i l l i n h i b i t f o r m a t i o n o f an extended l a m i n a r carbon
film. The mound t y p e o f g r o w t h w o u l d be more common, and p a r t i c u
l a t e m a t e r i a l w o u l d become a v a i l a b l e a t a n e a r l i e r s t a g e o f t h e
reaction. I n the r e d u c i n g environment, the o x i d e f i l m w i l l
provide a source o f metal p a r t i c l e s . I nindustrial plant, a
methane a t m o s p h e r e i s l i k e l y t o y i e l d f i l a m e n t a r y d e p o s i t s b e c a u s e
of h i g h e r hydrocarbon i m p u r i t i e s p r e s e n t . Trace o x i d a n t s i n the
gas s t r e a m w o u l d i n h i b i t c a r b o n e n c a p s u l a t i o n p r o c e s s e s . Another
e f f e c t o f p r o t e c t i v e o x i d e f i l m s and o f t r a c e o x i d a n t s i n t h e g a s
w o u l d be t o r e d u c e t h e r a t e o f c a r b o n d i s s o l u t i o n ( 2 6 ) , t h u s
e x t e n d i n g the i n i t i a l i n d u c t i o n p e r i o d o f the r e a c t i o n . When t h e
m e t a l had become s a t u r a t e d i n c a r b o n , t h e same d e p o s i t g r o w t h
p r o c e s s e s w o u l d be e x p e c t e d , and p a r t i c u l a t e m a t e r i a l w o u l d
r a p i d l y d i s r u p t the oxid laye exposin th l furthe
rapid attack.
Conclusions
The r e s u l t s o f t h i s i n - s i t u SEM w o r k s u g g e s t t h a t s o l u t i o n -
p r e c i p i t a t i o n p r o c e s s e s have some p a r t i n t h e d e v e l o p m e n t o f f o u r
of the m o r p h o l o g i c a l types d i s c u s s e d , i . e . continuous laminar
c a r b o n f i l m s , mound g r o w t h s , and two t y p e s o f p a r t i c u l a t e m a t e r i a l .
A l t h o u g h a s m a l l amount o f f i l a m e n t a r y c a r b o n was o b s e r v e d , i t
does n o t a p p e a r t o be a m a j o r c h a r a c t e r i s t i c o f t h e Fe-CH4
reaction.
The n e x t p r i o r i t y i n f u t u r e w o r k s h o u l d be t o s t u d y t h e
g r o w t h mechanisms o f t h e p a r t i c u l a t e m a t e r i a l s . T h e i r development
r e p r e s e n t s t h e most r a p i d d e p o s i t i o n s t a g e o f t h e r e a c t i o n and i s
the route by which m e t a l l i c m a t e r i a l i s t r a n s f e r r e d t o the d e p o s i t .
Auger m i c r o a n a l y s i s i s p o t e n t i a l l y a v a l u a b l e t o o l f o r
e s t a b l i s h i n g c o m p o s i t i o n a l v a r i a t i o n s i n the d e p o s i t s , b u t
p r o b l e m s o f m a k i n g r e l i a b l e measurements o n i o n e t c h e d s u r f a c e s
needs r e s o l v i n g .
Acknowledgment
The w o r k was c a r r i e d o u t a t t h e C e n t r a l E l e c t r i c i t y R e s e a r c h
L a b o r a t o r i e s and i s p u b l i s h e d by p e r m i s s i o n o f the C e n t r a l
E l e c t r i c i t y Generating Board.
Literature Cited
1. Presland, A.E.B.; Walker, P.L. Carbon 1969, 7, 1

2. Brown, A.M.; Emsley,, A.M.; H i l l , M.P. "Gas Chemistry in
Nuclear Reactors and Large Industrial Plant"; Dyer, ., Ed.;
Heydon; London 1980, p.26
3. Baird, T. Carbon 1977, 15, 379

222 COKE FORMATION
4. Baker, R.T.K.; Harris, P.S. "Chemistry and Physics of Carbon";

Walker, P.L. J r . ; Thrower, P..; Eds.; Dekker; New York;
1978, 14, 83
5. Baker, R.T.K. "Chemistry and Physics of Solid Surfaces";
Vanselow, R.; Tong, S.Y.; Eds.; C.R.C. Press; Cleveland,
Ohio; 1979, p.293
6. Irvin, S.M.; Walker, P.L. Carbon 1967, 5, 399
7. Baird, T.; Fryer, J.R.; Grant, B. Carbon 1974, 12, 591
8. Bernardo, C.; Lobo, L.S. Carbon 1976, 14, 287
9. Walker, P.L. J r . ; Raksawski, J.F.; Imperial, G.R. J. Phys.
Chem. 1959, 63, 140
10. Baker, R.T.K.; Barber, M.A.; Feates, F.S.; Harris, P.S.;
Waite, R.J. J. Catalysis 1972, 26, 51
11. Brown, A.M.; H i l l , M.P. "Electron Microscopy and Analysis";
Institute of Physics Conf Series; 1980 52, 379
12. Gjostein, N.A. "Meta
Kinetics"; America y , , p.9
13. Brown, A.M.; H i l l , M.P. Carbon 1981, 19, 51
14. Presland, A.E.B.; Roscoe, C.; Walker, P.L. J r . Proc. 3rd Int.
Conf. on Industrial Carbon and Graphite; Society of Chemical
Industry, London; 1970
15. Blau, G.; Presland, A.E.B. Proc. 3rd Int. Conf. on Industrial
Carbon and Graphite; Society of Chemical Industry, London;
1970
16. Emsley, A.M.; H i l l , M.P. 14th Amer. Carbon Conf., Penn State
Univ. 1979, p.131
17. Franks, J. Advs. in Electronics and Electron Physics; 1978,
47, 1
18. Robertson, S.D. Carbon 1972, 10, 221
19. Derbyshire, F.J.; Trimm, D.L. Proc. 4th Conf. on Industrial
Carbon and Graphite, Society of Chemical Industry, London;
1974, paper 14
20. Cooper, B.J.; Trimm, D.L. Proc. 5th London Carbon and
Graphite Conf., Society of Chemical Industry; 1978, 2, 768
21. Eckstrom, H.C.; Adcock, W.A. J. Amer. Chem. Soc. 1950, 72,
1042
22. Herbstein, F.H.; Snyman, J.A. Inorganic Chem. 1964, 3, 894
23. Audier, M.; Guinot, J.; Coulon, M.; Bonnetain, L. Carbon 1981,
19, 99
24. Baker, R.T.K.; Harris, P.S.; Henderson, J.; Thomas, R.B.,
Carbon 1975, 13, 17
25. Evans, E.L.; Thomas, J.M.; Thrower, P..; Walker, P.L. J r .
Carbon 1973, 11, 441
26. Emsley, A.M.; H i l l , M.P. Carbon 1977, 15, 205

11
Inhibition by Sulfur Poisoning of the
Heterogeneous Decomposition of Acetone
M. J. BENNETT, G. H. CHAFFEY, B. L. MYATT, and D. R. V. SILVESTER
Materials Development Division, A E R E Harwell, Didcot, Oxon, 11 ORA,
United Kingdom
Inhibition by sulphur poisoning of carbon deposition

from the heterogeneous decomposition of acetone on an
oxidised 20% Cr/25
representative scal
Cr O ) has been studied. Two procedures examined
2 3
were prior sulphiding and the continuous addition of

sulphur compounds (thiophene, H S, SO and COS) 2 2
to the gas phase. Deposition on Fe O was 3 4
reduced, and in certain circumstances prevented, as

catalytic intermediate formation was inhibited either
by the preferential adsorption of the additives
poisoning surface sites or by oxide conversion to
Fe S.
1-N Sulphur poisoning did not inhibit acetone
decomposition by Cr . The oxide behaviour
2 3
reflected that of the oxidised 20/25/Nb steel.

Sulphiding reduced deposition for a limited period
until new catalytic intermediates were generated by
the simultaneous oxidation of the steel. A l l the
gaseous additives were effective by extents which
increased with their partial pressure.
The coolant f o r the UK advanced gas-cooled power reactors i s

carbon dioxide containing minor c o n t r o l l e d l e v e l s of carbon
monoxide, methane and water vapour. Radiation-induced degradation
of the carbon monoxide and methane can r e s u l t i n gas-phase
precursors, which i n turn can be decomposed c a t a l y t i c a l l y to
produce carbonaceous deposits on the o x i d i s e d 20% Cr-25% N i niobium
s t a b i l i s e d (20/25/Nb) a u s t e n i t i c s t a i n l e s s s t e e l f u e l cladding
surfaces (J^, 2). This deposit forms as f l o c c u l e n t aggregates of
interwoven f i l a m e n t s , and i r o n and n i c k e l are the p r i n c i p a l
m e t a l l i c constituents of the c a t a l y s t s involved. This type of
d e p o s i t i o n has been simulated out of reactor from the thermal
degradation of acetone both on the 20/25/Nb s t e e l and a range of
oxides (such as Cr203, Fe304 and other s p i n e l s ) (3) These
are the p r i n c i p a l c o n s t i t u e n t s of the scales formed on t h i s s t e e l
This chapter not subject to U.S. copyright.

Published 1982 American Chemical Society.

224 COKE FORMATION
during o x i d a t i o n in carbon dioxide over the temperature range of

interest. Filamentary deposit growth on metals and a l l o y s from
hydrocarbon degradation has been studied e x t e n s i v e l y (4) with a
common feature being the high c a t a l y t i c a c t i v i t y of the t r a n s i t i o n
elements. This i s a l s o one of the main types of carbonaceous de
p o s i t formed on ESC p y r o l y s i s tubes during cracking operations
<!>
Previous work (6) has i n d i c a t e d that carbon d i s u l p h i d e and
other sulphur compounds (hydrogen sulphide, e t h y l mercaptan,
t h i o g l y c o l l i c a c i d , a l l y l i s o t h i o c y a n a t e and t r i t h i o a c e t a l d e h y d e ) ,
at a 0.1% concentration, were e f f e c t i v e gas phase poisons of the
thermal decomposition of ketones on heated nickel-chromium heat
r e s i s t a n t a l l o y r e a c t i o n v e s s e l s . In a d d i t i o n , sulphur compounds
prevented the d e p o s i t i o n of carbon on i r o n and various s t e e l s by
the Boudouard r e a c t i o n (7)
two approaches to reduc
s t e e l , Fe304 and 0 ^ 0 3 have been examined. The f i r s t was p r e t r e a t -
ment to form a sulphide surface l a y e r , which could be l e s s
c a t a l y t i c a l l y a c t i v e . The second was to add a sulphur bearing
compound continuously to the gas phase, which would be adsorbed on
the a c t i v e surface s i t e s p r e f e r e n t i a l l y to acetone. The r e l a t i v e
e f f e c t i v e n e s s has been compared of hydrogen sulphide, sulphur
d i o x i d e , carbonyl sulphide and the h e t e r o c y c l i c sulphur c o n t a i n i n g
organic compound, thiophene. The l a t t e r was s e l e c t e d because f o r
some r e a c t i o n s the r e l a t i v e t o x i c i t y of a number of poisons, each
c o n t a i n i n g the same t o x i c atom, increased with the covering power
of the r e s p e c t i v e molecules, i . e . with the complexity of the chain
or r i n g attached to the t o x i c atom ( 8 ) .
Experimental
M a t e r i a l s . The 20/25/Nb s t a i n l e s s s t e e l specimens, with

dimensions 2 cm 1 cm, were cut from 250 t h i c k annealed s t r i p
with the a n a l y s i s and g r a i n s i z e given in Table I . The specimen
TABLE I - A n a l y s i s and G r a i n Size of 20/25/Nb S t a i n l e s s S t e e l
Wt.% ppm
Grain s i z e
um
Cr Ni Nb Si C S
19.8 22.6 0.9 0.70 0.56 400 100 18 - 25
surfaces were abraded with 600 g r i t s i l i c o n carbide paper and then

were o x i d i s e d , in carbon d i o x i d e , f o r 1000 h, at e i t h e r 600 or
700C. The oxygen uptakes by the i n d i v i d u a l specimens are given in

11. BENNETT ET AL. Inhibition by Sulfur Poisoning 225
Tables I I I and V. The Fe3^ powder was a composite of three

batches, prepared by the o x i d a t i o n of Johnson-Matthey s p e c t r o s c o p i c
grade i r o n sponge in dry carbon d i o x i d e , at 350-500C, f o r
2000-3000 h. A n a l y s i s and X-ray d i f f r a c t i o n (Table I I ) i n d i c a t e d
the presence of some Fe203, in a d d i t i o n to Fe304 The
C r
2 3 powder was a high p u r i t y grade ( > 99.999%) s u p p l i e d by
Koch-Light L t d . The surface areas of both oxides, a l s o given in
Table I I , were determined by the BET method from the n i t r o g e n
a d s o r p t i o n measurements, at 78K, using a Perkin-Elmer sorptometer.
TABLE I I - Analyses and Surface Areas of Fe^04 and Crg03
Analyses
Surface Area
Oxide
m
F e
0.61 71.5% 1.0% 20 ppm
34
C r
43.8 50 ppm 100 ppm 20 ppm
23
The thiophene was supplied by Koch L i g h t L t d . , while the other

sulphur bearing gases (hydrogen sulphide,sulphur dioxide and
carbonyl sulphide) were obtained from BOC ( S p e c i a l Gases) L t d .
Experimental Procedure. As gold does not c a t a l y s e acetone

decomposition, i t was used to f a b r i c a t e c r u c i b l e s (1 cm diam., 1 cm
high) f o r the containment of oxide specimens and as support wires
f o r the 20/25/Nb specimens. The oxide sample weight used was 50 mg.
The specimens were exposed in s i l i c a r e a c t i o n v e s s e l s .
Acetone at p a r t i a l pressures o f ^ 0.15 and 0.31 atm, was
?
introduced i n t o the carbon dioxide c a r r i e r gas by passage through a

bubbler at 0C and ambient temperature r e s p e c t i v e l y . The carbon
d i o x i d e pressure was 1 atm and i t s flow rate was 200 cc/min. For
the experiments in which thiophene was added to the gas, the
bubbler was charged with a mixture of acetone and thiophene.
Although the acetone p a r t i a l pressure in the gas phase was
maintained e f f e c t i v e l y constant, that of the thiophene was a l t e r e d
by changing the thiophene c o n c e n t r a t i o n in the bubbler. Hydrogen
s u l p h i d e , sulphur dioxide and carbonyl sulphide were added to the
carbon d i o x i d e c a r r i e r gas p r i o r to s a t u r a t i o n with acetone. The
p a r t i a l pressures of the r e s p e c t i v e c o n s t i t u e n t s , other than
sulphur d i o x i d e , both before and a f t e r the r e a c t i o n v e s s e l , were
measured by gas chromatography. The r e s p e c t i v e sulphur dioxide
concentrations were evaluated by gas a n a l y s i s , i n v o l v i n g a b s o r p t i o n
by hydrogen peroxide and subsequent sulphur determination by a
Technicon autoanalyser. There was no marked d e p l e t i o n in any

Table III - The Effect of Sulphiding Upon Carbon Deposition from Acetone on Oxidised 20/25/Nb Stainless Steel
Oxidation by 1st exposure to CO^ + acetone 2nd exposure to C0 + acetone

2
fi^S treatment
00 , 1000 h
2
(0.31 atm. pressure) (0.15 atm. pressure)
Sulphur remaining
after exposure
Deposition Weight Deposition to 00 + agetone
2
Weigjht Weight Carbon
Temp, Exposure Temp. Time Reduction Temp. Time gair^ Reduction mg/cm
gain 2
gain 2 uptake,
C Conditions C h Factor C h mg/cm Factor
mg/cm mg/cm mg/cm
(a) (b) (a)
700 0.095 24h, 20C N.M. 700 6 0.10 6-160 600 115 50.0 Nil N.D.
600 0.801 lh, 600C 0.113 600 7.5 0.18 4-270 600 28 2.08 Nil 0.120
115 0.13
700 0.0% lh, 600C 0.010 700 7 0.03 20-560 600 10-375 0.018
213 0.13

N.M. = none measurable N.D. = not determined
m

(a) The ratio of the extents of deposition on oxidised and sulphided 20/25/Nb stainless steel for similar conditions. The ^
former data are frcm reference (3). g
(b) Accumulative values for successive exposures. H

experiment of e i t h e r acetone or a sulphur-bearing gas c o n s t i t u e n t

across the r e a c t i o n v e s s e l . As a consequence only the i n l e t values
are quoted in Tables I I I - V I I I .
The d e p o s i t i o n k i n e t i c s were determined, e i t h e r d i s c o n t i n u -
ously by weighing the specimens a f t e r i n t e r m i t t e n t exposure, or
continuously by measuring the extension of a s i l i c a s p r i n g
balance.
Results
Sulphiding. Oxidised 20/25/Nb s t a i n l e s s s t e e l and FeÔ^

were sulphided by exposure to hydrogen sulphide, e i t h e r f o r 24 h at
room temperature or f o r 1 h at 600-625C. The ( ^ 0 3 , however,
was only sulphided at the higher temperature. The r e s p e c t i v e
sulphur uptakes are give in Table I I I IV d V X-ra
d i f f r a c t i o n examinatio
the higher temperature partia
Fej_flS and Cr2S3 from F e 3 0 4 and 0 ^ 0 3 r e s p e c t i v e l y .
The extents of d e p o s i t i o n on the sulphided 20/25/Nb s t a i n l e s s
s t e e l during 6-7.5 h exposure to carbon dioxide c o n t a i n i n g acetone
(0.31 atm pressure) at 600 and 700C are given in Table I I I . For
s i m i l a r exposure c o n d i t i o n s these were lower by f a c t o r s between 4
and 560 than those on o x i d i s e d 20/25/Nb s t a i n l e s s s t e e l ( 3 ) .
However, during longer exposures of the sulphided s t e e l to carbon
d i o x i d e c o n t a i n i n g 0.15 atm acetone, p r o t e c t i o n ceased on two out
of the three specimens as comparable d e p o s i t i o n occurred to that
expected f o r the o x i d i s e d s t e e l . Nevertheless, i n h i b i t i o n was
s t i l l maintained on the t h i r d specimen. Loss of p r o t e c t i o n was not
due to the removal of sulphur, as the amounts analysed a f t e r
exposure to acetone were s i m i l a r to the weight gains of
sulphiding.
The sulphide l a y e r on Fe304 d r a m a t i c a l l y reduced the
extent of d e p o s i t i o n at 600 and 700C (Table I V ) . For comparable
exposures at the lower temperature the f a c t o r by which d e p o s i t i o n
was reduced increased with the sulphur content of the Fe304
This c o r r e l a t i o n could not be a s c r i b e d to any change in surface
area, as that of the most completely sulphided FeÔ^ (0.97
m
^/g) was s i m i l a r to that of the o r i g i n a l m a t e r i a l (0.61 m^/g).
As with the 20/25/Nb s t a i n l e s s s t e e l , the sulphur contents of the
sulphided Fe304 before and a f t e r exposure to the d e p o s i t i n g gas
were s i m i l a r to w i t h i n a f a c t o r of two.
The exposure of C r 0 3 to hydrogen sulphide r e s u l t e d in i t s
2
almost complete conversion to Cr2S3 with a corresponding

r e d u c t i o n in surface area from 43.8 to 8 m^/g. The k i n e t i c s of
d e p o s i t i o n on the sulphided m a t e r i a l at 600C were s i m i l a r to those
on Cr203 ( F i g . 1) and w h i l s t the extent of d e p o s i t i o n was at
l e a s t comparable, i t could have been s l i g h t l y increased (Table V ) .
Gas Phase Poisons. The e f f e c t i v e n e s s was examined of four

sulphur compounds, thiophene, hydrogen sulphide, sulphur d i o x i d e
and carbonyl sulphide, as gas phase poisons.

228 COKE FORMATION
TABLE IV - The Effect of Sulphiding by H?S on Carbon

Deposition from Acetone on F e ^
H S treatment
2 Exposure to carbon dioxide containing acetone
Sulphur
Deposition
Sulphur Acetone Carbon content
Temp Time Temp Time reduction
content pressure uptake after
C h C h factor
% (a) atm. % (a) exposure
(c)
% (a)
70
20 24 0.06
600 115 0.15 378 40

(b)
600 1 9.2 700 11.5 0.31 5.1 90 N.D.
8 0.31 62 250
600 1 10.3 600 6.7
221 0.15 468 90

(b)
600 1 38.4 600 266 0.15 3.5 9.4 10 3

35.5
N.D. = Not determined
(a) Expressed as a percentage of the original F e ^ sample weight.

Value for complete conversion to FeS = 41.5.
(b) Successive exposures.
(c) The ratio of the extents of deposition on untreated control and

sulphided Fe34 for comparable exposure conditions. The former
data are from reference (3).

TABLE V - Influence of S u l p h i d i n g and the Continuous A d d i t i o n of a Sulphur Compound
to the Gas Phase upon the I n t e r a c t i o n between CrpO/i and Acetone at 600C
P a r t i a l pressure Carbon uptake a f t e r 75h

Sulphur
(atm) Exposure Ug/cm (b)
treatment/ Sulphur uptake
duration
gas phase (a)
Sulphur h With sulphur Without sulphur
additive Acetone
additive treatment treatment
Sulphided by Decreased from

( c )
by H S ?
- 0.15 266 56.1 to 40.4 0.99 0.39
( l h , 600C) during exposure
4
Thiophene 8 10" 0.38 50 0.013 1.02 0.92
Thiophene 0.10 0.20 50 0.95 0.68 0.92
6
HS2
8 10" 0.11 73 0.23 0.43 0.39
4 ( C )
HS2 6 10" 0.11 72 13.4 0.44 0.39
3
so 2
4 10~ 0.31 69 1.1 0.49 0.92

(a) Expressed as a percentage of the C r 0 3 weight; value f o r complete conversion to
2

C r S = 63.2%.
2 3
(b) C a l c u l a t e d from C r 0 3 surface area, except ( c ) c a l c u l a t e d from sulphided

2 Cr 03
2
surface area.
230 COKE FORMATION
TABLE VI - Influence of the Continuous Gas Phase Addition of a Sulphur Compound

on the Decomposition of Acetone by 20/25/Nb Stainless Steel at 6Q0C
Deposition exposure conditions

Weight gain
during 1000h Sulphur Carbon Deposition
Acetone
oxidation Sulphur Partial uptakg uptake^ reduction
partial Duration
in (XL at bearing pressure ug/em mg/cm f a c t o r ^
pressure h
mere additive atm.
atm.
0.157 Thiophene 1.5x1" 4

0.19 17 4 14.0 1-6
0.077 Thiophene 6xl0""
0.080 E^S 2x1" 6

0.09 4 N.D. 18.4 1-3
0.095 H^S 2xl0~ 5

0.11 72 15 0.13 6-1100
0.135
3xl0" 5
0.14 50 <5 0.24 3-470
0.055 H^S SxlO" 5

0.12 73 <5 0.04 18-3400
-4
0.085 H^S 0.12 73 50 0.04 18-3400
5x10
0.125 90 2 " 6
0.10 75 <5 1.15 1-12
0.105 so 2 4xl0~ 5
0.12 75 5 0.65 1-210
0.070 so 2
41" 3
0.31 71 2 0.06 13-2500
0.055 COS 0.3x1" 6

0.07 75 8 0.25 3-550
0.160 COS 4x1" 5

0.10 75 4 0.70 1-200
N.D. - Not determined
(a) The ratio of the extents of deposition for g-fnrMar exposure conditions without
and with the addition of sulphur compounds to the gas phase. The former data
are from reference (3).

TABLE VII - Influence of Continuous A d d i t i o n of Thiophene to the Gas

Phase upon Carbon Deposition from Acetone Decomposition on
FeÔa a t 600C
P a r t i a l pressure
Exposure Sulphurv Carbon Deposition
(atm)
duration uptake uptake reduction
h ppm % factor C B 7
Thiophene Acetone
7
2 10" 0.28 2 N.D. 68 Nil
5
l(f 0.31 71 <125 3.5 5.7 1 0 4
5
4 l(f 0.24 7 N.D. N.M. (c)
1.5 10" 4
0.19 4.25 <50 N.M. (c)
3
1.6 10" 0.32 7 100 N.M. (c)
8.7 10" 3
0.28 7 125 N.M. (c)
3.7 l ( f 2
0.13 5.75 3000 N.M. (c)
N.D. - Not determined. N.M. - Not measurable.
(a) A f t e r exposure, expressed as a r a t i o of the FeÔ^ weight.
(b) The r a t i o of the extents of d e p o s i t i o n on Fe$0^ f o r s i m i l a r

exposure conditions without and with thiophene a d d i t i o n to the
gas phase.
(c) Not q u a n t i f i a b l e as no d e p o s i t i o n measured.

COKE FORMATION
232
TABLE VIII - Influence of the Continuous Addition of Either Hydrogen Sulphide,

Sulphur Dioxide or Carbonyl Sulphide to the Gas Phase upon Carbon
Deposition from Acetone Decomposition on Feqfy at 60QC
Partial pressure
Sulphur Deposition
(atm) Carta.
bearing Exposure Sulphur^ reduction
uptake
gas phase duration uptake factor^
Sulphur %
additive ketone
additive
fi^S 3 Kf6
4
HS
2 2.5 l ( f 5
0.12 72 0.04 0.1 2 10
-4
HS 0.12 50 0.17 0.3 6 10 3
2 5 x 10
fi^S 1.7 10" 3

0.31 7 19.7 4.8 3 103
so 8 10", 6
0.11 75 0.01 0.4 7 10 3
so 2
9 10" 5
0.14 80 0.01 0.8 3 10 3
so 2
4 10" 3
0.31 72 3.9 1.1 1.8 10 5
so 2
4 K f3 0.26 65 0.2 0.9 2 10 5
COS 0.25 10" 6

0.07 75 0.04 1.7 1.5 10 3
CDS 4 10" 5
0.11 75 0.08 0.8 3.1 10 3
(a) After exposure, expressed as a percentage of the original Fe%0^

weight.
(b) The ratio of the extents of deposition for similar exposure conditions
without and with the addition of a sulhur bearing compound to the gas
phase.

(a) Thiophene. The 20/25/Nb s t a i n l e s s s t e e l , p r e o x i d i s e d at

600C, was exposed at 600C to carbon dioxide c o n t a i n i n g 0.15-0.19
atm acetone and e i t h e r 150 uatm or 0.6 atm thiophene. D e p o s i t i o n
was i n h i b i t e d p a r t i c u l a r l y by the exposure to the higher thiophene
p a r t i a l pressure, when i t was reduced by a f a c t o r of 45-7500 (Table
VI). T h i s apparent i n f l u e n c e of thiophene p a r t i a l pressure cannot
be a t t r i b u t e d to sulphur pick-up by the 20/25/Nb s t a i n l e s s s t e e l as
these were comparable in the two experiments.
On exposure of F e 3 0 ^ at 600C to carbon dioxide c o n t a i n i n g
0.28 atm acetone the smallest thiophene p a r t i a l pressure examined
(0.19 uatm) d i d not a f f e c t d e p o s i t i o n (Table V I I ) . However, with a
thiophene pressure of between 10 uatm and 0.04 atm maintained
continuously, although FeÔ^ i n i t i a l l y ( < 1 h) l o s t weight,
there was then no s u b s t a n t i a l weight change during ^ 6 h f u r t h e r
exposure. The only exceptio small f depositio
between 3-18 h exposure
t h i s was s t i l l a f a c t o r anticipate
for the same exposure c o n d i t i o n s in the absence of thiophene. As
no f u r t h e r weight change occurred during the f o l l o w i n g 56 h
exposure to t h i s environment the r e s u l t s of the shorter term
t e s t s with higher thiophene p a r t i a l pressures were u n l i k e l y to have
been misleading due, f o r example, to an i n d u c t i o n p e r i o d . The
carbon contents of the Fe30^ exposed to 0.13-0.32 atm acetone
c o n t a i n i n g thiophene p a r t i a l pressures between 150 uatm-3.7
10""2 a t r a r e analysed and were comparable to those of the
w e
o r i g i n a l m a t e r i a l (1.0%). Thus, the thiophene at these p a r t i a l

pressures had completely i n h i b i t e d carbon d e p o s i t i o n . The
corresponding sulphur uptakes ranged between 50-3000 ppm and f o r
comparable exposure periods increased with the thiophene p a r t i a l
pressure. X-ray examination of exposed specimens i n d i c a t e d the
presence of Fe30^ only, whereas o r i g i n a l l y Fe 03 was a l s o 2
present. Consequently, the small i n i t i a l weight l o s s e s , e q u i v a l e n t

to 1-2% of the o r i g i n a l sample weight, were due to reduction of the
higher oxide.
The e f f e c t of d i s c o n t i n u i n g the thiophene a d d i t i o n was
examined at 600C on Fe304 exposed i n i t i a l l y to carbon dioxide
c o n t a i n i n g 0.28-0.33 atm acetone and 8.7 10"^ atm thiphene.
A f t e r 24 h subsequently in acetone alone the carbon content of the
r e a c t i o n product had increased to 46.7% of the o r i g i n a l Fe30^
sample weight. The extent of d e p o s i t i o n âs lower by a f a c t o r of
1.4 103 than that which would have been a n t i c i p a t e d on
FeÔ^. The low (100-125 ppm) sulphur uptake during the i n i t i a l
exposure to thiophene, was u n l i k e l y to have been the sole cause of
t h i s i n h i b i t i o n as i t i s not conceivable how i t could have provided
greater p r o t e c t i o n to acetone decomposition than the more extensive
p r i o r s u l p h i d i n g (compare with Table I V ) .
With C r 0 3 the a d d i t i o n of thiophene, at pressures of
2
e i t h e r 1000 uatm or 0.1 atm, d i d not i n f l u e n c e e i t h e r the k i n e t i c s

or extent of acetone decomposition at 600C ( F i g . 1 and Table V ) .
The sulphur uptakes f o r s i m i l a r exposure conditions increased with
thiophene p a r t i a l pressure (Table V ) .

234 COKE FORMATION
Acetone
Partial
Symbol Pressure Sulphur Poisoning Conditions
(atm)
0 15 None

0 31 None
0 15 Sulphided
A 0 38 Thiophene a d d e d (lOOOjjatm pressure)
0 20 Thiophene added (0-10atm pressure)
0 31 SO2 a d d e d (AOOOjjatm pressure)
X 0 11
0 10 20 30 40 50 60 70 80 90 100
Time (h)
Figure 1. Influence of sulfur poisoning on the catalytic decomposition of acetone

by Cr O at 600C.
2 s

(b) Hydrogen s u l p h i d e , sulphur d i o x i d e and carbonyl s u l p h i d e .

R e a c t i o n between the 20/25/Nb s t a i n l e s s s t e e l and acetone was
reduced i n c r e a s i n g l y with i n c r e a s i n g hydrogen sulphide and sulphur
d i o x i d e p a r t i a l pressures (Table V I ) , although in no case was i t
prevented. The sulphur compounds at the lowest p a r t i a l pressures
examined could have i n h i b i t e d the r e a c t i o n as the r e s u l t i n g carbon
uptakes during these exposures were at the lower end of the s c a t t e r
band of values f o r the 20/25/Nb s t a i n l e s s steel-acetone r e a c t i o n
under s i m i l a r c o n d i t i o n s . The e f f e c t of carbonyl sulphide was
s t u d i e d only at lower p a r t i a l pressures and in t h i s range i t
exerted a s i m i l a r i n f l u e n c e to the other a d d i t i v e s .
The decomposition of acetone (0.07-0.17 atm pressure) by
Fe304 at 600C was i n h i b i t e d markedly by the continuous
a d d i t i o n to the gas phase of hydrogen sulphide, sulphur d i o x i d e and
carbonyl sulphide over th f partial examined
(Table V I I I ) . These wer
5.0-3700 uatm f o r sulphu carbony
s u l p h i d e . With i n c r e a s i n g p a r t i a l pressure the e f f e c t i v e n e s s of
hydrogen sulphide decreased s l i g h t l y , while that of sulphur d i o x i d e
i n c r e a s e d by 100 f o l d . The observed i n i t i a l decrease in specimen
weight during these exposures, probably again arose from the
r e d u c t i o n of the Fe 03 present. In every case there was a
2
measurable sulphur uptake, which was greatest f o r the FeÔ^

exposed to the highest hydrogen sulphide, sulphur d i o x i d e and
carbonyl sulphide p a r t i a l pressures. There was always a small
carbon uptake, which nevertheless was lower by f a c t o r s between 3
10^-2 10-> than would have been expected f o r the acetone-
FeÔ/^ r e a c t i o n under the same c o n d i t i o n s . C o n t r o l experiments
were c a r r i e d out during each s e r i e s of experiments with the v a r i o u s
i n h i b i t o r s and e s t a b l i s h e d that the e f f e c t i v e n e s s of the lower
a d d i t i v e p a r t i a l pressures was not a t t r i b u t a b l e to any r i g memory
e f f e c t , e.g. d e s o r p t i o n of sulphur compounds or degradation
products from the r e a c t i o n v e s s e l s u r f a c e s .
Neither hydrogen sulphide (3.7-570 uatm pressure) nor sulphur
d i o x i d e (4000 uatm pressure) a d d i t i o n s a f f e c t e d the k i n e t i c s or
i n h i b i t e d the extent of decomposition of acetone by C r 0 3 , at 2
600C ( F i g . 1 and Table V ) . The sulphur uptakes were 1.1% of the

o r i g i n a l C r 0 3 weight, except in the experiment with the
2
highest hydrogen sulphide p a r t i a l pressure, when i t was 13.4%.

Since the C r 0 3 surface area was decreased by s u l p h i d i n g t h i s
2
was used to c a l c u l a t e the carbon uptake on t h i s specimen. The

value so obtained, normalised to 75 h, 0.44 ug/cwr was in c l o s e
2
agreement with that (0.39 ug/cm ) f o r C r 0 2 3 (Table V ) .
Discussion
Before c o n s i d e r i n g the p o s s i b l e r o l e s of sulphur, some of the

e s s e n t i a l f e a t u r e s of acetone degradation on the two oxides and the
20/25/Nb s t a i n l e s s s t e e l (3) need to r e i t e r a t e d . Fe304 was

236 COKE FORMATION
extremely a c t i v e in promoting t h i s r e a c t i o n . G r a p h i t i c filaments

were formed through which i r o n became f i n e l y d i s t r i b u t e d . X-ray
d i f f r a c t i o n i n d i c a t e d that t h i s was present as Fe3C and FeO,
although n e i t h e r n e c e s s a r i l y was the a c t i v e c a t a l y t i c s t a t e .
# Both
the t h r e s h o l d temperature (,,-550C) and the i n d u c t i o n period
proceeding r e a c t i o n were a s s o c i a t e d with c a t a l y s t formation. The
extent of r e a c t i o n on chromia, in c o n t r a s t , was extremely small and
the amount of carbon formed was i n s u f f i c i e n t f o r d e t a i l e d
characterisation. Chromia was not a f f e c t e d chemically by the
r e a c t i o n with acetone, whose degradation was b e l i e v e d to have been
c a t a l y s e d by the oxide, with the primary adsorption s i t e p o s s i b l y
being the chromic i o n .
Oxidation of the 20/25/Nb s t a i n l e s s s t e e l in carbon dioxide at
600-700C r e s u l t e d in the formation of a scale c o n s i s t i n g of
C r 0 3 where the g r a i n boundarie
2 i n t e r a c t e d with th surfac
and an (FeCrNi) s p i n e l ove
p e r i o d , again a t t r i b u t e catalys probably
i n v o l v i n g the r e d u c t i o n of the s p i n e l , acetone was decomposed
f o l l o w i n g pseudo-parabolic k i n e t i c s . The deposit produced was
again f i l a m e n t a r y in s t r u c t u r e , with the main m e t a l l i c c o n s t i t u e n t
being i r o n , present as Fe3C. The r o l e of the oxide scale formed
on the 20/25/Nb s t e e l mirrored, t h e r e f o r e , the r e s p e c t i v e behaviour
of Fe304 and C r 0 3 . 2
Two p o s s i b l e complementary mechanisms were r e s p o n s i b l e f o r the

r e d u c t i o n , or in some circumstances complete i n h i b i t i o n , by sulphur
of carbon d e p o s i t i o n from acetone on Fe30^. The f i r s t was
operative on m a t e r i a l sulphided before exposure to acetone, and
p o s s i b l y a l s o when high p a r t i a l pressures of hydrogen sulphide and
sulphur dioxide were added continuously to the gas phase, as t h i s
a l s o r e s u l t e d in appreciable F e j ^ S formation. In these
instances reduced d e p o s i t i o n could be a t t r i b u t e d , at l e a s t p a r t l y ,
to a slower rate of formation of the r e a c t i o n intermediary, e.g.
i r o n c a r b i d e s , on Fej_jjS as compared with Fe304
Thiophene carbonyl sulphide, together with hydrogen sulphide and
sulphur dioxide at lower p a r t i a l pressures, i n h i b i t e d d e p o s i t i o n by
a second mechanism. These compounds were adsorbed p r e f e r e n t i a l l y
on the a c t i v e surface s i t e s to the e x c l u s i o n of acetone and
thereby, prevented the i n i t i a l c a t a l y s t formation. That t h i s was
p r i m a r i l y a surface phenomenon i s demonstrated by the sulphur
uptakes which were extremely s m a l l . A value of 100 ppm represented
~ 2 0 % coverage of the i r o n s i t e s on the surface of F e 3 0 ^ and
t h e r e f o r e , the measured uptakes corresponded to surface coverages
of t h i s order extending up to the formation of a few monolayers of
sulphide. Thiophene was s l i g h t l y more e f f e c t i v e in preventing
d e p o s i t i o n than the simpler sulphur compounds, p o s s i b l y due to i t s
l a r g e r molecular area b l o c k i n g adjacent s i t e s . The c o n t i n u i n g
i n h i b i t i o n of acetone decomposition was considerably greater than
would have been obtained by the a s s o c i a t e d s u l p h i d a t i o n alone.
The extents of adsorption of the poison would be pressure depen-
dent, so that i t was not s u r p r i s n g that at low p a r t i a l pressures

(e.g. 0.19 uatm thiophene) the surface coverage was i n s u f f i c i e n t to

block c r i t i c a l adsorption s i t e s .
With C r 0 3 , n e i t h e r s u l p h i d i n g nor sulphur-containing gas
2
phase a d d i t i v e s , which a l s o sulphided the surface, i n h i b i t e d

acetone d e p o s i t i o n . This r e f l e c t e d the d i f f e r e n t mechanism
involved in carbon d e p o s i t i o n on t h i s oxide such that whether the
surface anion was e i t h e r oxygen or sulphur, d i d not a f f e c t e i t h e r
acetone adsorption or the subsequent decomposition of the adsorbed
molecules.
The r e a c t i o n between acetone and p r e o x i d i s e d 20/25/Nb
s t a i n l e s s s t e e l was c a t a l y s e d p r i m a r i l y by i r o n . I t would have
been a n t i c i p a t e d , t h e r e f o r e , as observed that i t would have been
i n h i b i t e d a l s o by sulphur poisoning. However, the i n f l u e n c e of
sulphur was not so marked as f o r FeÔ^, The smaller amount of
d e p o s i t i o n on the s t e e l c a t a l y s e d b th chromium-containin oxide
would not have been a f f e c t e
demonstrated f o r C r 0 3 2
f o r the small carbon uptakes always observed, even when that

p r i n c i p a l l y responsible f o r d e p o s i t i o n was i n h i b i t e d . Sulphiding
was e f f e c t i v e i n i t i a l l y as again t h i s i n h i b i t e d the formation of
the c a t a l y t i c i n t e r m e d i a r i e s . The decreased p r o t e c t i o n on extended
exposure to the carbon dioxide containing environment was not
caused by sulphur removal. This r e s u l t e d probably from outward
i r o n d i f f u s i o n from the underlying s t e e l to form a surface oxide
l a y e r and the r e s u l t i n g generation of c a t a l y s t s f o r acetone
decomposition. High p a r t i a l pressures of sulphur a d d i t i v e s to the
gas phase, as on Fe304, again r e s u l t e d in sulphide formation.
However, lower p a r t i a l pressures, which prevented d e p o s i t i o n on
Fe304 were not e f f e c t i v e in poisoning the o x i d i s e d s t e e l
surface p o s s i b l y because absorptive bonding was l e s s strong on the
mixed (FeCrNi) s p i n e l than on Fe304.
Conclusions
(1) The heterogeneous decomposition of acetone by FeÔ^, at

600 and 700C r e s u l t i n g in carbon d e p o s i t i o n , was reduced
s i g n i f i c a n t l y , and in some instances prevented, by sulphur
poisoning. Two procedures examined were p r i o r s u l p h i d i n g and
the continuous a d d i t i o n to the gas phase of e i t h e r thiophene,
H S, S0 or COS.
2 2 These i n h i b i t e d the formation of the
c a t a l y t i c intermediates responsible f o r d e p o s i t i o n e i t h e r by
p r e f e r e n t i a l adsorption poisoning a c t i v e surface s i t e s or by
oxide conversion to F e i - ^ S . Thiophene was the most
e f f e c t i v e a d d i t i v e as i t s l a r g e r molecular area than the
simple sulphur compounds enhanced surface a c t i v e s i t e
blockage.
(2) A c t i v e decomposition on C r 0 3 at 600C was not diminished
2
e i t h e r by p r i o r s u l p h i d i n g or sulphur bearing gaseous

a d d i t i v e s , which r e f l e c t e d the d i f f e r e n t r e a c t i o n mechanism
than with Fe304.

238 COKE FORMATION
(3) The e f f e c t i v e n e s s of these procedures to i n h i b i t acetone

decomposition by an o x i d i s e d 20% Cr/25% Ni/niobium s t a b i l i s e d
s t a i n l e s s s t e e l , at the same temperatures, r e f l e c t e d the
behaviour of the two oxides which were r e p r e s e n t a t i v e
p r i n c i p a l c o n s t i t u e n t s of the scale on the s t e e l . Prior
s u l p h i d i n g reduced d e p o s i t i o n f o r a l i m i t e d period u n t i l new
c a t a l y t i c intermediates were generated by the simultaneous
o x i d a t i o n of the s t e e l by the carbon dioxide c a r r i e r gas.
D e p o s i t i o n was decreased throughout the exposure by sulphur
bearing gaseous a d d i t i v e s , whose e f f e c t i v e n e s s increased w i t h
p a r t i a l pressure.
Acknowledgement s
We g r a t e f u l l y acknowledg th analytical k carried t b

A. Parker, G.S. S p i c e r ,
d i s c u s s i o n s with Dr. J.E.
Literature Cited
1. Campion, P.J., "Gas chemistry in nuclear reactors and large

industrial plant"; Dyer A. Ed; Heyden, London, 1980, 53.
2. Bennett, M.J.; Faircloth, R.L.; Firth, R.J.; Houlton, M.R.;
Norwood, K.S.; Prior, H.A. "Gas chemistry in nuclear reactors
and large industrial plant"; Dyer A. Ed; Heyden, London, 1980,
81.
3. Bennett, M.J.; Chaffey, G.H.; Langford, A.J.; Silvester,
D.R.V. UKAEA Report AERE-R7407; HMSO, London, 1973.
4. Baker,R.T.K.;Harris, P.S. "Chemistry and Physics of
Carbon", Walker J r . , P.L.: Thrower, P.A. Eds; M. Dekker, New
York, 1978, 14, 83.
5. Bennett, M.J.: Price, J.B. J. Mater. Sci. 1981, 16, 170.
6. B r i t i s h Patents 629,211 (1949); 698,121 (1953).
7. Karcher, W.; Glaude, P. Carbon, 1970, 9, 617.
8. Maxted, E.B. Advances i n Catalysis, 1951, 3, 129.

12
Influence of Total Pressure and
Hydrogen:Hydrocarbon Ratio on Coke
Formation over Naphtha-Reforming Catalyst
NORA S. FGOLI, JORGE N. BELTRAMINI, A M A D O F. BARRA,
E L O Y E . MARTINELLI, MARIO R. SAD and JOS M . PARERA
Instituto de Investigaciones en Catlisis y Petriqumica-INCAPE-Santiago del Estero
2654, 3000 Sante Fe, Argentina
The decreasing of the total pressure and of the

hydrogen to naphth
the coke formatio
below which there i s a great increment of the amount
of coke and i t s degree of polymerization exist. For
a given feed the catalyst deactivation i s a function
of the deposited coke obtained either by diminution
of the pressure or of the hydrogen to naphtha ratio.
A great carbon deposition -mainly on the metal- i s
observed during the f i r s t hours of operation, and
later a slow deposition -mainly on the alumina-
-continues.When the soluble fraction of the coke i s
extracted with solvents, a C to H ratio 0.79 i s
obtained.
The o b j e c t i v e s of the c a t a l y t i c reforming of naphtha are to

increase the naphtha octane number (petroleum r e f i n a t i o n ) or to
produce aromatic hydrocarbons (petrochemistry). B i f u n c t i o n a l
c a t a l y s t s that promote hydrocarbon dehydrogenation, i s o m e r i z a t i o n ,
cracking and d e h y d r o c y c l i z a t i o n are used t o accomplish such
purposes. Together with these r e a c t i o n s , a carbon d e p o s i t i o n which
d e a c t i v a t e s the c a t a l y s t takes p l a c e . T h i s d e a c t i v a t i o n l i m i t s the
i n d u s t r i a l operation to a time which depends on the o p e r a t i o n a l
c o n d i t i o n s . As t h i s time may be very long, to study c a t a l y s t
s t a b i l i t y i n laboratory, accelerated deactivation tests are
r e q u i r e d . The knowledge of the i n f l u e n c e of o p e r a t i o n a l c o n d i t i o n s
on coke d e p o s i t i o n and on i t s nature, may help i n the e f f o r t s to
avoid i t s formation.
The i n f l u e n c e of the t o t a l pressure and hydrogen t o naphtha
molar r a t i o on the amount and nature of the coke deposited on a
monometallic b i f u n c t i o n a l c a t a l y s t was s t u d i e d by means of a
standardized c a t a l y s t t e s t .
0097-6156/82/0202-0239$06.00/0

240 COKE FORMATION
Experimental
Catalyst. A P t / A l 0 3 - C l c a t a l y s t c o n t a i n i n g 0.375% P t and

2
0.87% C I was u s e d . I t was p r e p a r e d i m p r e g n a t i n g w i t h H PtCl 2
s a m p l e s o f CK 300 a l u m i n a f r o m K e t j e n f o l l o w i n g t h e method o f
2
C a s t r o e t a l . ( 1 ) . The s u p p o r t s u r f a c e a r e a was 200 m /g and t h e
c a t a l y s t had 90% m e t a l d i s p e r s i o n .
Catalyst Tests. They w e r e p e r f o r m e d in a b e n c h s c a l e

equipment t h a t was d e s c r i b e d e l s e w h e r e ( 2 ) . O c t a n e number (RON)
was t a k e n a s a m e a s u r e o f a c t i v i t y and l i q u i d y i e l d (r|C^) as a
measure o f s e l e c t i v i t y . These p r o p e r t i e s , the p e r c e n t a g e o f
a r o m a t i c s in t h e l i q u i d (%ArL) and t h e p e r c e n t a g e o f C 1 - C 3 w e r e
c a l c u l a t e d from c h r o m a t o g r a p h i c a n a l y s i s d a t a , as p r e v i o u s l y
described (2).
The a d o p t e d s t a n d a r
the c a t a l y s t at normal
r a t i o = 8) d u r i n g s e v e n h o u r s ( p e r i o d I ) . Then p r e s s u r e and
H : n a p h t h a r a t i o were d e c r e a s e d d u r i n g twenty h o u r s ( p e r i o d I I ) .
2
F i n a l l y , p r e s s u r e and H : n a p h t h a r a t i o w e r e r e t u r n e d t o i n i t i a l
2
v a l u e s f o r s e v e n h o u r s ( p e r i o d I I I ) . A l l t h e t e s t was c a r r i e d o u t
1
a t 515C and WHSV = 6 h ' .
An example o f t h e t e s t i s shown in F i g u r e 1. Two i m p o r t a n t
t y p e s o f v a l u e s c a n be o b t a i n e d t h a t a r e u s e f u l f o r i n v e s t i g a t i n g
c a t a l y s t d e a c t i v a t i o n by c o k e :
a) The d i f f e r e n c e s b e t w e e n t h e v a l u e s o b t a i n e d d u r i n g p e r i o d s
I I I and I : m o d i f i c a t i o n in RON (AR0N), in T)C (^), e t c . , due t o
the a c c e l e r a t e d d e p o s i t i o n of coke.
b) The s l o p e o f change o f RON, T)C$, e t c . d u r i n g p e r i o d I I
p r o d u c e d by t h e c o n t i n u o u s d e p o s i t i o n o f c o k e .
The c o k e c o n t e n t o f t h e c a t a l y s t s was m e a s u r e d by c o m b u s t i o n -
v o l u m e t r y a f t e r t h e r u n . The d i f f e r e n t i a l t h e r m a l a n a l y s i s (DTA)
o f t h e u s e d c a t a l y s t s was p e r f o r m e d w i t h an Aminco T h e r m o a n a l y z e r
u s i n g o x y g e n as dynamic g a s . The s o l u b l e f r a c t i o n o f c o k e f r o m
u s e d c a t a l y s t s was e x t r a c t e d w i t h s o l v e n t s and t h e s o l u t i o n s w e r e
a n a l y z e d by s e v e r a l t e c h n i q u e s in o r d e r t o d e t e r m i n e t h e i r n a t u r e .
Feed. P u r e L a O x i g e n a h y d r o g e n was u s e d . I t was p r e v i o u s l y

p u r i f i e d by p a s s a g e t h r o u g h a d e o x y g e n a t i n g c o p p e r bed and
dehydrated p a s s i n g t h r o u g h a M o l e c u l a r S i e v e s 4 A bed.
The n a p h t h a had t h e f o l l o w i n g p r o p e r t i e s :
D e n s i t y : 0.736 g/ml
Mean M o l e c u l a r W e i g h t : 109
B o i l i n g p o i n t r a n g e : 65-147C
RON: 59
C o m p o s i t i o n ( w e i g h t % ) : P a r a f f i n s : 64.2
N a p h t h e n i c s : 24.2
A r o m a t i c s : 11.6

FiGOLi ET AL. Coke Formation over Naphtha-Reforming Catalyst 241
30 atm
H2:naphtha=8 2: naphtha = 4 2: naphtha =8
100

-
x
^ ^ _ [ " """"

,
50

&
+ - +
I I I II I1 II L_J
I
I I
U_
0 5 10 15 20 25 30 35
TIME, hour
Figure 1. Diagram of a standard test, showing modifications of RON (O), rjC , 5
(X), % Ar (A), and CJd

L + C + C 10 (+). Conditions: temperature,
2 3
2
515C, andWHSV,6hK

242 COKE FORMATION
Results
Influence of Pressure. In order t o study the i n f l u e n c e of

t o t a l pressure on coke d e p o s i t i o n , the operating pressure was
v a r i e d between 2 and 20 atm in p e r i o d I I , keeping the other
c o n d i t i o n s p r e v i o u s l y d e s c r i b e d as standard. So, when r e f e r i n g to
an experiment a t 2 atm pressure, i t i s meant beginning at 30 atm
and H :naphtha molar r a t i o 8 f o r seven hours, then decreased and
2
maintained the pressure a t 2 atm and H :naphtha molar r a t i o at 4 2
for twenty hours, and coming afterwards back t o the i n i t i a l

c o n d i t i o n s . The r e s u l t s are presented in Table I .
I t may be observed that decreasing the pressure during p e r i o d
I I , increments in the amount of coke deposited on the c a t a l y s t and
in the negative d i f f e r e n c e s ARON and A % A r between I and I I I are L
produced. Lower pressure

C o r r e l a t i o n s between th
pressures and ARON were d e r i v e d using the l e a s t square method.
L i n e a r , e x p o n e n t i a l , power law and semilog r e l a t i o n s h i p s were
considered in a l l cases, t a k i n g that w i t h the best c o r r e l a t i o n
c o e f f i c i e n t ( r ^ ) as the most accurate one.
The best c o r r e l a t i o n obtained f o r the carbon percentage and
pressure was:
0 9 6 2
%C = 7.71 " r = 0.95 (1)
The amount of carbon deposited on the c a t a l y s t m o d i f i e d ARON

according t o :
0 , 3 9 ( % C ) 2
ARON = 2.50 e r = 0.97 (2)
The r e l a t i o n between pressure during p e r i o d I I and ARON was:

0 , 9 8 P 2
ARON = 11.76 e " r = 0.99 (3)
The slope of decay of RON during I I was higher when a lower
pressure was used and i t s r e l a t i o n s h i p was:
0 , 1 2 P 2
Slope of RON = -1.52 e ~ r = 0.99 (4)
The d i f f e r e n t i a l thermal a n a l y s i s of the d i f f e r e n t c a t a l y s t s

i s shown in F i g u r e 2. Two d i f f e r e n t combustion zones can be
observed, which may be considered as produced by the combustion of
substances of d i f f e r e n t nature: one zone from 123 to 369C and the
second one from 369 to 555C. The f i r s t zone i s not very w e l l
defined: d i f f e r e n t peaks can be seen and there i s an i n c r e a s e of
the zone when the pressure i s decreased.
The second zone appears as more s e n s i t i v e to the pressure
change. The pressure decreasing produced a great increment of t h i s
zone and p a r t i c u l a r l y of the peaks appearing a t h i g h combustion
temperatures.
I t i s important to observe that m o d i f i c a t i o n s of pressure
above 7.5 atm d i d not produce a very s i g n i f i c a t i v e change in the
amount and nature of the coke. But very important changes were
produced when pressure was below 7.5 atm, being s p e c i a l l y m o d i f i e d

12. FiGOLi ET AL. Coke Formation over Naphtha-Reforming Catalyst 243
vO vO vO in CO
r-H CN m <r
-

I I I I I I
CO <f CO
vO <-<

cd
CM vO
U < co
LO CM
- I I I
o0| <4
G
H
-i < 00
CM m
1I <fr II vO
u CM rH
I I I I
H
>

s +
H m \ 00 m CO

cd CM rH rH - rH
u 1 1 1 I
c

00

rH co CO in
-l - VO 00 00 \ CO
CO - <f co m m
CO

vO vO co
J-l rH rH
- 1 1 I

rH 00 > rH
\ CT> m m CM

1 1 I

<r rH vO <!
CO 00 un
Cd
<f CM

U m
co e CM m un
CO 4-
cd - rH CM
U w
Ph

244 COKE FORMATION

12. FIGOLI ET AL. Coke Formation over Naphtha-Reforming Catalyst 245
the amount of coke that burns at higher temperatures which i s more

s t a b l e and d i f f i c u l t to e l i m i n a t e . The c r i t i c a l pressure value
seems to be 7.5 atm, as i t can be seen in Figure 3.
Influence of hydrogen-hydrocarbon r a t i o . Molar values from 8

to 2 and a pressure of 10 atm during p e r i o d I I were used, being
the r e s u l t s presented in Table I I . More severe c o n d i t i o n s , as
smaller hydrogen to naphtha r a t i o s , meant more carbon d e p o s i t i o n
and higher slopes of decrease of RON and %ArL Comparing the
c a t a l y s t behavior before and a f t e r the severe p e r i o d , i t may be
seen that when smaller the used r a t i o s , higher was ARON as w e l l as
the A % A r and a smaller increment in Ar|C was n o t i c e d .
L
As when pressure m o d i f i c a t i o n s were s t u d i e d , c o r r e l a t i o n s

between %C, ARON and H :naphtha molar r a t i o , were d e r i v e d :
2
%C = 4.72 (H :naphtha)"
2
0 , 4 4 ( % C ) 2
ARON = 3.05 e r = 0.97 (6)
0 , 6 7 2
ARON = 11.88 (H :HC)"
2 r = 0.97 (7)
Slope of RON during I I = -1.18 e "0.21(H :naphtha)

2
r = 0.99 (8)
When the carbon nature was s t u d i e d by d i f f e r e n t i a l thermal
a n a l y s i s , two zones appeared c l e a r l y d i s t i n c t i v e , as shown in
Figure 4. In the f i r s t zone there were l i t t l e d i f f e r e n c e s between
the c a t a l y s t s operated at d i f f e r e n t hydrogen to naphtha r a t i o s ,
being g r e a t e r the d i f f e r e n c e s in the second. Smaller r a t i o s
increased the peaks of the second zone and a l s o produced a f u r t h e r
i n c r e a s e on the ones of higher combustion temperatures.
As when c o n s i d e r i n g the e f f e c t of pressure, a c r i t i c a l value
f o r hydrogen to naphtha r a t i o -approximately 3- may be pointed out,
as shown in F i g u r e 5.
Discussion
The amount and nature of coke deposited on the c a t a l y s t i s

a f f e c t e d by s e v e r a l f a c t o r s , as the o p e r a t i o n a l c o n d i t i o n s
(pressure, H :naphtha r a t i o , temperature and WHSV) and the c a t a l y s t
2
nature, such as i t s c h l o r i n e content (4).

Studying the i n f l u e n c e of t o t a l pressure and hydrogen to
naphtha r a t i o , i t was found that there are c r i t i c a l values that
must be avoided during o p e r a t i o n in order to prevent g r e a t e r and
more polymerized coke d e p o s i t s , which make decrease the c a t a l y s t
a c t i v i t y and modify i t s s e l e c t i v i t y , as had been shown in Figures
3 and 5. I f the data from DTA a n a l y s i s i s considered, i t may be
a l s o n o t i c e d that when the carbon deposit i s higher than 1%, there
i s a great increment of the peaks which corresponds to a more
stable deposit.

246 COKE FORMATION
V
\
I U
0 5 10 15 20
PRESSURE, a t m
Figure 3. Modifications of ARON (-o-), A% Ar (-X-),

L and AyC 5
+
() and percentage of carbon on catalysts (- | -) used under differ

ent pressures during the standard test. Conditions: temperature, 515C; and
WHSV, 6 hr . 1

CM
00 ON VO
+ rH CO <f 00

d d
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I
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tu a
American Chemical
Society Library
1155 16th St. N. w .
Washington,
ACS Symposium Series; D. C.
American Chemical 20030
Society: Washington, DC, 1983.
248 COKE FORMATION
T E M P E R A T U R E , C
Figure 4. Differential thermal analysis of catalysts used under different H : 2
naphtha molar ratios. Conditions: heating rate, 24 C/min; and oxygen flow rate
60 cm /min. 3
I i 1
I I
0 2 U 6 8
H : NAPHTHA,
2 molar
Figure 5. Modifications of ARON(-o-), A% Ar (-X-), , + L(----),

and percentage of carbon on catalysts (- | -) used under different H : 2
naphtha molar ratios during the standard test. Conditions: temperature, 515 C; U
and WHSV, 6 hr . 1

Considering that t h i s c a t a l y s t i s a b i f u n c t i o n a l one, many

authors have s t u d i e d whether the carbon d e p o s i t i o n i s produced on
the m e t a l l i c or on the a c i d i c f u n c t i o n . Barbier e t a l . (5) studying
coke formed from cyclohexane, found two peaks in t h e i r temperature
programmed o x i d a t i o n s t u d i e s , which they s t a t e d belong to carbon
A
2
IO3
deposited over the m e t a l l i c and over the a c i d i c f u n c t i o n of the
c a t a l y s t . We obtained s i m i l a r r e s u l t s by DTA a n a l y s i s . Using an
c a t a l y s t w i t h the same c h l o r i n e content than / ^ in the
standard t e s t , the thermogram showed only one peak, the one of the
second zone, as shown in Figure 6. As the pure alumina had not
m e t a l l i c f u n c t i o n , i t can be supposed that the peaks of the f i r s t
zone correspond to carbon deposited on the m e t a l l i c f u n c t i o n ,
Cy
jC]+C2+C3
whereas the peaks of the second zone, correspond to carbon
deposited on the a c i d i c f u n c t i o n .
The values
considered as a way to
(or in other words m e t a l l i c and a c i d i c f u n c t i o n s ) , because i t i s
known that C^ i s formed through hydrogenolysis on the m e t a l l i c
f u n c t i o n and C and C3 mainly through hydrocracking on the a c i d i c
C1
C
/1+C2+C3
2
function.
During coke a c c e l e r a t e d d e p o s i t i o n (period II)
A(C^/C^+C2+C3)
decreased (negative s l o p e ) , being the decrease higher f o r more
severe c o n d i t i o n s , and the d i f f e r e n c e (between
periods I I I and I) negative. This means that coke on the c a t a l y s t
p r i n c i p a l l y diminishes the hydrogenolysis that occurs on the
m e t a l l i c s i t e . Looking back to Figures 2 and 4 i t can be seen that
f o r more severe c o n d i t i o n s , the r a t i o between the f i r s t and the
second zone i s lower. I f the f i r s t peak corresponds to coke on the
C
2+
C3
m e t a l l i c s i t e , the lower value may be because the m e t a l l i c
component i s almost completely covered and the s e v e r i t y increases
A(C^/C^+C2+C3).
the d e a c t i v a t i o n of the a c i d p a r t producing then a smaller
difference I t must a l s o be taken i n t o account that
the number of m e t a l l i c s i t e s i s much lower than the number of a c i d
s i t e s ( c o n s i d e r i n g a c a t a l y s t with 0.37% P t ) .
I t has been shown that more severe c o n d i t i o n s mainly
increase the carbon of the second zone, which corresponds to the
one on the a c i d i c f u n c t i o n . I t can be considered that the e f f e c t s
of a higher s e v e r i t y may be a s s i m i l a t e d with l a r g e r periods of
operating time, as by DTA we have found the same k i n d of coke
from a c c e l e r a t e d d e a c t i v a t i o n t e s t s and long time operation under
normal c o n d i t i o n s . Our r e s u l t s are c o n s i s t e n t with Gates et a l .
(6): f o r long time d e a c t i v a t i o n , carbon i s deposited on the a c i d i c
f u n c t i o n of the c a t a l y s t .
The d i f f e r e n c e s in RON (ARON), before and a f t e r the severe
p e r i o d i s r e l a t e d to the percentage of carbon on the c a t a l y s t ,
independently i f the s e v e r i t y was achieved changing pressure or
H 2 : n a p h t h a r a t i o . This i s shown in Figure 7, where i t may be seen
that a l s o the slope of d e a c t i v a t i o n during I I i s only r e l a t e d to
the amount of carbon. The curves in Figure 7 do not go to the
o r i g i n , showing that there i s a very r a p i d i n i t i a l coke d e p o s i t i o n

250 COKE FORMATION
15r
TEMPERATURE, C
Figure 6. Differential thermal analysis of an alumina used during 30 h. Condi-

tions: pressure, 30 atm; H :naphtha molar ratio, 8; temperature, 515C;
2 and
WHSV, 6 hr . 1
Figure 7. Influence of different amounts of carbon produced through modifications

of pressure and H :naphtha ratio of RON and on the slope of RON during Period II.
2
Key: O, pressure; and X, H :naphtha ratio.

2

12. FIGOLI E T AL. Coke Formation over Naphtha-Reforming Catalyst
251
which amount i s approximately 0.2-0.4%. T h i s f a c t was checked

studying the amount of carbon deposited under normal o p e r a t i o n a l
c o n d i t i o n s as a f u n c t i o n of time, as shown in F i g u r e 8.
Coke d e p o s i t i o n on Pt/Al203 i s a very complicate phenomena.
There i s an i n i t i a l r a p i d d e p o s i t i o n that mainly a f f e c t s the
m e t a l l i c f u n c t i o n . That i n i t i a l d e p o s i t i o n produces a decreasing
of the great i n i t i a l h y d r o g e n o l y t i c a c t i v i t y . Tennison (7) a l s o
s t a t e d that the i n i t i a l coke d e p o s i t i o n i s on the metal
c r y s t a l l i t e s . Then the d e p o s i t i o n i s slower and a t longer times o r
more severe c o n d i t i o n s , the d e p o s i t i o n of coke tends to occur on
the a c i d i c f u n c t i o n , p a r t l y because the m e t a l l i c f u n c t i o n i s almost
completely covered, even i t i s not poisoned, as coke i s not a
poison f o r the r e a c t i o n . I t must be remembered t h a t the c a t a l y s t
has only 0.37% metal on a h i g h s u r f a c e area alumina. The coke
i n c r e a s e i t s degree of s t a b i l i t w i t h th s e v e r i t f th
operational conditions
The nature of cok y
f r a c t i o n with d i f f e r e n t s o l v e n t s (benzene-methanol (8) and carbon
t e t r a c h l o r i d e ) with a Soxhlet. A f t e r the evaporation of the s o l v e n t
at room temperature, the e x t r a c t was analyzed by ^HNMR, IR and
mass spectrometry. The s o l u b l e f r a c t i o n o f the coke i s the l e s s
polymerized, and can be taken as c o n t a i n i n g the p r e c u r s o r s that
determine coke composition.
By ^HNMR and a p p l y i n g the methods o f C l u t t e r e t a l . (9) and
Herod e t a l . (10) the percentage o f the d i f f e r e n t types of carbons,
as w e l l as the mean molecular weight and C/H r a t i o f o r a c a t a l y s t
operated during a standard t e s t (P = 10 atm, H :naphtha (molar) 2
= 4 during I I ) were determined. The r e s u l t s are shown in Table I I I .
Table I I I
Percentage of D i f f e r e n t Carbon Types, Mean M o l e c u l a r

Weight and C/H o f the S o l u b l e F r a c t i o n o f Coke from
a C a t a l y s t Operated During a Standard Test
PM alkylic naphthenic aromatic C/H

carbon, % carbon, % + olefinic
carbons, %
227.1 38.5 21.6 39.9 0.79
The presence of the d i f f e r e n t carbon types was confirmed by

IR a n a l y s i s as has been a l s o done by B a k u l i n e t a l . (11). In
a d d i t i o n v i b r a t i o n s in the 560-970 cm""^ r e g i o n i n d i c a t e d the
presence of condensed aromatics w i t h a l k y l i c s u b s t i t u e n t s as shown
by E b e r l y e t a l . (12).
The mass s p e c t r o m e t r i c a n a l y s i s of the e x t r a c t e d coke showed
components of molecular weights between 100 and 300.
A n a l y z i n g the r e s u l t s obtained through d i f f e r e n t techniques,
of the coke s o l u b l e f r a c t i o n , we can say that coke p r e c u r s o r s are

252 COKE FORMATION
m o l e c u l e s o f a n a p p r o x i m a t e l y m o l e c u l a r w e i g h t 220, i n c l u d i n g
condensed a r o m a t i c s o r a r o m a t i c s p l u s n a p h t h e n i c s j o i n e d b y
a l k y l i c chains, with a general formula \22'
Figure 8. Percentage of carbon over a catalyst used during different periods of

time. Conditions are the same as in Figure 6.
Literature Cited
1. Castro, A.A.; Scelza, O.A.; Benvenuto, E.R.; Baronetti, G.T.;

Parera, J.M. 6th Iberoamerican Symposium on Catalysis, Rio de
Janeiro, Brazil, 1978, Paper No. 55.
2. Sad, M.R.; Fgoli, N.S.; Beltramini,J.N.;Jablonski, E.L.;
Lazzaroni, R.A.; Parera, J.M. J. Chem. Tech. Biotechnol. 1980,
30, 374.
3. Fgoli, N.S.; Sad, M.R.; Beltramini,J.N.;Jablonski, E.L.;
Parera, J.M. Ind. Eng. Chem. Prod. Res. Dev. 1980, 19, 545.
4. Parera, J.M.; Fgoli, N.S.; Jablonski, E.L.; Sad, M.R.;
Beltramini, J.N. "Catalyst Deactivation"; Delmon, B.; Froment,
G.F. (eds.); Elsevier Publ. Co.: Amsterdam, 1980; p. 571.
5. Barbier, J.; Marecot, P.; Martin, N.; Elassal, L.; Maurel, R.
"Catalyst Deactivation"; Delmon, B., Froment, G.F. (eds.);
Elsevier Publ. Co.: Amsterdam, 1980, p. 53.
6. Gates, B.C.; Katzer, J.R.; Schuit, G.C.A.; "Chemistry of
Catalytic Processes"; McGraw-Hill: New York, 1979, p. 287.
7. Tennison, S.R. Chem. i n Brit. 1981, 17 (11), 536.
8. Bodzek, D.; Marzek, A. Fuel 1981, 60, 47.
9. Clutter, D.R.; Petrakis, L.; Stenger, R.L.; Jensen, R.K. Anal.
Chem. 1972, 44 (8), 1395.
10. Herod, ..; Ladnev, W.R.; Snape, C.E. Phil. Trans. R. Soc.
Lond. 1981, A 300, 3.
11. Bakulin, R.A.; Levinter, M.E.; Unger, F.G. Neftekhimiya 1978,
18 (1), 145.
12. Eberly, P.E.; Kimberlin, R.N.; M i l l e r , W.H.; Drushel, H.V.
Ind. Eng. Chem. Proc. Des. and Dev. 1966, 5, 2.
RECEIVED June 2 8 , 1 9 8 2 .

13
Reactivity of Surface Carbon on Nickel Catalysts:
Temperature-Programmed Surface Reaction with
Hydrogen and Water
J. G. McCARTY, P. Y. HOU, D. SHERIDAN, and H . WISE

SRI International, Menlo Park, C A 94025
The nature of the carbon deposits formed on an

alumina-supporte
terized by their
temperature-programmed surface reaction (TPSR).
Carbon deposits formed by exposure to hydrocarbons
and carbon monoxide exhibit, depending primarily on
the temperature during deposition, seven reactive
carbon states during TPSR with 1-atm H , including 2
two very reactive states of chemisorbed carbon, a

carbon film, nickel carbide, and two types of fila-
mentary carbon. Filamentary carbon was identified
by transmission and scanning electron microscopy,
and Ni C was identified from x-ray d i f f r a c t i o n mea-
3
surements.
These results suggest that the deactivation of
nickel catalysts i s due to the accumulation of a
carbonaceous film at low temperature, the rapid for-
mation of filamentary carbon at moderate tempera-
tures, and the formation of encapsulating carbon
layers at very high temperature.
Carbon can e x i s t on the metal surfaces o f n i c k e l c a t a l y s t s i n

a v a r i e t y of forms. Hydrocarbon exposure to n i c k e l c r y s t a l l i t e s
at elevated temperature (> 700 K) can r a p i d l y produce a mass o f
long-growing carbon filaments (ly 2) as i d e n t i f i e d i n numerous ex-
periments analyzed by t r a n s m i s s i o n e l e c t r o n microscopy (TEM). Yet
very r e a c t i v e forms o f s u r f a c e carbon can e x i s t , s i n c e carbon
atoms chemisorbed on n i c k e l surfaces apparently p l a y a c e n t r a l
r o l e i n the mechanism o f s e v e r a l n i c k e l - c a t a l y z e d r e a c t i o n s , such
as hydrocarbon s y n t h e s i s , (3 ,4, 5) hydrocarbon steam reforming,
(6, 7) and hydrogenolysis ( 8 ) .
In a previous study (9) we used temperature-programmed sur-
face r e a c t i o n (TPSR) with 1 atm hydrogen to determine the
0097-6156/82/0202-0253$08.50/0

254 COKE FORMATION
r e a c t i v i t y o f carbon deposited on alumina-supported n i c k e l . In

that study s e v e r a l forms o f v e r y r e a c t i v e carbon were d i s t i n
guished by t h e i r r e l a t i v e r e a c t i v i t y as determined by the tempera
ture a t maximum g a s i f i c a t i o n r a t e with hydrogen. The two most
r e a c t i v e forms o f s u r f a c e carbon (' , ) were a t t r i b u t e d to chem-
isorbed carbon atoms followed in order o f r e a c t i v i t y by the i n i
t i a l l a y e r s o f n i c k e l c a r b i d e () and f i n a l l y a l a y e r o f amorphous
carbon ( ) . These carbon forms were deposited by exposure to both
CO and 0 ^ over a temperature range from 473 t o 750 K.
2
In recent work, supported by the F o s s i l Fuels D i v i s i o n o f the

U.S. Department o f Energy, we have extended the range o f exposure
c o n d i t i o n s f o r carbon d e p o s i t i o n by CO and 0^1^ decomposition on
N i / A ^ O ^ s u r f a c e s and more f u l l y explored the nature o f such
deposits. The TPSR s t u d i e s with 1 atm H as r e a c t a n t were a l s o
2
extended by s t u d i e s with 0.03 atm H 0 in He d i l u e n t as the reac

tant gas. The b u l k carbo
sure were a l s o examine
and scanning e l e c t r o n microscopy so that the r e a c t i v i t y o f each
form o f carbon was i d e n t i f i e d with i t s morphology.
Experimental D e t a i l s
M i c r o r e a c t o r System f o r TPSR. The r e a c t i v i t y o f carbon

d e p o s i t s on reforming c a t a l y s t s has been s t u d i e d w i t h a quartz
m i c r o r e a c t o r system using the TPSR technique ( F i g u r e 1). A s m a l l
bed (10 t o 40 mg) o f a powdered c a t a l y s t i s placed on the porous
f r i t t e d d i s k o f a 1-cm q u a r t z m i c r o r e a c t o r . The c a t a l y s t bed can
be heated up t o 1375 by r a d i a t i o n and c o n v e c t i o n from a 12-mm by
25-mm c o i l of 0.81-mm-diameter Nichrome wire, which i s suspended
around the m i c r o r e a c t o r . The wire i s e l e c t r i c a l l y heated with a
programmable DC power supply t h a t i s c o n t r o l l e d by a custom-desig
ned temperature programmer. A steam o f dry N purges a i r from 2
c o n t a c t with the heater wire to extend i t s l i f e t i m e and to c o o l

the r e a c t o r . The c a t a l y s t bed can be cooled from 1375 t o below
500 in l e s s than one minute, and when a steady stream of n i t r o
gen i s passed through a Dewar f l a s k o f l i q u i d n i t r o g e n , the bed
can be cooled to below 180 K. The programmer can heat the r e a c t o r
1
at l i n e a r from 0.1 t o 4 K s"" . The c a t a l y s t bed temperature i s
measured with an unshielded 0.075-mm Chromel-Alumel o r 0.25-mm P t -
10% Rh/Pt thermocouple that penetrates the bed. The thermocouple
output i s compensated f o r ambient temperature with an Omega MCJ
reference junction. The thermal response time o f the c a t a l y s t bed
thermocouple system i s about one second.
The TPSR experiments were conducted a t one atmosphere p r e s
sure with a stream o f helium o r r e a c t i v e gas mixtures flowing
through the c a t a l y s t bed. High p u r i t y r e a c t a n t gases, i n c l u d i n g
hydrogen, carbon monoxide and l i g h t hydrocarbons, could be blended
with a helium c a r r i e r before i n t r o d u c t i o n i n t o the r e a c t o r . We
p u r i f i e d the helium c a r r i e r by passing i t through a bed o f copper
turnings a t 573 and then through a l i q u i d N~ c o o l e d molecular

3. MCCARTY ET A L . Surface Carbon on Nickel Catalysts
Vacuum
Cooling M
N 2 X
Reactor
Variable
Assembly
Leak
T o Quadrupole Valve
Mass S p e c t r o m e t e r
Figure 1. TPSR and pulsedflowsystem.

256 COKE FORMATION
s i e v e t r a p . Hydrogen, i n i t i a l l y 99.99% p u r i t y , was f u r t h e r p u r i

f i e d by d i f f u s i o n through a Ag/Pd a l l o y tube. The other r e a c t a n t
gas mixtures, 3.0-vol% CO in helium, 1.0-vol% C 2 H 2 in helium were
used as r e c e i v e d from the s u p p l i e r . Steam was generated at the
d e s i r e d rate by a s p e c i a l v a p o r i z e r fed by a s y r i n g e pump. Water
was d e l i v e r e d through a s y r i n g e to a l a y e r o f g l a s s thread wrapped
around a g l a s s c y l i n d e r l o c a t e d i n s i d e a l a r g e r c o n c e n t r i c g l a s s
vessel. The feed r a t e of water was adjusted to a t t a i n the d e s i r e d
vaporizaton rate. A c a r t r i d g e heater i n s i d e the c y l i n d e r provided
the heat necessary f o r steady steam e v a p o r a t i o n .
We c o n t i n u o u s l y monitored the composition o f the m i c r o r e a c t o r
e f f l u e n t gas with a quadrupole mass spectrometer (EAI Quad 300C)
by sampling a small p o r t i o n o f the e f f l u e n t gas stream with a var
iable leak valve (Granville P h i l l i p s ) . The pressure, i n d i c a t e d by
a nude i o n i z a t i o n gauge in the mass spectrometer chamber was con
t r o l l e d a t 9 10 tor
sure c o n t r o l l e r ( G r a n v i l l
tem was c a l i b r a t e d by i n j e c t i n g known amounts of pure gases i n t o a
He c a r r i e r stream. A c o n v e r s i o n f a c t o r was obtained f o r each gas,
g i v i n g q u a n t i t a t i v e e x p r e s s i o n of the TPSR r a t e data in terms of
e i t h e r c o n c e n t r a t i o n in the e f f l u e n t gas o r net r e a c t i o n r a t e from
the product o f e f f l u e n t c o n c e n t r a t i o n and c a r r i e r flow r a t e . In
l a t e r experiments, 0.1-vol% argon was added (premixed) to the
helium c a r r i e r as an i n t e r n a l standard f o r c a l i b r a t i n g the mass
spectrometer. The mass spectrometer could monitor up to eight
i n d i v i d u a l i o n mass peaks with an automatic mass peak s e l e c t o r
(Vacuumetries) and transmit the s i g n a l from selectedmass fragments
to r e c o r d e r s and an e l e c t r o n i c i n t e g r a t o r ( S p e c t r a p h y s i c s ) o r ,
more r e c e n t l y , to a l a b o r a t o r y microcomputer (Dual Systems). The
mass spectrometer s e n s i t i v i t y during TPSR was about 30 ppm f o r H 2
and CO and 10 ppm f o r other gases. By c a r e f u l l y measuring the
mass 32 peak, we kept the l e v e l of oxygen i m p u r i t y in the pure H 2
and He c a r r i e r streams reaching the r e a c t o r always below 1 ppm and
t y p i c a l l y at 0.1 ppm.
TPSR C h a r a c t e r i z a t i o n of Deposited Carbon. In an experiment

to analyze the TPSR c h a r a c t e r i s t i c s of a carbon d e p o s i t , 15 to 35
mg of powdered (170/250 T y l e r mesh) c a t a l y s t was placed on the
porous d i s k o f a quartz m i c r o r e a c t o r . T y p i c a l l y , a f r e s h sample
of c a t a l y s t was reduced f o r 15 hr at 773 in 1 atm flowing H2 and
a p r e v i o u s l y reduced c a t a l y s t was heated to 773 f o r a t l e a s t 1
hr before a TPSR experiment. Following r e d u c t i o n , the c a t a l y s t
was flushed with pure He and cooled or heated to a predetermined
carbon d e p o s i t i o n temperature. Carbon was deposited by exposure
to a stream o f d i l u t e hydrocarbon ( t y p i c a l l y 0.14-vol% C0H4) in
helium using a s p e c i a l 10-port switching v a l v e ( F i g u r e 1 ) .
Following carbon d e p o s i t i o n , the c a t a l y s t was cooled to room
temperature while the bed was flushed with pure He, and the He
c a r r i e r (now in r e a c t o r by-pass mode) was r e p l a c e d by the TPSR
reactant gas stream (1-atm H2 or 0.03-atm H2O in He). A f t e r the

13. MCCARTY ET A L . Surface Carbon on Nickel Catalysis 257
c a t a l y s t bed cooled to ambient temperature, the r e a c t i v e gas was

switched through the c a t a l y s t bed and temperature programming
began.
During TPSR, the r a t e o f g a s i f i c a t i o n o f the carbon deposit
(as determined by continuous measurement o f the e f f l u e n t gas
composition) was recorded as a f u n c t i o n i f time. The data are
represented by the c a l c u l a t e d gas production r a t e versus bed
temperature as in c o n v e n t i o n a l thermal a n a l y s i s . TPSR a n a l y s i s
was performed f o r v a r i o u s c o n d i t i o n s o f exposure temperature, ex
posure d u r a t i o n , and exposure gas (CO, 0 ^ or C 2 H 2 ) f o r both 1-
2
atm H and 0.03-atm H 0 in He as the g a s i f y i n g r e a c t a n t .

2 2
E l e c t r o n Microscopy. Some of the carbon produced on G-56H by

C H^ exposure has been a s s o c i a t e d with f i l a m e n t a r y carbon growing
2
from n i c k e l c r y s t a l l i t e through observation f deposited carbo

using TEM and SEM. Fo
Formvar-coated 200-mes grids imag p l a t e
were exposed f o r 2 s a t an a c c e l e r a t i n g v o l t a g e o f 80,000 eV on a
P h i l i p s 200 e l e c t r o n microscope. A m a g n i f i c a t i o n range o f 3,000-
200,000 diameters was used. For SEM, the samples were mounted in
c o l l o i d a l s i l v e r on microscope chucks and observed in the
Cambridge Mark I l a SEM instrument. The m a g n i f i c a t i o n range was
100 to 50,000 diameters.
C a t a l y s t s . The n i c k e l c a t a l y s t s used in the TPSR s t u d i e s G-

56H and G-65, both were commercial (united C a t a l y s t s Incorporated)
h i g h metal-weight-loading c a t a l y s t s with alumina supports. The
17-wt% N i / A l 0 q c a t a l y s t (G-56H) had a r e l a t i v e l y low metal sur
2
face area (4 n r / g Ni) but r e s i s t e d s i n t e r i n g since i t o n l y l o s t

20% o f i t s surface area a f t e r heating to 1273 in 1 atm The 2
2
25-wt% N i / A l 0 (G-65) had a modest surface area (29 m /g Ni) and
2 3
contained some CaO (see Table I f o r a summary o f the c a t a l y s t

properties).
Table I
PROPERTIES OF NICKEL CATALYSTS
Total Specific
Surface Metal
Metal Area Area
Catalyst Support Loading 2
(m /g c a t ) 2
(m /g Ni)
G-56H/UCI A 1 17 - 4
23
G-65/UCI A1 0 + CaAl 0
2 3 2 4 25 56 28
The metal surface area was determined by a d s o r p t i o n of CO a t

1 5
300 presuming 1.1 1 0 molecules CO/cm .

258 COKE FORMATION
Results
Carbon Deposited on N i c k e l v i a CgH^ Exposure; TPSR w i t h 1-

atm Carbon deposited on alumina-supported n i c k e l (17 wt%)
f o l l o w i n g ethylene exposure a t v a r i o u s temperatures has a wide
range of a c t i v i t y f o r r e a c t i o n with H2 ( F i g u r e 2 ) . D i f f e r e n t
s t a t e s of carbon are i d e n t i f i e d by maxima in the r a t e of CH^ pro
d u c t i o n . The temperature o f the rate maximum (T ) f o r a p a r t i c u
l a r carbon s t a t e was g e n e r a l l y found to be independent of both the
amount of carbon in that s t a t e and the temperature of d e p o s i t i o n .
Thus w i l l be taken as c h a r a c t e r i s t i c o f the r e a c t i v e s t a t e of
carbon in a d e p o s i t . I n c r e a s i n g the temperature of carbon deposi
t i o n s v i a CoH/ produced carbon s t a t e s with higher and hence
lower r e a c t i v i t y with 2
The TPSR (H ) r e s u l t s d i d not d i f f e r s i g n i f i c n a t l y f o r e i t h e r
2
of the alumina-supporte
v a r i o u s carbon s t a t e s (Tabl
(H ) with 1-atm H and TPSR (H 0) with 0.03-atm H 0 in He.
2 2 2 2
Exposure o f G-65 to a l i q u o t s o f C H^ in He at low temperature

2
(573 K) produced s e v e r a l v e r y r e a c t i v e s t a t e s o f carbon. A small

amount of the carbon d e p o s i t , i . e . the ' carbon s t a t e (9) with
l e s s than one monolayer coverage which i s taken to be equal to the
CO uptake at 300 K, had a peak temperature at 400 and even had
an observable CH^ p r o d u c t i o n r a t e at room temperature (300 K ) .
The ct TPSR peak with H2 was o f t e n obscured by a l a r g e r peak a t
T
495 i 20 r e p r e s e n t i n g the carbon s t a t e . Below 600 the

s t a t e was populated up to about one monolayer before g i v i n g r i s e
to another s t a t e (the carbon s t a t e ) produced at very h i g h
exposure (Figure 2 ) .
Because the carbon s t a t e could be populated to an extent
e q u i v a l e n t to 10 monolayers, i t seems obvious t h a t t h i s s t a t e was
a bulk s t a t e and was e i t h e r bulk n i c k e l c a r b i d e , N13C, or some
form of f r e e carbon. Based on x-ray d i f f r a c t i o n a n a l y s i s , and the
f a c t that t h i s s t a t e was never populated a t 773 (N13C i s known
to decompose above 600 (10)), the carbon s t a t e was most l i k e l y
Ni^C. X-ray d i f f r a c t i o n measurements of reduced 17-wt% N i / A ^ O ^
always show m e t a l l i c n i c k e l l i n e s even a f t e r d e p o s i t i o n of l a r g e
amounts o f carbon a t 773 and higher temperatures. However, f o l
lowing long exposure to C2H4 a t 573 K, the n i c k e l x-ray d i f f r a c
t i o n l i n e s showed a pronounced decrease in i n t e n s i t y . D i f f r a c t i o n
l i n e s f o r Ni^C were not observed probably because most of the n i c
k e l c r y s t a l l i t e s were transformed i n t o amorphous N13C o r c r y s t a l
l i t e s of N i C w i t h small domain s i z e (10).
3
Another form o f carbon (the carbon s t a t e ) was a l s o observed

f o l l o w i n g the C0H4 exposure at 573 to both the 25-wt% / ^
and 17-wt% Ni/A203 c a t a l y s t s . The carbon s t a t e had a peak tem
perature that increased from 660 at low coverage to 740 a t
h i g h coverage. The amount of carbon deposited i n t o the carbon
state was observed not to exceed 4 monolayers. T h i s s t a t e has not
been p o s i t i v e l y i d e n t i f i e d , but i t s coverage i s l i m i t e d to a few

13. MCCARTY ET A L . Surface Carbon on Nickel Catalysts 259
300 400 500 600 700 800 900 1000 1100 1200 1300
T E M P E R A T U R E (K)
Figure 2. TPSR with hydrogen of carbon deposited on G-56H by exposure to

ethylene. Key to carbon deposition temperature: , 573 K; , 773 K; ,
1073 K; and , 1273 K.

Os
Table I I
TPSR CHARACTERIZATION OF CARBON DEPOSITED ON

NICKEL CATALYSTS FOLLOWING ETHYLENE EXPOSURE
Deposition Product/ Temperature (K) a t Maximum R a t e

Catalyst T e m p e r a t u r e (K) R e a c t a n t Gas ' ' Carbon
G-65 573 CH /H
4 2 400 480 685 - - 1105 -
773 CH /H
4 2 395 505 625 850 - 1115 -
573 C0 /H 0
2 2 - 630 865 - - 1210
773 C0 /H 0
2 2 - 575 830 - - 1295
773 co /o
2 2 - - - - 895 - 1215
G-56H 573 CH /H
4 2 - 505 655 - - - -
773 CH /H
4 2 395 505 - 815 - - -
873 CH /H
4 2 - 510 - 835 950 1090 -
973 CH /H
4 2 385 510 - 850 955 1160 -
1073 CH /H
4 2 400 515 - - 965 1130 -
1273 CH /H
4 2 - 525 - - 1005 1150 -
773 C0 /H 0
2 2 - - - 855 - 1220
873 C0 /H 0
2 2 - - 855 985 - 1255

973 C0 /H 0
2 2 - - - 860 - - 1280
1073 C0 /H 0
2 2 - - - 860 945 - -
C0 /H 0
2 2 - - 830 935 1115 1280

1273 -
1073 C0/H 0 2 - - - 850 950 1070 -
1273 CO/H 0 2 - - - 815 925 1095 1265
' and s t a t e s n o t r e s o l v e d . 2
13. MCCARTY ET AL. Surface Carbon on Nickel Catalysts 261
monolayers, and t h i s makes i t l i k e l y to be an amorphous carbon

f i l m ( p o s s i b l y with some hydrogen present (11). The carbon
state i s not populated a t 873 and higher temperature (see Table
I I I , f o r 17-wt% N i / A l 0 ) .
2 3
A number of l e s s r e a c t i v e forms of carbon are produced f o l

lowing C H^ exposure to the Ni/A^CU c a t a l y s t s a t 773 and higher
2
temperature. At 773 K, ( F i g u r e 2; exposure produces a b u l k

1
form of carbon (the carbon s t a t e ) with a t 875 20 K. At
873 two forms of carbon are produced ( F i g u r e s 3 and 4) on the
17-wt% Ni c a t a l y s t f o l l o w i n g steady exposure to a stream of 1.0-
v o l % C 2 H 4 in helium. One form i s the carbon s t a t e ; the other
1
form with a t 960 15 ( a l s o a bulk form) i s the carbon

1
s t a t e . Following C H^ exposure a t 973 the carbon s t a t e
2
appears as a shoulder on the much l a r g e r peak r e p r e s e n t i n g the

g a s i f i c a t i o n of the carbon state ( F i g u r e 4) and at 1073 t h i s
s t a t e i s no longer presen
Both the ' and
carbon by e l e c t r o n microscopy. Transmission e l e c t r o n micrographs
of G-56H, a f t e r a r e l a t i v e l y long exposure (10 min) to 0.1-atm
C9H4 a t 875 K, show the e x t e n s i v e formation of filamentous carbon
(Figures 6a through 6e). The micrographs show a wide d i s t r i b u t i o n
of filament diameters from 70 to 1000 , with approximately
bimodal d i s t r i b u t i o n centered at 100 and 800 . The TEM
micrographs are very s i m i l a r to the c l a s s i c carbon filament p i c -
tures published by Baker and H a r r i s (1) and others ( 2 ) , (12-19).
The f i l a m e n t s appear to have narrow hollow i n t e r i o r s with low
d e n s i t y (more transparent) cores and denser ( l e s s transparent)
outer s h e l l s , and o f t e n have a v e r y dense p a r t i c l e (presumably a
n i c k e l c r y s t a l l i t e ) at t h e i r t i p s ( F i g u r e 6b). The SEM r e s u l t s
showed the e n t i r e c a t a l y s t p a r t i c l e s are completely coated w i t h a
t h i c k mat of carbon f i l a m e n t s ( F i g u r e s 6c through 6e).
The e l e c t r o n micrographs of the 17-wt% Ni c a t a l y s t (G-56H)
a f t e r 100-s exposure to 0.004-atm C H^ a t 1073 a r e s i m i l a r to
2
the r e s u l t s obtained a t 875 K, except that the extent o f carbon

formation at 1073 was s u b s t a n t i a l l y l e s s : ~ 3% weight gain
versus > 50% weight g a i n a t 875 K. The r a t e o f f i l a m e n t growth
was f a s t e r at 873 than at 1073 K, and the average filament
length was much longer a t the lower temperature. Again, l a r g e
(800 ) and small (100 ) carbon f i l a m e n t s were produced; however,
many metal p a r t i c l e s appeared to be completely encapsulated by
carbon f i l m s .
At 1273 K, 1073 K, and 873 (with > 100-s exposure) C H 2 4
exposure produces yet another form of carbon ( carbon s t a t e ) with

very low c h a r a c t e r i s t i c r e a c t i v i t y with hydrogen ( F i g u r e 2 ) . The
peak temperature of the carbon s t a t e was about 1120 K, although
the TPSR (H ) peak produced by t h i s s t a t e v a r i e d some f 40 and
2
was o f t e n d i f f i c u l t to r e s o l v e from the peak produced by the

carbon s t a t e .
A unique f e a t u r e of the CH^ p r o d u c t i o n during TPSR w i t h 1-atm
H 2 at temperatures above 1100 in g e n e r a l , and f o r the peak

Table III
P O P U L A T I O N OF T P S R STATES FOR CARBON D E P O S I T E D ON AN

ALUMINA-SUPPORTED N I C K E L CATALYST ( G - 5 6 H )
FOLLOWING E T H Y L E N E EXPOSURE
CH,/H 0 TPSR 2
C H ^ Exposure T e m p e r a t u r e (K)
4 2
,
(K) 573 773 873 1073 1273
State Identification
f X X
a Chemisorbed carbon 410 + 15 X X
a Chemisorbed carbon 480 + 25 X X X X
+
Nickel carbide 550 X
1
3 Beta carbon film 660 + 30 , X X
Filamentous carbon ( T E M , SEM) 8 7 5 + 20 X X
Encapsulating carbon (TEM) 960 + 15 X X X
Platelet (?) carbon 1120 + 20^^ X X X

Peak temperature p
(T ) for heating rate =0.9 K/s. The TPSR p r o d u c t is CH^, the reactant i s H,

Increases with increasing coverage; T^ f o r low coverage limit.
Equilibrium limited for TPSR w i t h H . 9

McCARTY ET A L . Surface Carbon on Nickel Catalysts
300 400 500 600 700 800 900 1000 1100 1200 1
Figure 3. TPSR with hydrogen of carbon deposited on G-56H at 873

increasing exposure to ethylene.

264 COKE FORMATION
300 400 500 600 700 800 900 1000 1100 1200 1300
Figure 4. TPSR with hydrogen of the ' carbon state deposited on G-56H by
exposure to ethylene. Key to carbon deposition temperature: , 773 K; ,
873 K; , 973 K; and - -, 1073 K.

13. McCARTY ET A L . Surface Carbon on Nickel Catalysts 265
300 400 500 600 700 800 900 1000 1100 1200 1300
Figure 5. TPSR with hydrogen of carbon deposited on G-56H at 1073 by

increasing exposure to ethylene.

266 COKE FORMATION
Figure 6. Electron micrographs of carbon deposited on G-56H by decomposition

of ethylene at 875 and 1073 K.
Key: a, low-magnification (2340X) transmission electron micrograph (TEM) of carbon
deposited at 875 K; b, high-magnification (21J75X) TEM of the same sample as in a;
c, low magnification (65 X) scanning electron micrograph (SEM) of a G-56H catalyst
particle exposed to ethylene at 875 K; d, medium-magnification (3,250X) SEM of the
protrusion arrowed in c; and e, SEM micrograph of the same sample at near the limit
of resolution (32,500x).

r e p r e s e n t i n g the carbon s t a t e in p a r t i c u l a r , i s that the r a t e

not o n l y decreases with i n c r e a s i n g temperature as expected but in
creases again upon c o o l i n g . Apparently the c o n c e n t r a t i o n of CH^
in the e f f l u e n t gas i s l i m i t e d by the opposing r e a c t i o n s o f carbon
g a s i f i c a t i o n with H and methane decomposition, i . e . , the methane-
2
carbon e q u i l i b r i u m . It i s a l s o apparent that a t 1 K s heating

3 1
r a t e s and 1 cm s " gas flow r a t e s , the TPSR (H ) experiments can 2
not completely g a s i f y the carbon state except when very l i t t l e

i s present (< 5 ) . G a s i f i c a t i o n with steam does not approach
the e q u i l i b r i u m c o n c e n t r a t i o n s under TPSR c o n d i t i o n s and allows a
more complete examination o f thee carbon s t a t e .
Carbon Deposited on N i c k e l C a t a l y s t s by Exposure t o
Carbon Monoxide. In a previous TPSR study (9) carbon was d e p o s i
ted on a t 25-wt% N i / A l 0 c a t a l y s t (G-65) by exposure to CO a t
2 3
temperatures between 550 and 610 K TPSR (H ) o f carbon produced

by the d i s s o c i a t i o n ^ i s p r o p o r t i o n a t i o
presence o f l a r g e an
sorbed CO may have c o n t r i b u t e d to the s t a t e s , i t was, c o n c l u s i v e
l y shown that most o f the carbon state was more r e a c t i v e than a
monolayer of chemisorbed CO. In t h i s study, we extended the depo
s i t i o n o f carbon by CO exposure to higher temperatures to d e t e r
1
mine i f the and filament carbon s t a t e s in a d d i t i o n to the
and s t a t e s can be populated by a hydrogen-free source. The
TPSR ( H ) r e s u l t s ( F i g u r e 8) c l e a r l y show the presence o f the f i l
2
1
ament carbon ( carbon) s t a t e a t 773 K. Comparison o f the peak
temperatures f o r carbon deposited by C H^ and CO exposure (Table 2
IV) shows l i t t l e d i f f e r e n c e in the r e a c t i v i t y o f the carbon

states.
Table IV
TPSR, CARBON STATES ON G-56H
AFTER EXPOSURE TO C H,, AND CO 0
Carbon Temperature (K a t Maximum Rate [T ] )

State Identification CH 2Exposure
/f CO Exposure
' R e a c t i v e carbon 410 15 380 15

a Chemisorbed carbon 480 25 460 20
Carbon f i l m 660 30 660 20
Y Ni C
3 -555 -480
' Filament carbon 875 20 850 db 40
Encapsulating carbon 960 15 -
P l a t e l e t carbon 1120 20
Methane production from TPSR with 1-atm hydrogen.

268 COKE FORMATION
1
0 5
I I I I I I I I I I I
300 400 500 600 700

TEMPERATURE
Figure 7. TPSR with hydrogen of carbon deposited on G-65 by CO exposure at

550 K. Key to relative carbon deposit: a, 0.48; b, 1.19; and c, 3.14 normalized to
CO adsorption at 300 K.

MCCARTY ET A L . Surface Carbon on Nickel Catalysis
1
300 500 700 900 1100
Figure 8. TPSR with hydrogen of carbon deposited on Ni/Al O 2 s by exposure

CO. Key: , 573 K; and , 773 K.

270 COKE FORMATION
TPSR w i t h 0.03-atm HÔ o f Carbon Deposited on N i c k e l v i a C H 2 7|
Exposure. The g a s i f i c a t i o n of carbon d e p o s i t s with 0.03-atm steam

( F i g u r e 9 and Table V) shows that the s t a t e carbon r e a c t s more
r a p i d l y with 0.03-atm H 0 than with 1-atm H , as i n d i c a t e d by the
2 2
lower temperature (some 50 to 120 K) a t which the g a s i f i c a t i o n

r a t e reaches a maximum. The y i e l d o f carbon deposited above 873
during exposure to 0.01-atm C H^ decreases with i n c r e a s i n g c a t a
2
l y s t temperatures seen by the TPSR (H 0) r e s u l t s ( F i g u r e 9 ) , which

2
i s in agreement with the TPSR ( H ) r e s u l t s . However, TPSR ( H 0 ) ,

2 2
u n l i k e TPSR ( H ) , does not r e s o l v e the low temperature s t a t e s

2
( F i g u r e 9) and l i t t l e o r no g a s i f i c a t i o n i s seen below 475 K.
Table V
COMPARISON OF H 0 AND H TPSR RESULTS AFTER
EXPOSUR
Temperature (K)
at Maximum Rate (T ) T e n t a t i v e I d e n t i f i c a t on
TPSR States 0.03-atm H 0 2 1-atm H 2 of Carbon Species
' 825 875 Filament carbon

870 960 E n c a p s u l a t i n g carbon
1000 1120 P y r o l y t i c carbon
Carbon Formation on N i c k e l Catalysts
Morphology of Carbon Deposits on N i c k e l . The morphology o f

carbon deposited on n i c k e l by exposure to hydrocarbons and CO v a r
i e s d r a m a t i c a l l y with d e p o s i t i o n c o n d i t i o n s , as shown p r e v i o u s l y
by numerous i n v e s t i g a t i o n s with e l e c t r o n microscopy ( 1_). The most
dramatic f i n d i n g of these s t u d i e s i s the growing carbon f i l a m e n t s
with n i c k e l c r y s t a l l i t e s attached a t t h e i r t i p s ( 1 ) , (2^,) ( 6 ) ,
(12-20). The carbon f i l a m e n t s ( o f t e n hollow) can grow r a p i d l y ,
p u l v e r i z i n g c a t a l y s t p e l l e t s ( 2 1 ) and forming a t h i c k , v i s c o u s mat
of carbon. The mechanism of formation o f filamentous carbon i s
b e l i e v e d to be the c o n c e n t r a t i o n - d r i v e n (20) o r temperature-driven
d i f f u s i o n o f carbon through e n t r a i n e d , small (~ 10 nm)
nickel c r y s t a l l i t e s . Because carbon i s c o n t i n u o u s l y removed by
d i f f u s i o n from the surface r e g i o n s where i t f i r s t d e p o s i t s and i s
t r a n s f e r r e d to the growing f i l a m e n t , the s u r f a c e where carbon i s
f i r s t deposited need not d e a c t i v a t e . Thus coking proceeds r a p i d l y
and c o n t i n u o u s l y , as long as carbon continues to move from the ex
posed metal surface i n t o the growing f i l a m e n t . The TEM data,
e s p e c i a l l y a t higher temperature, a l s o show that the f i l a m e n t s may
stop growing and that a carbon s h e l l may encapsulate the metal
crystallites. Such a p a s s i v a t i n g s h e l l stops f u r t h e r f i l a m e n t

13. MCCARTY ET AL. Surface Carbon on Nickel Catalysis 271
0.30
0.25
0.20 h
<
oc 0.15

)

oc
.

0.05
500 600 700 800 900 1000 1100 1200 1300
T E M P E R A T U R E ()
Figure 9. TPSR with 0.03 atm H 0 in He of carbon deposited on G-56H by

2
exposure to ethylene. Key to carbon deposition temperature: , 1273 K; ,

1073 K; - -, 973 K; , 873 K; and - , 773 K.

272 COKE FORMATION
growth and presumably slows any c a t a l y z e d r e a c t i o n s such as

hydrocarbon steam r e f o r m i n g .
Other types o f carbonaceous d e p o s i t s found on n i c k e l surfaces
f o l l o w i n g exposure to hydrocarbons include e n c a p s u l a t i n g polymer
f i l m s p o s s i b l y c o n t a i n i n g hydrogen) formed a t low temperature,
(20) c r y s t a l l i n e f l a k e o r p l a t e l e t carbon formed on f l a t metal
surfaces a t h i g h temperatures (1_), (20), (22), and amorphous car
bon f i l m s a l s o formed a t h i g h temperature (1_). In a d d i t i o n , pyro-
l y t i c carbon ( e s s e n t i a l l y formed in the gas phase) can c o l l e c t on
the e x t e r i o r s u r f a c e s o f c a t a l y s t p a r t i c l e s and may e v e n t u a l l y
coat the c a t a l y s t p a r t i c l e s w i t h a l a y e r o f carbon (20) and block
the pores that lead to t h e i r i n t e r i o r s (23), (24). A d e s c r i p t i o n
of the v a r i o u s forms and p r o p e r t i e s o f carbonaceous d e p o s i t s a r e
summarized in Table VI. Given the wide range in morphology, we
expected, as observed in our TPSR s t u d i e s , that these v a r i o u s car
bon forms would have q u i t
We have been a b l e
have c h a r a c t e r i s t i c TPSR s p e c t r a in flowing H and H 0/He mix
2 2
tures. Such carbon s t a t e s can be q u a n t i t a t i v e l y i d e n t i f i e d by

t h e i r c h a r a c t e r i s t i c TPSR s p e c t r a .
?
In p a r t i c u l a r , the a and s t a t e s have been i d e n t i f i e d as
i n d i v i d u a l carbon atoms, probably chemisorbed a t two d i f f e r e n t
s i t e s (perhaps t e r r a c e and ledge or step s i t e s (25). We made t h i s
i d e n t i f i c a t i o n because (9) (1) these s t a t e s a r e v e r y r e a c t i v e with
hydrogen to produce methane, as we expect f o r C atoms; (2) they
are populated only up to about monolayer q u a n t i t i e s in terms o f CO
a d s o r p t i o n capacity; (3) they are not hydrocarbon fragments be
cause they are populated by CO d i s s o c i a t i o n as w e l l as hydrocarbon
decomposition; and (4) t h e i r r e a c t i v i t y i s o n l y a l i t t l e g r e a t e r
than the carbon s t a t e , which we b e l i e v e i s bulk n i c k e l carbide
because there are no n i c k e l l i n e s in the x-ray d i f f r a c t i o n o f G-
56H c a t a l y s t with a carbon d e p o s i t composed o f the carbon
state. Thus the and carbon s t a t e s both have metal-carbon
bonding r a t h e r than carbon-carbon bonding.
I d e n t i f y i n g the carbon s t a t e s as the polymeric "beta"
carbon f i l m mentioned in the l i t e r a t u r e (6) i s l e s s c e r t a i n than
1
assignments f o r , a, and carbon TPSR s t a t e s . Rostrup-Nielsen
(6), (11) and others (25) have r e f e r r e d to t h i s s t a t e on n i c k e l
c a t a l y s t s as a polymeric s u r f a c e carbonaceous d e p o s i t , which in
cludes w i t h i n i t a c o n s i d e r a b l e amount o f hydrogen. The formation
of the carbon s t a t e by CO exposure suggests that t h i s f i l m may
not c o n t a i n hydrogen; however, t h e r e are s e v e r a l reasons to
b e l i e v e that our carbon s t a t e i s a surface hydrocarbon polymeric
f i l m : (1) the maximum amount o f the carbon s t a t e was produced by
C H^ decomposition a t moderate temperature (573 K); (2) the c a r
2
bon state was o n l y observed a f t e r TPSR in H o f the ( o r ) c a r

2
bon state and in the case of CO exposure may be formed by t r a n s

formation o f the o r carbon s t a t e s during TPSR; (3) f i n a l l y ,
the maximum amount o f the carbon s t a t e was observed was 3 to 4
times the amount o f CO adsorbed on f r e s h l y reduced 25 wt% N i / A ^ O ^

( G - 6 5 ) , o r about 4 . 5 1
5
carbon atoms per cn^ N i s u r f a c e area
(assuming 1 . 1 1 0 1 5
molecules adsorbed CO/cm Ni a t 2 9 8 K)2
Such
a mass o f carbon i s l e s s than expected f o r a bulk phase but more
than expected f o r a s u r f a c e l a y e r , andtherefore we c o n s i d e r i t a
polymeric hydrocarbon s u r f a c e f i l m .
The TPSR r e s u l t s s t r o n g l y suggest that the ' carbon s t a t e i s
a s s o c i a t e d with the l o n g , r a p i d l y growing carbon f i l a m e n t s obser
ved by TEM. Filamentous carbon was observed in t r a n s m i s s i o n e l e c
t r o n micrographs of c a t a l y s t s exposed to CoH/ a t 8 7 3 and 1 0 7 3 K,
but not f o r those exposed a t 5 7 3 and 1 2 7 3 ( F i g u r e 2 ) . X-ray
d i f f r a c t i o n s t u d i e s o f the same samples showed no l i n e s a t t r i b u t a
ble to g r a p h i t i z e d carbon. The d e t a i l e d TPSR ( H ) s t u d i e s ( F i g u r e
2
4 ) c l e a r l y showed that the p o p u l a t i o n of the lower s t a t e ap ?
pears only with the higher temperature s t a t e , but at 1 0 7 3 and

1 2 7 3 the s t a t e appears alone. T h i s o b s e r v a t i o n l e a d s to our
s p e c u l a t i o n that the' carbo
carbon observed (I) occupyin
carbon i s the hard outer s h e l l of f i l a m e n t s and perhaps i s a l s o
the e n c a p s u l a t i n g carbon o f t e n observed ( 1 9 ) surrounding n i c k e l
p a r t i c l e s d u r i n g high temperature exposure to hydrocarbons. TPSR
and g r a v i m e t r i c observations o f the r a p i d decrease in the rate
of carbon s t a t e formation with i n c r e a s i n g time exposure at 1 0 7 3
a l s o support the view t h a t the carbon s t a t e could i n c l u d e the
encapsulating form o f carbon.
Whether the ' or carbon s t a t e s are formed depends e n t i r e l y
on the temperature during carbon d e p o s i t i o n . There i s a gradual
1
t r a n s i t i o n between d e p o s i t i o n i n t o carbon and d e p o s i t i o n i n t o
carbon f o r C H a expousre to N i / A l 0 o with temperature between
2 2
7 7 3 and 1 0 7 3 ( F i g u r e 2 ) .
The nature of the carbon s t a t e seen d u r i n g TPSR w i t h H 0 i s 2
u n c e r t a i n . TPSR w i t h H could not be used to r e s o l v e the carbon

2
s t a t e from f r e e g r a p h i t i c carbon because at 1 1 0 0 and higher

temperatures, CH^ decomposition becomes favored over carbon g a s i
f i c a t i o n by H?. The s t a t e seen d u r i n g TPSR with 0 . 0 3 - a t m H~0
was o f t e n small amounting to s e v e r a l monolayers carbon, and d i f
f i c u l t to r e p r o d u c i b l y populate. For t h i s reason, we s p e c u l a t e
t h a t the s t a t e may r e p r e s e n t a f i l m of p l a t e l e t carbon ( 2 2 ) , a
h i g h l y g r a p h i t i z e d monolayer o f carbon o f t e n observed f o l l o w i n g
p r e c i p i t a t i o n from carbon d i s s o l v e d in l a r g e specimens o f m e t a l l i c
nickel ( 2 6 ) . However, the s t a t e could a l s o represent H 0 g a s i 2
f i c a t i o n of carbon c a t a l y z e d by the support m a t e r i a l s , such as

A 1
23 o r
e s p e c i a l l y CaO, a known c a t a l y s t f o r H 0 g a s i f i c a t i o n of
2
carbon (2_7, 2 8 ) .
The formation o f c a t a l y s t carbon as carbon f i l a m e n t s or en
c a p s u l a t i n g carbon could profoundly i n f l u e n c e carbon f o u l i n g dur
ing reforming. Carbon f i l a m e n t s can grow v e r y r a p i d l y , b l o c k the
c a t a l y s t pores, and u l t i m a t e l y lead to r e s t r i c t e d flow and a l a r g e
pressure drop through the r e a c t o r (Table V I ) . The r e s t r i c t e d flow
could lead to increased p y r o l y s i s of unsaturated hydrocarbons and
f u r t h e r carbon f o u l i n g . E n c a p s u l a t i n g carbon would lead to a much

274 COKE FORMATION
Table VI. CHARACTERISTICS OF DEACTIVATING CARBON DEPOSITS ON
Carbon Carbon
TPSR S t a t e Morphology Mechanism o f F o r m a t i o n
Carbon film Slow p o l y m e r i z a t i o n o f C H X
r a d i c a l s on N i s u r f a c e s i n t o
an amorphous f i l m (containing
some H)
'
growth, p i t a t i o n at favored s i t e s
1
helical ( ) creating long (often hollow)
growth f i l a m e n t s c a r r y i n g the c r y s
tallite
Encapsu- Formation s i m i l a r to f i l a m e n t
lating carbon except carbon l a y e r s
carbon s h e l l p r e c i p i t a t e and grow on a l l
c r y s t a l planes
Platelet P r e c i p i t a t i o n of ( c r y s t a l
carbon l i n e ) g r a p h i t i c carbon from
dissolved carbon
Pyrolytic Thermal c r a c k i n g of hydro

carbon c a r b o n and d e p o s i t i o n o f
c a r b o n p r e c u r s o r s on e x t e r i o r
of c a t a l y s t
Soot Homogeneous n u c l e a t i o n and

growth of c a r b o n p a r t i c l e s

NICKEL HYDROCARBON REFORMING AND SYNTHESIS CATALYSTS
Effect on Parameters
Catalyst and R e a c t o r Favoring Deposition References
Progressive, rever Low temperature (< 625 K) 2, 6, 20

sible deactivation
Low H 0 / C
2 ratio
Little carbon
A r o m a t i c s and o l e f i n s in
buildup
feed
No d e a c t i v a t i o n
C a t a l y s t breakdown Low H 2 O / C ratio
Rapid increase in A r o m a t i c s and o l e f i n s in

r e a c t o r feed
Massive deposit Low activity
Deactivation High temperature (> 800 K) 2, 17, 18, 19

22
Slow carbon Low H 0 / C
2 ratio
buildup
Rapid rate of carbon
deposition
Deactivation High temperature (> 900 K) 1, 25
Small carbon Low pressure

buildup
Aging deposit
Difficult to
remove deposit
Encapsulation of High temperature (> 900 K) 1, 20

catalyst particles
High void fraction
Deactivation due t o
Low H2O/C
pore blocking
High pressure
I n c r e a s e
Low s p a c e velocity
Acidic catalyst support
Increasing Low reforming activity 20
Large carbon Low space velocity

deposit
High temperature
High pressure

276 COKE FORMATION
reduced l e v e l of c a t a l y s t i c a c t i v i t y f o r H 0 reforming with a cor

2
responding increase in the r e s i d e n c e time f o r r e a c t i v e hydrocar

bons, again l e a d i n g to p y r o l y s i s .
The Reaction Network. The chemisorbed carbon s t a t e s are

l i k e l y reforming i n t e r m e d i a t e s . Chemisorbed carbon i s formed by
the a b s o r p t i o n and r a p i d d i s s o c i a t i o n of C H^ and i s removed as CO
2
by r e a c t i o n with s u r f a c e oxygen, which i s produced in t u r n by d i s

s o c i a t i v e a d s o r p t i o n of H 0 or C 0
2 2 ( F i g u r e 10). Given the h i g h
r e a c t i v i t y of chemisorbed carbon, the ( i n c l u d i n g a,) s t a t e i s
probably an intermediate in the production o f other forms o f c a t a
1
l y s t carbon, and , and at lower temperature , , and . A
s i m i l a r set of equations would apply to other r e a c t i v e hydrocar
bons, other hydrocarbon products, and CH^.
The s e l e c t i v i t y between reforming and carbon growth i s d e t e r
mined in t h i s mechanisti
of chemisorbed carbon, C
surface oxygen from the d i s s o c i a t i v e a d s o r p t i o n of H 0 and r e l a
2
t i v e l y low c o n c e n t r a t i o n of C ( a ) , then we expect o n l y reforming

products and no bulk carbon formation. However, i f the C (a) f o r
mation r a t e i s v e r y h i g h and the 0(a) c o n c e n t r a t i o n low, ?hen the
thermochemical p o t e n t i a l of C (a) c o u l d be high enough to produce
f i l a m e n t carbon C^(a). I f fiament carbon i s produced, and subse-
quently the c o n c e n t r a t i o n of C (a) a g a i n f a l l s due e i t h e r to lower
p a r t i a l pressure of C H^(g) or a g r e a t e r c o n c e n t r a t i o n of 0(a) v i a
2
increased p a r t i a l pressure of H 0 ( g ) , then C^(a) c o u l d be consumed

2
by the r e v e r s a l o f the too t r a n s f o r m a t i o n .

Other r e a c t i o n s important to reforming are a l s o considered in
the r e a c t i o n network in Figure 10, i n c l u d e the w a t e r - g a s - s h i f t
r e a c t i o n and i t s r e v e r s e , the r e v e r s i b l e a d s o r p t i o n and decompo
s i t i o n of water, the d e s o r p t i o n and a d s o r p t i o n o f reforming pro
ducts l i k e CO, C0 , and H , and the formation of hydrocarbons l i k e
2 2
CH^. The formation of d i s s o l v e d carbon, oxygen, and hydrogen in

bulk n i c k e l i s a l s o considered. D i s s o l v e d C, 0, o r may be
important in the t r a n s p o r t of those elements to or from i n t e r f a c e s
with other s o l i d phase (carbon, c a r b i d e s , oxides, s u p p o r t ) . The
p o s s i b l e formation of NiO from H 0 i s a l s o shown. F i n a l l y , an
2
important r e a c t i o n to c o n s i d e r i s the formation of a d e a c t i v a t i n g

l a y e r o f carbons ( o r carbon s t a t e s ) .
Carbon G a s i f i c a t i o n Rates. Because the reforming r a t e s we

observed during t h i s work were o f t e n c o n t r o l l e d by d i f f u s i o n , i t
was not p o s s i b l e to determine i n d i v i d u a l r e a c t i o n r a t e s and rate
constants. However, from the TPSR measurements we were able to
estimate r a t e constants f o r the g a s i f i c a t i o n of c a t a l y s t and non-
c a t a l y s t carbons. These r a t e s are l i s t e d in Table V I I along with
s e l e c t e d r e s u l t s taken from the l i t e r a t u r e (29, 30, 31). We found
that the c a t a l y s t carbon g a s i f i c a t i o n r a t e s were f i r s t order in
carbon amounts up to e q u i v a l e n t (CO adsorption) monolayer

13. MCCARTY ET A L . Surface Carbon on Nickel Catalysts 277
GAS PHASE SURFACE STATES BULK STATES
H(a)
CH(g) 4 CH(a)
3
H(g)
9
H(a)
Alkanes (g)
Aromatics J) H(a)
Alkenes (g) CH(a)
Alkynes
H(a) '(5)
C(d)
C(a) (s)
CO(g) 0(a) NiC(s)
3
e(s)
CO(a)
C0 (g)
2 C(a) 0(d)
o(a) :
H(a) NiO(s)
H0(g)
2 OH(a)
H(a)
0(a)
H(g)
9 H(a) H(d)
Figure 10. Hydrocarbon synthesis and reforming reaction network on nickel

surfaces. Key: a, adsorbed phase; g, gas phase; s, solid phase; and d, bulk solution.

278 COKE FORMATION
Table V I I . Carbon G a s i f i c a t i o n Rate Parameters
Activation Pre-Exponential
Carbon Reactant Product Energy
Factor
1 1
State Gas Gas (kJ-mol- ) (S-l-ymolC ")
1 X lCT^-atm H 2 CH. 71 + 10 3 X ,, 1
4
Y 1-atm H 2

9 3
1-atm H 2 CH. 130 + 40 2 X io
4

1 5
?
1-atm H 2 CH.
4
108 + 20 7 X ^
' 3 X
2
10" -atm H 0 co 210 + 40 2 X 1 0 10 1.9
2 2
\
4
1-atm Ho CH 134 3 X io
,
1 1.5x1(^+9 ^ - a t m H 0 2
CO 185 8 X 10 7
6l-2

1 0
1-atm H 2
CH. 182 + 20 1 X
4
(?) 1 X 10-3-atm H 2 CH. 220 + 40
4
3 X 10-2-atm H 0 212 + 45 2 X 10112.6
2 C 0
2
G(char) 1-atm H 2
C H
172 2 X 102
4
G(soot) 3 X
2
10" -atm H 0 2 CO 238 + 30 3 X 107+1.6
G(char) 1-atm H 0
2 CO 146 8 X

G(char) 5 X 10-3l-atm H 0 2
CO 227 2 X 109

The u n c e r t a i n t y in p r e - e x p o n e n t i a l -actor d i r e c t l y f o l l o w s the
u n c e r t a i n t y in a c t i v a t i o n e n e r g y w i t h i n t h e s p e c i f i c t e m p e r a t u r e
range.
^ A s s i g n e d same a s s t a t e .

f r o m Temperature-Programmed S u r f a c e Reactions
Experimental Temperature Reaction Reaction Literature

Methodt Range ( K ) Order Carbon O r d e r Gas Reference
TPSR/HRV 450-520 1 ~0.2 9
TPSR 530-55
TPSR/HRV 680- -720 < 1 - 9
TPSR/IR 630- -760 -

TPSR/IR 700- -750 -
GA 773- -927 1 2 29
GA 821- -895 1 0 29
TPSR/IR 810- -820 - -

TEM 975- -1240 - - 22
TPSR/IR 710- -810 -
GA 900- -1400 - 31
TPSR/IR 920- -1240 -
GA 820- -1400 < 1 31
GA 1003-1123 1 0-1 38

1
Methods i n c l u d e : TPSR/HRV - v a r i a t i o n o f h e a t i n g r a t e w i t h
TPSRj TPSR- IR - i n i t i a l r a t e s w i t h TPSR; GA - m i c r o b a l a n c e
s t u d i e s ; TEM - movement o f N i p a r t i c l e s o n a c a r b o n s u b s t r a t e
d u r i n g TEM s t u d i e s .
I n i t i a l rates only.
Âssumed f i r s t order.

280 COKE FORMATION
q u a n t i t i e s , and n e a r l y f i r s t order (n = 0.5 to 1.0) in carbon up

to 30 monolayers f o r filament carbon.
We d i d not attempt to determine r e c t i o n orders f o r g a s i f i c a
t i o n with HÔ and H9; however, we d i d note that the h y d r o g a s i f i -
c a t i o n of the carbon state was n e a r l y zero order with respect to
H2 p a r t i a l pressure. At higher temperature (~ 800 K) we expect
the r e a c t i o n order f o r hydrogen to i n c r e a s e due to the d e s o r p t i o n
of hydrogen, and indeed F i g u r e i r e d o (20) reports second-order re
a c t i o n in H 2 f o r h y d r o g a s i f i c a t i o n of carbon deposited on n i c k e l
f o i l by decomposition of propylene at 720 30 K. Under
1
F i g u r e i r d o ' s c o n d i t i o n s , we would expect the carbon s t a t e to
comprise most of the d e p o s i t . The r e a c t i o n order f o r steam g a s i
f i c a t i o n o f such carbon f i l a m e n t d e p o s i t s v a r i e s between 0 and 1
depending on temperature (29, 30).
Apparent a c t i v a t i o
carbon s t a t e s were a l s
r e s u l t s (Table V I I ) . Because the r a t e s were f i r s t order in our
s t u d i e s ( i . e . , d i r e c t l y p r o p o r t i o n a l to the mass o f deposited
carbon), p l o t s of the logarithm of normalized r a t e s ( r a t e d i v i d e d
by remaining carbon s t a t e mass) v s . r e c i p r o c a l temperature f o r the
l e a d i n g edge of the TPSR curves have slopes p r o p o r t i o n a l to the
apparent a c t i v a t i o n energy ( E ) . Our values of E are g e n e r a l l y
a a
in good agreement with the l i t e r a t u r e values given the experimen

t a l u n c e r t a i n t i e s in t h i s type o f data. Rates e x t r a p o l a t e d to
1273 are very l a r g e f o r the ' carbon s t a t e ; thus under t y p i c a l
high temperature a d i a b a t i c steam reforming c o n d i t i o n s we do not
expect t h i s form of carbon to be present. However, the carbon
state i s not so r e a d i l y g a s i f i e d and could be s t a b l e and accumu
l a t e under ATR c o n d i t i o n s .
It i s l i k e l y that the carbon TPSR on / ^ represents
g a s i f i c a t i o n of r e l a t i v e l y dense carbon in contact with n i c k e l
surfaces. In f a c t , the t r a n s i t i o n from low d e n s i t y f i l a m e n t
() to encapsulating s h e l l c a t a l y s t carbon i s gradual (see F i g u r e
3 ) . At 1073 and higher temperatures the range of carbon forma
t i o n decreased r a p i d l y (< 50 s) probably because of the formation
of a carbon s h e l l around the n i c k e l c r y s t a l l i t e s .
G a s i f i c a t i o n o f dense c a t a l y s t carbon s h e l l s or tubes may be
s i m i l a r to c a t a l y t i c g a s i f i c a t i o n of a graphite substrate by small
nickel particles. D i r e c t c o n t r o l l e d atmosphere e l e c t r o n micros
copy (CAEM) of n i c k e l - c a t a l y z e d h y d r o g a s i f i c a t i o n of c r y s t a l l i n e
g r a p h i t e (22, 23) has provided many i n t e r e s t i n g observations about
the nature of the g a s i f i c a t i o n process; one i s that the n i c k e l
c r y s t a l l i n e s s o f t e n and change shape as they s t a r t to g a s i f y g r a
p h i t e at temperatures w e l l below the melting point of n i c k e l
(~ 100 K) (32). The i n t e r a c t i o n of g r a p h i t e lowers the s u r f a c e
energy of the n i c k e l c r y s t a l l i t e s with diameters o f ~ 100 nm, and
at 1075 the n i c k e l d i s s o l v e s i n t o the graphite s u b s t r a t e . This
may e x p l a i n why long f i l a m e n t s can be g a s i f i e d by metal c r y s t a l
l i t e s ; the "wetting" a c t i o n o f the carbon keeps the metal in
contact with the filament even as g a s i f i c a t i o n proceeds. With

13. McCARTY E T A L . Surface Carbon on Nickel Catalysts 281
metal carbon c o n t a c t assured, g a s i f i c a t i o n proceeds as long as the

reactant gas has d i f f u s i o n a l access to the c r y s t a l l i t e .
Another important CAEM o b s e r v a t i o n i s that some n i c k e l c r y s
t a l s d e a c t i v a t e a t elevated temperature 1175 and become immobile
(22, 32). This phenomena was a t t r i b u t e d to d i s s o l u t i o n o f carbon
i n t o the n i c k e l c r y s t a l l i t e s and i t s eventual p r e c i p i t a t i o n as
g r a p h i t e p l a t e l e t s , s i m i l a r to o b s e r v a t i o n s on w e l l - d e f i n e d n i c k e l
(33), platinum, (34) and i r o n (35, 36) s u r f a c e s . Under CAEM pres
sure (< 1 - t o r r H ) p l a t e l e t carbon i s not f u l l y g a s i f i e d and r e
2
mains a hollow s h e l l as the n i c k e l c r y s t a l d i s s o l v e s away a t 1225

K. S i m i l a r phenomena may g i v e r i s e to the TPSR carbon s t a t e ,
which a t 1-atm H2 o r 2 0 - t o r r l O i s g a s i f i e d a t higher tempera
t u r e . In H 0, n i c k e l c r y s t a l l i t e s observed i n CAEM a r e s t a b l e and
2
do not d i s s o l v e i n t o the bulk a t elevated temperature. However,

even i n the presence o f 1 0 th i n i t i a l ste i c r a c k i n
l a y e r of p l a t e l e t carbo
b i l i z e d Ni c r y s t a l l i t e ma
The r a t e s o f n i c k e l - c a t a l y z e d g a s i f i c a t i o n o f g r a p h i t e are i n
reasonable accord with our TPSR r e s u l t s f o r the carbon s t a t e .
For the carbon s t a t e , our E was 182 2 0 kJ m o l " i n good agree
a
1
1
ment with the r e s u l t s o f Keep e t a l . (22) 220 i 40 k J mol"" .
Because o f the d i f f e r e n c e s i n H2 pressure and technique, i t i s
d i f f i c u l t to compare a c t u a l r a t e s . Tomita e t a l . (37) observed
s u b s t a n t i a l l y lower apparent a c t i v a t i o n energies 130 db 12 kJ mol"
f o r nickel-impregnated carbons, but those r a t e s may have been l i m
i t e d by d i f f u s i o n (22).
Literature Cited
1. Baker, R. T. K.; Harris, P. S., The Formation of Filamentous

Carbon, i n "Chemistry and Physics of Carbon; "Walker, P.,
Jr.; Thrower, P. ., Eds.; Marcel Dekker: New York, 1978,
Vol. 14.
2. Trimm, D. L. Catal. Rev. 1977, 16, 155.
3. Ekerdt, J. G.; Bell, A. T. J. Catal. 1977, 48, 155.
4. Ponec, V. Catal. Rev. S c i . Eng. 1978 18, 151.
5. Niemantsverdriet, J. W.; van der Kraan, A. M. J. Catal. 1981,
72, 385.
6. Rostrup-Nielsen, J. R.; Trimm, D. L. J. Catal. 1977, 48, 155.
7. Munster, P.; Grabke, H. J. J. Catal. 1981, 72, 279.
8. Martin, G. A. J. Catal. 1979, 60, 345.
9. McCarty, J. G.; Wise, H. J. Catal. 1979,57,406.
10. Nagakura, S. J. Phys. Soc. Japan 1957, 12, 482; 1958, 13,
1005.
11. Rostrup-Nielson, private communication.
12. Baker, R. T. K. Catal. Rev. 1979,19,161.
13. Hofer, L. J. E.; Sterling, E.; McCartney, J. T. J. Phys.
Chem. 1955, 59, 1153.
14. Benshaw, G. D.; Roscoe, C.; Walker P. L. J. Catal., 22, 394.

282 COKE FORMATION
15. Baker, R. T. K.; Barber, . .; Harris P. S.; Feates, F. S.;

Waite, R. J. J. Catal. 1977, 26, 51.
16. Bohm, H. P. Carbon 1973, 11 583.
17. Baird, T.; Fryter, J. B.; Grant, B. Carbon 1974, 12, 591.
18. Audier, M.; Coulon, M.; Oberlin, A. Carbon, 1980,18,73.
19. Audier, M.; Oberlin, .; Oberlin, M; Coulon, M.; Bonnetain,
L. Carbon 1981, 19, 217.
20. Rostrup-Nielsen, J. R.; Trimm, D. L. J. Catal. 1977,48,155.
21. Rostrup-Nielsen, J. R.; Tottrup, P. B., Steam Reforming of
Heavy Feedstocks i n "Symposium on Science of Catalysis and
Its Application i n Industry;" FPDIL Sindri, India, 22-24
February 1979, paper 39 p. 397.
22. Keep, C. W.; Terry, S.; Wells, M. J. Catal. 1980, 66, 451.
23. Froment, G. F. Proc. Int. Congr. Catal., 6th, The Chemical
Society: Letchworth England 976
24. Beeckman, J. W.; Froment
805.
25. Jackson, S. D.; Thomson, S. J. Webb, G. J. Catal. 1981, 70,
249.
26. Isett, L. E.; Blakley, J. M. Surf. S c i . 1976, 58, 397.
27. McKee, D. W. Fuel, 1980, 59, 308.
28. Otto, K.; Bartosiewicz, L.; Shelef, M. Carbon 1979, 17, 351.
29. Figueiredo, J. L. Carbon 1981, 19, 146.
30. Bernardo, C. .; Trimm, D. L. Carbon 1979, 17, 115.
31. Wen, C. Y. Dutta, S. i n "Coal Conversion Technology;" Wen, C.
Y.; Lee, E. S., Eds.; Addison Wesley, 1979.
32. Baker, R. T. K.; Sherwood, R. D. J. Catal. 1981, 70, 198.
33. Derbyshire, F. J.; Presland, .; Trimm, D. L. Carbon 1978,
13, 111.
34. Baker, R. T. K.; Sherwood, R. D., Dumesic, J. A. J. Catal.
1980, 66, 56.
35. Baker, R. T. K.; Feats, F. S.; Harris, P. S. Carbon 1972, 10,
93.
36. Brown, . .; Hill, M. P. Carbon 1981, 19, 51.
37. Tomita, .; Sato, N.; Tamari, Y. Carbon 1974, 12, 143
38. Chihara, K.; Matsui, I.; Smith, J. M. AIChE Journal 1981,
220.
R E C E I V E D August 15, 1982.

14
Reaction of Steam with Coke on Solid Substrates
1
T. Y. Y A N and M. P. ROSYNEK
Mobil Research and Development Corporation, Central Research Division,

Princeton, NJ 08540
The kinetics of coke gasification are

markedly influence
on which the cok
of coke deposited on a silica-alumina substrate
followed first-order kinetics, with respect to
carbon remaining, with an activation energy of
55.5 kcal/mole and a reaction rate constant of
-3 -1
5 x 10 min at 1500F. Prior impregnation of
the substrate with copper, iron, or vanadium
oxides had v i r t u a l l y no effect on the rate of
subsequent coke gasification. Nickel oxide, on
the other hand, caused a three-fold increase in
i n i t i a l gasification rate, up to 30% of coke
conversion. Coke deposited on an alumina
substrate was three to six times more reactive
toward steam gasification at 1500F than that on
silica-alumina. Alumina apparently influences
both the rate and the structure of coke deposited
on it.
Reaction of steam w i t h carbon i s one of the b a s i c processes

i n v o l v e d i n the g a s i f i c a t i o n of c o a l s or chars to produce clean
fuels. The i n d u s t r i a l importance of t h i s r e a c t i o n i s consider-
able, p a r t i c u l a r l y at t h i s time of s p i r a l i n g energy c o s t s . In
a d d i t i o n , the steam-carbon r e a c t i o n f i n d s other important i n d -
u s t r i a l a p p l i c a t i o n s , such as preventing or minimizing the
coking of o l e f i n - p l a n t cracker-tubes. Because of i t s commercial
importance, the steam-carbon r e a c t i o n has been studied
e x t e n s i v e l y , and e x c e l l e n t reviews are a v a i l a b l e L,2). In
a d d i t i o n to r e a c t i o n k i n e t i c s and mechanisms, the e f f e c t s of
carbon s t r u c t u r e , c a t a l y s i s by metals, and i m p u r i t i e s (anions)
have been i n v e s t i g a t e d (3,.4,5) .
1
Current address: Texas A&M University, Department of Chemistry, College Station, TX 77843.
0097-6156/82/0202-0283$06.00/0

284 COKE FORMATION
Except f o r s p e c t r o s c o p i c g r a p h i t e , carbons used in the

steam-carbon r e a c t i o n , v i z . , a c t i v e carbon, coke, and char,
t y p i c a l l y c o n t a i n v a r y i n g amounts of hydrogen, i . e . , the
"carbons" are hydrocarbons in a broader sense. In a d d i t i o n to
i m p u r i t i e s , v a r i a t i o n s in the compositions of the carbons (e.g.,
hydrogen content) complicate the measurements and are a cause of
d i s c r e p a n c i e s among previous s t u d i e s . The r e a c t i o n s of steam
with c o a l s , cokes and chars have been reported and compared w i t h
the corresponding steam-graphite r e a c t i o n s (6-9). References in
the open l i t e r a t u r e to the r e a c t i o n of steam w i t h carbon that
has been deposited on v a r i o u s i n o r g a n i c s o l i d s u b s t r a t e s ,
however, are l a c k i n g .
In the c a t a l y t i c p r o c e s s i n g of heavy o i l and r e s i d u a over
s o l i d c r a c k i n g or hydrocracking c a t a l y s t s , a s i g n i f i c a n t amount
of "coke" i s deposited th c a t a l y s t s thu lowerin th
catalytic activities.
burning o f f the coke wit
c a t a l y s t i s high, e x c e s s i v e heat can be generated during
regeneration, causing temperature run-away, and r e s u l t i n g in
p o s s i b l e i r r e v e r s i b l e c a t a l y s t s i n t e r i n g and permanent l o s s of
activity. Furthermore, the p o t e n t i a l heating value of the coke
i s l o s t , because recovery of waste heat from the f l u e gas i s
r e l a t i v e l y expensive. Various schemes have been suggested f o r
regenerating s e v e r e l y coked c a t a l y s t s u s i n g steam and oxygen
(10,11). We have p r e v i o u s l y reported a process f o r upgrading
petroleum r e s i d u a that i n v o l v e s c o n t a c t i n g i t with a s o l i d
c a t a l y s t , followed by g a s i f i c a t i o n of the coke-laden s u b s t r a t e
with steam and oxygen (12).
The present study was undertaken in an e f f o r t to gain a
b e t t e r understanding of c e r t a i n aspects of the r e a c t i o n s
i n v o l v e d in the g a s i f i c a t i o n of cokes deposited on c a t a l y s t
s u b s t r a t e s in these a p p l i c a t i o n s . S o l i d s u b s t r a t e s were coked
with a petroleum residuum under simulated c o n d i t i o n s and the
substrate-supported coke was then r e a c t e d with steam. Effluent
gases were analyzed, and the k i n e t i c s of g a s i f i c a t i o n and the
e f f e c t s of s u b s t r a t e s i d e n t i t i e s and metal impregnations were
examined.
Experimental Methods
Materials. P h y s i c a l p r o p e r t i e s of the s o l i d s u b s t r a t e s
employed in t h i s study are summarized in Table I. The s i l i c a -
alumina was an e q u i l i b r a t e d Durabead TCC c a t a l y s t from Mobil
O i l Corp., w i t h an a c t i v i t y index of ^50. The b a u x i t e extrudate
was of the North American v a r i e t y used in the Claus process f o r
s u l f u r recovery, and contained 2.3 and 12.5 wt % of i r o n and
S i 0 , respectively.
2 The m o n t m o r i l l o n i t e c a t a l y s t was obtained
from Chemetron Corp. (No. K306), and was used in the form of
i r r e g u l a r 14/60 mesh granules. I t s wt % composition was S1O2,
71.7; A 1 0 , 12.5; F e 0 , 5.2; CaO, 2.7; MgO, 3.6; i g n i t i o n
2 3 2 3

14. YAN AND ROSYNEK Reaction of Steam with Coke 285
l o s s , 4.0. The two -alumina s u b s t r a t e s were obtained from

C o n t i n e n t a l O i l Co. (Catapal S, in p e l l e t e d form) and from
Harshaw Chemical Co. (A1-1706E, 1/8 in. e x t r u d a t e ) . A l l sub
s t r a t e s were c a l c i n e d in a i r f o r 16 hrs at 1000F before use.
Table I
P h y s i c a l P r o p e r t i e s of S o l i d Substrates
S.A. Pore V o l . Ave. Pore App. Dens. Real Dens.

2
Substrate (m /g) (cc/g) Diam. () (g/cc) (g/cc)
Silica-Alumina 150 0.46 92 1.13 2.35

(Durabead)
Silica-Alumina 25
(Montmorillonite)
Y-Alumina 250 0.53 65 0.69 3.32

(Catapal S)
-Alumina 218 0.77 0.51

(Harshaw)
Bauxite 62 0.44 261 1.39 3.55
For experiments i n v o l v i n g metal-containing s u b s t r a t e s ,

samples of the Durabead s i l i c a - a l u m i n a were impregnated w i t h the
n i t r a t e s a l t s of copper, i r o n , or n i c k e l , or w i t h vanadyl
s u l f a t e , at a l e v e l of 5 wt % metal, and then c a l c i n e d in a i r
f o r 10 hrs at 1000F. The r e s u l t i n g metal o x i d e - c o n t a i n i n g
m a t e r i a l s were then subjected to the coking procedure d e s c r i b e d
below without f u r t h e r treatment.
Residuum b o i l i n g at >650F and d e r i v e d from an Agha J a r i
crude o i l was used f o r the coking procedure. The residuum had
an API g r a v i t y of 17.3, a pour p o i n t of 75F, a kinematic
v i s c o s i t y of 800 cs. at 100F, and n i t r o g e n and s u l f u r contents
of 2.42 and 0.33 wt %, r e s p e c t i v e l y .
Procedures. Coke was deposited on each of the v a r i o u s

s o l i d s u b s t r a t e s by i n t i m a t e l y mixing with Agha J a r i residuum at
a s o l i d / o i l r a t i o of 0.5 by weight in a r e a c t o r equipped w i t h a
s t i r r e r and a r e f l u x condenser> The coking r e a c t i o n was allowed
to proceed at 900F f o r 24 hrs under 1 atm. of n i t r o g e n . The
coked s u b s t r a t e was then s t r i p p e d f o r 3 hours w i t h flowing
n i t r o g e n in a t u b u l a r r e a c t o r at 950F, and f i n a l l y cooled under
n i t r o g e n to room temperature. The composition of cokes on the
s u b s t r a t e s were determined by a combustion method. The composi
t i o n of coke on the s i l i c a - a l u m i n a c a t a l y s t was CHQ.25 The
r e s u l t i n g l e v e l s of coke deposited on the v a r i o u s s u b s t r a t e s are
contained in Table I I .

286 COKE FORMATION
Table I I
Steam/Coke Reaction Rates At 1500F
Basic T o t a l Coke F i r s t Order Rate

2 1
Run Material Substrate (wt %) Const, (x 1 0 min" )
17 Durabead Silica-Alumina 4.9 0.50

59 Montmoril- Silica-Alumina 10.0 0.45
lonite
56 Catapal Alumina 7.0 2.17
Pellets
58 Catapal Alumina 11.4 1.37
Pellets
52 -Alumina Alumina 15.2 1.31
Extrudate
60 Bauxite Alumin
Extrudate
Two grams of e x t e r n a l l y - c o k e d s u b s t r a t e were charged to a

1/2" OD 12" long Vycor, downflow r e a c t o r that contained a
t h i n - w a l l e d l o n g i t u d i n a l thermowell. The r e a c t o r space above
and below the s u b s t r a t e bed was packed w i t h 10-20 mesh Vycor
chips. Water was fed with a syringe pump at 2 g/hr, and vapor
i z e d upon contact w i t h the hot Vycor c h i p s . Unreacted steam was
condensed at the r e a c t o r e x i t , and the t o t a l volume of gas flow
was measured w i t h a wet t e s t meter. Samples of the e f f l u e n t gas
were taken p e r i o d i c a l l y and analyzed mass s p e c t r o m e t r i c a l l y f o r
H , CO, C0 , N
2 2 2 and 0 .
2 From these analyses, the r a t e s of
disappearance of carbon and appearance of carbon monoxide and
carbon d i o x i d e were c a l c u l a t e d . The g a s i f i c a t i o n r e a c t i o n s were
c a r r i e d out in the temperature range 1400-1600F.
G a s i f i c a t i o n K i n e t i c s of Coke Deposited on S i l i c a - A l u m i n a .
Within the temperature range 1400 to 1600F and in the presence
of excess steam, the g a s i f i c a t i o n r e a c t i o n of coke deposited on
the s i l i c a - a l u m i n a c r a c k i n g c a t a l y s t c l o s e l y followed f i r s t -
order k i n e t i c s with respect to unreacted carbon (Figure 1).
F i r s t - o r d e r r a t e constants were c a l c u l a t e d from the slopes of
these p l o t s (Table I I I ) , and y i e l d e d an a c t i v a t i o n energy of
55.5 Kcal/mole.

YAN AND ROSYNEK Reaction of Steam with Coke 287
Figure 1. Kinetics of steam gasification of coke deposited on silica-alumina, for

reaction temperatures of 1400F (O), 1500F ({J), 1550F (A), and 1600F (V).

288 COKE FORMATION
Table I I I
Rate Constants f o r Carbon + Steam Reaction
on S i l i c a - A l u m i n a Substrate
F i r s t - O r d e r Reaction
(F) Rate Constant (min" ) 1
1400 .00121
1500 .00463
1550 .00906
1600 .01668
3 - 1
The r e a c t i o n r a t e constant at 1500F of 4.6 10" m i n i s
s t r i k i n g l y s i m i l a r to
and Synthane processe
r e s u l t s o f Fuchs et a l . ) ( 6 ) . The a c t i v a t i o n energy o f 55.5
Kcal/mole i s w i t h i n the range (51.3 to 56.6 Kcal/mole) reported
p r e v i o u s l y by T y l e r and Smith f o r g a s i f i c a t i o n o f petroleum coke
and e l e c t r o d e m a t e r i a l s (13). In a d d i t i o n , our r e s u l t i s much
lower than the 83 5 Kcal/mole found by Long and Sykes (14) f o r
g a s i f i c a t i o n o f p u r i f i e d c h a r c o a l , but c l o s e to the 55 7
Kcal/mole that they observed f o r contaminated c h a r c o a l .
E f f e c t o f Impregnated Metals on Coke G a s i f i c a t i o n Rate.

The steam-carbon r e a c t i o n i s known to be c a t a l y z e d by metals,
p a r t i c u l a r l y t r a n s i t i o n metals (_3,4 ). In an e f f o r t to improve
the r a t e o f g a s i f i c a t i o n , separate samples o f the s i l i c a -
alumina (Durabead) c a t a l y s t were impregnated with one of v a r i o u s
metals p r i o r to coke d e p o s i t i o n , and the r e s u l t s f o r the subse
quent steam-carbon r e a c t i o n at 1500F over these m a t e r i a l s a r e
shown in F i g u r e 2 and Table IV. The e f f e c t s o f the deposited
metal oxides can be summarized as f o l l o w s :
Cu, V, Fe: No e f f e c t on the g a s i f i c a t i o n r e a c t i o n r a t e .

Ni: A c c e l e r a t i o n o f the i n i t i a l g a s i f i c a t i o n
r a t e ( f o r coke conversions up to ^30%).

YAN AND ROSYNEK Reaction of Steam with Coke 289
Figure 2. Kinetics of steam gasification at 1500F of coke deposited on silica-

alumina impregnated with oxides of copper (A), vanadium (Q), iron (V), and
nickel (O, 3, Q, # [various preparations]).

290 COKE FORMATION
Table IV
Coke/Steam Reaction Rates on Metal-Impregnated Durabead
( S i l i c a - A l u m i n a ) TCC C a t a l y s t s at 1500F
1
Rate Constant (min" ) R e l a t i v e Rate Constant
Run Metal Wt % 0-30% Conv. >30% Conv. 0-30% Conv. >30% Conv.
17 _ _ .0046 __ 1.00
39 Fe 5 .0058 1.25
40 Cu 5 .0049 1.05
41 V 5 0046 1.00
38 Ni 5 .0139 .0059 3.00 1.28
42 Ni 5 .0137 .0063 2.96 1.37
43 Ni 5 .0140 .0067 3.02 1.46
Impregnated Cu, V
of subsequent coke g a s i f i c a t i o n
f o r a s i l i c a - a l u m i n a c r a c k i n g c a t a l y s t contaminated w i t h metals
up to a l e v e l of MD.2 wt %, the r a t e of o x i d a t i o n o f deposited
coke d i d not i n c r e a s e in comparison w i t h that over the uncon-
taminated c a t a l y s t . These metals are known to a c c e l e r a t e the
r e a c t i o n , however, when they are admixed i n t i m a t e l y w i t h the
coke. I t i s apparent in t h i s case that contact between the
impregnated metals and the coke was not s u f f i c i e n t l y c l o s e to be
catalytically significant. Haldeman and Botty (16) found that
on a s i l i c a - a l u m i n a c r a c k i n g c a t a l y s t c o n t a i n i n g 6% coke by
weight, the dimensions of the average coke p s e u d o c r y s t a l l i t e
were 17 and 10-12 f o r Le (normal to l a y e r s ) and La ( i n p l a c e
of l a y e r s ) , r e s p e c t i v e l y . For an i n t e r l a y e r s p a c i n g of 3.47 ,
t h i s represents about 5 p a r a l l e l l a y e r groups. Coke d e p o s i t s
were a l s o found to be l o c a t e d p r e f e r e n t i a l l y on the metal s i t e s .
At h i g h e r coke l e v e l s , the p s e u d o c r y s t a l l i t e s should be l a r g e r
and c o n t a i n more l a y e r s . Thus, at the coking l e v e l o f ^10% used
in t h i s study, the metals could be completely covered w i t h coke,
be impermeable to steam, and, hence, i n e f f e c t i v e c a t a l y t i c a l l y .
Since the g a s i f i c a t i o n r e a c t i o n followed f i r s t - o r d e r k i n e t i c s up
to coke conversion l e v e l s of 50%, i t i s apparent t h a t , assuming
uniform g a s i f i c a t i o n , even p s e u d o c r y s t a l l i t e s one-half the
o r i g i n a l s i z e are s t i l l too l a r g e f o r the metals to be e f f e c t i v e .
An a l t e r n a t i v e , but l e s s l i k e l y , e x p l a n a t i o n f o r the c a t a l y t i c
i n e f f e c t i v e n e s s of deposited Fe, Cu, and V i s that these metals
r e a c t w i t h s i l i c a - a l u m i n a at the h i g h g a s i f i c a t i o n temperatures
to form c a t a l y t i c a l l y i n a c t i v e s i l i c a t e s , aluminates, or s o l i d
mixtures.
There i s another p o s s i b l e e x p l a n a t i o n f o r the apparent l a c k
of e f f e c t of metals on the steam g a s i f i c a t i o n r e a c t i o n r a t e .
The metals deposited on s u b s t r a t e s could c a t a l y z e the dehydro-
genation r e a c t i o n during the coking step l e a d i n g to "cokes" of
lower hydrogen content. Such low-hydrogen "coke" i s known to
react w i t h steam more slowly. Thus, the metals could a f f e c t the

steam carbon r e a c t i o n in two opposite ways; v i z . , to i n c r e a s e

the r a t e by c a t a l y z i n g the r e a c t i o n on one hand and to decrease
the r e a c t i o n r a t e by forming slow r e a c t i n g cokes on the other
hand. Except f o r n i c k e l , these two e f f e c t s counteract each
other so that the deposited metal shows no o v e r a l l e f f e c t on the
r a t e of steam coke r e a c t i o n .
In marked c o n t r a s t to the e f f e c t s observed w i t h i r o n ,
vanadium and copper oxides, p r i o r impregnation of s i l i c a - a l u m i n a
w i t h n i c k e l oxide l e d to a c o n s i d e r a b l e i n c r e a s e in the i n i t i a l
r a t e of subsequent coke g a s i f i c a t i o n , up to a coke conversion
l e v e l of V30% (Figure 2).
The k i n e t i c s of carbon d e p o s i t i o n on n i c k e l have been
s t u d i e d in d e t a i l p r e v i o u s l y (17,18,19), and a mechanism which
e x p l a i n s most observations has been advanced. Coke p r e c u r s o r s
proceed through a s e r i e s of dehydrogenation steps on the n i c k e l
surface, r e s u l t i n g eventuall
s p e c i e s d i s s o l v e in, an
detaching n i c k e l c r y s t a l l i t e s from the s u r f a c e of the bulk
n i c k e l or the s i l i c a - a l u m i n a surface. Further coke d e p o s i t i o n
i n c o r p o r a t e s a d d i t i o n a l n i c k e l i n t o the growing carbon l a y e r , as
shown by e l e c t r o n m i c r o s c o p i c examination of the d e p o s i t s (18).
In the experiments reported here, some n i c k e l may, there-
f o r e , be t r a n s p o r t e d by the growing carbon c r y s t a l l i t e s to the
s o l i d s u r f a c e d u r i n g coke d e p o s i t i o n . When the carbon-steam
r e a c t i o n i s subsequently begun, t h i s n i c k e l i s p a r t i c u l a r l y
a c c e s s i b l e and r e a c t i v e , and r e s u l t s in an i n c r e a s e d i n i t i a l
r e a c t i o n r a t e . In a d d i t i o n , however, there i s apparently a
second f r a c t i o n of coke, deposited on the s i l i c a - a l u m i n a sub-
s t r a t e , which i s not a s s o c i a t e d with the n i c k e l . T h i s coke i s
not a f f e c t e d by impregnated n i c k e l and r e a c t s more slowly,
p a r a l l e l i n g the behavior of coke on metal-free s i l i c a - a l u m i n a .
The presence of these two types of coke r e s u l t s in the observed
k i n e t i c behavior. Our data i n d i c a t e that about 30% of the coke
r e a c t s at a r a t e approximately 3 times greater than that
deposited in the absence of n i c k e l , w h i l e the remaining 70% of
the coke r e a c t s at the same r a t e as that without n i c k e l (Table
III). This r e s u l t suggests that the f r a c t i o n of coke a s s o c i a t e d
with the n i c k e l i s about 30%.
E f f e c t of Substrate on Coke G a s i f i c a t i o n Rate. The e f f e c t

of s u b s t r a t e v a r i a t i o n s on the steam-carbon r e a c t i o n r a t e at
1500F i s shown in Table I I and in F i g u r e 3. The s u b s t r a t e s can
be c l a s s i f i e d i n t o two c a t e g o r i e s according to t h e i r e f f e c t on
coke g a s i f i c a t i o n r e a c t i o n r a t e s :
Low activity: S i l i c a - a l u m i n a ( c r a c k i n g c a t a l y s t and

Montmorillonite)
High a c t i v i t y : Alumina, ( c a l c i n e d Catapal, alumina
and b a u x i t e ) .

292 COKE FORMATION
At 1500F, the steam-coke r e a c t i o n on alumina occurs

approximately three to s i x times f a s t e r than on s i l i c a - a l u m i n a
type s u b s t r a t e s . Comparison of r e s u l t s from Runs 56 and 58
i n d i c a t e s the extent of r e p r o d u c i b i l i t y of the experiments. In
comparison with t h i s r e p r o d u c i b i l i t y and in c o n s i d e r a t i o n of the
observed consistency, the increased g a s i f i c a t i o n r a t e s on the
alumina substrates are s i g n i f i c a n t . A l l alumina-based m a t e r i a l s
t e s t e d , v i z . , -alumina, c a l c i n e d Catapal, and bauxite, showed
e q u a l l y high a c t i v i t i e s .
The a c t i v a t i o n energies f o r coke g a s i f i c a t i o n on the three
substrates shown in Figure 4 were ^33 Kcal/mole f o r the three
alumina-based m a t e r i a l s and 54 Kcal/mole, f o r the s i l i c a - a l u m i n a
catalysts. The increased a c t i v i t y and lower a c t i v a t i o n energy
f o r the coke deposited on the aluminas (compared to that on the
s i l i c a - a l u m i n a s ) cannot be due to a d i r e c t c a t a l y t i c e f f e c t of
alumina on the g a s i f i c a t i o
e f f e c t o f the alumina tha
(surface area and s t r u c t u r a l d i s o r d e r ) of the coke during i t s
deposition.
The coke formed on alumina appears to be more s t r u c t u r a l l y
disordered. I t i s l e s s g r a p h i t i c , more porous, higher in
surface area, and lower in d e n s i t y than that deposited on the
silica-alumina catalyst. This type of coke w i l l be more r e a c t i v e
in the g a s i f i c a t i o n r e a c t i o n (6). Q u a l i t a t i v e l y , i t was a l s o
observed that the v a r i o u s aluminas coked more q u i c k l y and at
lower temperatures during the coking procedure than d i d the
silica-aluminas. This i s in agreement with the r e s u l t s of
Tantarov et a l . , who found that during c a t a l y t i c c r a c k i n g o f
-methyl styrene at 450C, the i n i t i a l coking r a t e on alumina
was twice that on s i l i c a - a l u m i n a (20). The alumina c a t a l y z e s
the coke d e p o s i t i o n on the s u b s t r a t e and, perhaps, promotes
formation of more r e a c t i v e coke. The enhanced r e a c t i v i t y o f
coke on alumina could be the r e s u l t of increased s u r f a c e area
(higher p o r o s i t y ) , but the nature o f the coke could be a l t e r e d
as w e l l , as suggested by the lower a c t i v a t i o n energy (54 v s . 33
Kcal/mole) of g a s i f i c a t i o n . This c o n c l u s i o n i s c o n s i s t e n t with
the observation that coke which i s deposited q u i c k l y i s
g e n e r a l l y l e s s dense and more r e a c t i v e to g a s i f i c a t i o n . An
i n v e s t i g a t i o n of the nature and p h y s i c a l p r o p e r t i e s o f cokes
deposited on v a r i o u s substrates may be h e l p f u l in e l u c i d a t i n g
the mechanism.
The high carbon r e a c t i o n r a t e on alumina makes t h i s
m a t e r i a l the s u b s t r a t e o f choice f o r the proposed petroleum
upgrading scheme (12). For example, i f a r e a c t i o n r a t e constant
- 1
of 0.011 m i n i s r e q u i r e d (corresponding to about 210 min
residence time f o r 90% coke removal), a temperature advantage
of 65F (1495 v s . 1560F) would e x i s t f o r alumina over s i l i c a -
alumina.

0.21 . . . . . .
0 20 40 60 80 100 120
Reaction Time, min.
Figure 3. Kinetics of steam gasification at 1500F of coke deposited on mont-

morillonite (A), silica-alumina ( American Cyanamid alumina (\Zi)> Catapal
alumina, Run 58 (), Catapal alumina, Run 56 (O), and fresh bauxite
/// k
1000/T, K - 1
Figure 4. Arrhenius plots for steam gasification of coke deposited on American

Cyanamid alumina (A), fresh bauxite ([J), and silica-alumina (O). Corresponding
activation energies are 32.6, 33.8, and 53.1 kcal/mol, respectively.

294 COKE FORMATION
Acknowledgment
The authors wish to thank Dr. W. K. B e l l f o r v a l u a b l e

discussions.
Literature Cited
1. Walker, P.L., J r . ; Rusinko, J.F., Jr.; Austin, L.G.

"Advances i n Catalysis"; Eley, D.D., Selwood, P.W., Weisz,
P.B., Eds.; Academic Press: New York, 1959; Vol. XI, 133.
2. Ergun, S.; Mentser, M. "Chemistry and Physics of Carbon";
Walker, P.L., Jr., Ed.; Marcel Dekker: New York, 1965;
Vol. 1, 203.
3. Walker, P.L., Jr.; Shelef, M.; Anderson, R.A. "Chemistry
and Physics of Carbon"; Walker P.L. Jr. Ed.; Marcel
Dekker: New York
4. Rewick, R.T.; Wentreck, , , ,
5. Wilks, K.A.; Gardner, N.C.; Angus, J.C. Symposium on
Structure and Reactivity of Coal and Char; 170th National
ACS Meeting, Chicago, 1975.
6. Fuchs, W.; Yavorsky, P.M. Symposium on Structure and
Reactivity of Coal and Char; 170th National ACS Meeting,
Chicago, 1975.
7. Nandi, S.P.; Lo, R.; Fischer, J. Symposium on Structure
and Reactivity of Coal and Char; 170th National ACS
Meeting, Chicago, 1975.
8. Johnson, J.L. "Coal Gasification"; Massey, L.G., Ed.; ACS
Advances i n Chemistry Series, No. 131, 1974; 145.
9. Willson, W.G.; Sealock, L.J., J r . ; Hoodmaker, F.C.;
Hoffman, R.W.; Stinson, D.L.; Cox, J.L. "Coal Gasification";
Massey, L.G., Ed.; ACS Advances i n Chemistry Series, No.
131, 1974; 203.
10. Kirk, M.C., Jr. U.S. Patent 3,691,063, 1972.
11. Kimberlin, C.N., Jr.; Hamner, G.P. U.S. Patent 3,726,791,
1973.
12. Rosynek, M.P.; Shipman, G.F.; Yan, T.Y. U.S. Patent
3,983,030, 1976.
13. Tyler, R.J.; Smith, I.W. Fuel, 1975, 54, 99.
14. Long. F.J.; Sykes, K.W. J. Chim. Phys. 1950, 47, 361.
15. Hall, J.W.; Rase, H.F. Ind. Eng. Chem. Process Design
Develop. 1963, 2, 25.
16. Haldeman, R.G.; Botty, M.C. J. Phys. Chem. 1959, 63, 489.
17. Lobo, L.S.; Trimm, D.L. J. Catal. 1973, 29, 15.
18. Lobo, L.S.; Trimm, D.L.; Figueiredo, S.L. Proc. 5th Intern.
Congr. Catal. 1972; Vol. 2, 1125.
19. Figueiredo, S.L.; Trimm, D.L. J. Catal. 1975, 40, 154.
20. Tanatarov, M.A.; Akhmetshina, M.I.; Levinter, M.E. Kinet.
Katal. 1971, 12, 511.

15
Process of Coke Formation in Delayed Coking
C . A . A U D E H and T . Y . Y A N
Mobil Research and Development Corporation, Central Research Division,

Princeton, N J 08540
The process of coke formation in a delayed

coker has bee
s e l e c t i v i t i e s hav
overall sequence of coke development i s
suggested.
Kinetic, tracer and quenching studies have
shown that feed entering the coker at the
incipient coking temperature undergoes a two
stage thermal decomposition to gas and liquid
products and coke. In the f i r s t stage, thermal
cracking takes place producing gas and liquid
products at a fast rate R , with simultaneous
f
condensation reactions which result in the

formation of non-volatile semicoke. The
volatiles leave the coking zone rapidly. Steam
injected with the feed f a c i l i t a t e s the removal
of v o l a t i l e s to minimize secondary cracking.
Hot feed continues to enter the drum and
pushes the semicoke upward with l i t t l e or no
mixing. Meanwhile, in the second stage, the
semicoke continues to undergo pyrolysis, leading
to more gas, l i q u i d and coke, at a slower rate
At 915 P, in the f i r s t stage the reaction

rate i s 10.9 times that of the second stage
(R /R 10.9) and the liquid yield i s higher.
f s
The product s e l e c t i v i t i e s for gas, l i q u i d and

coke were 4, 57 and 39 and 7, 21 and 72% wt. for
the fast and slow stages respectively.
In connection with thermal and catalytic processes such

as coking, pyrolysis and catalytic cracking f o r the
conversion of petroleum fractions, there i s considerable
interest in the mechanism of the transformation of various
0097-615 6/82/0202-0295 $06.00/0


296 COKE FORMATION
organic materials into coke. In particular, Singer (1)

studied the i n i t i a l steps associated with the coking of a
series of pure organic compounds. Whittaker e t . a l . , ( 2)
concentrated on the coking of residual o i l s and studied the
nature of coke precursors and their p l a s t i c i t y . Others
(3,4) have studied other aspects, with particular emphasis
on kinetics, and have developed complex mathematical models
to describe the coking process (4). A l l these studies agree
that coking i s a thermal process"in which feed i s decomposed
to generate free radicals and light products. Some free
radicals undergo condensation/polymerization reactions which
result in the formation of coke.
Published kinetic data were generally obtained in batch
reactors (1-5). The data obtained were observed to f i t
f i r s t order kinetics notwithstanding the complexity of the
feeds studied and
product-forming intermediates
batch coking has a definite induction period and that the
usually observed f i r s t order coking behavior of complex
feeds i s only apparent. Also i t was determined that the
rates observed could f i t third order kinetics for
decomposition and fourth order for polymerization/
condensation (5). Clearly, kinetics of batch coking are
only approximations.
Delayed coking i s a well developed commercial process
(6), and operates on a semi-continuous basis. Feed, usually
vacuum residue, mixed with steam, i s continuously pumped
through tubular heaters in which i t i s heated to i t s
incipient coking temperature. At this temperature the feed
i s injected into an insulated drum where coking takes place.
The vapors produced in the drum during coking are
continuously removed and fractionated. The fractions
usually include coker naphtha and light and heavy coker gas
o i l s . As a drum f i l l s up, feed i s switched to another drum.
Meanwhile, the f u l l drum i s steam stripped, cooled and the
coke d r i l l e d out. Whereas feed i s continuously supplied to
the drum, the coke i s recovered intermittently.
In considering the nature of delayed coking in a
continuous process i t i s clear that no specific amount of
feed i s under consideration i f only part of the coking
period i s studied. Also, feed i s continuously transformed
during the coking process. Volatiles, with the help of
steam, leave the coking zone continuously as soon as they
are formed and pass through layers of material that are at
various stages of the coking process. It would appear that
a yet more involved model would be needed to describe the
coking process in the continuous mode than in the case of
batch coking.
An aspect of coking which has received l i t t l e or no
attention in the published literature (7) concerns the gross

15. AUDEH AND YAN Coke Formation in Delayed Coking 297
physical changes involved in delayed coking. Such

information could be helpful in commercial unit design and
in the interpretation of commercial unit performance. Some
information i s , however, available about the apparent
densities of the vapor phase within a commercial coke drum
(8). Apparent density i s a measure of the relative position
of the solid phase in a coke drum, usually such information
i s used as an aid in determining optimum operating levels of
a specific coke drum.
We have studied the process of coke formation in a
laboratory-scale continuous coker from which the overall
sequence of coke development could be described.
Experimental
Figure 1 depict
used in these experiments
furnace, f i t t e d with three independently controlled zones,
and was equipped with gas and liquid measurement and
recovery systems. Coke recovery in the form of plugs was
carried out by the use of a hydraulic ram or lathe operating
on an aluminum rod with the same diameter as the preheater
plug.
The feed used was a 1050 F+ residue from a
commercially operated unit and was processed at typical
commercial conditions, 915F and 40 psig. In addition,
operation at lower temperatures and pressures as well as
higher temperatures were explored in these studies. In a l l
the coking experiments, steam, 2% by wt. of the feed, was
introduced with feed in the preheating zone.
For tracer experiments, where two residues with
different metals content were used, feed to the coker was
interrupted to allow for the feed change. Metals p r o f i l e in
the coke was obtained by taking sections from the coke plug
and determining the metals concentration in each section.
The metals, nickel and vanadium, were determined by atomic
absorption.
In the quenching experiments, the usual coking
procedure was i n i t i a l l y followed. However, after the
required amount of feed was pumped into the drum, the
experiment was stopped by quickly removing the drum from the
furnace and immersing i t in a mixture of ice and water. The
quenched contents were carefully removed from the drum,
inspected and sectioned. Each section was then extracted in
a Soxhlet extractor with toluene, u n t i l the toluene extract
became colorless.
Formation of Coke. Tracer and quenching studies were

298 COKE FORMATION
carried out to follow the progress of feed conversion from

the point of entry into the coking drum. In the tracer
studies two residues with different metals concentrations
were used. I n i t i a l l y i t was determined that coke prepared
from each of the residues had a s i g n i f i c a n t l y different
concentration of metals. Thus by taking contiguous sections
from the coke plug and determining the metals concentration,
the metals p r o f i l e of the coke plug recovered from the coker
could be determined. Since coke produced from each of the
feeds has a known metals concentration, i t i s possible to
determine from which feed the coke was derived and thus
assess the flow pattern of each residue.
Figure 2 depicts the concentration p r o f i l e of the
metals in the coke. It i s apparent that the coke formation
i s representative of plug flow through the coker The top
portion of the cok
and 125 ppm Ni, and th
Ni. These metals concentrations correspond to those of coke
derived from the f i r s t residue followed by coke from the
second residue.
This observation shows that feed entering the drum does
not penetrate and mix with the material already in the coke
drum. The carbonizing mass continues i t s reaction process
with l i t t l e or no co-mingling of the materials at the
various intermediate stages that, ultimately lead to coke
formation. Early (9) and recent (2) reports have shown that
coking of residues involves a sequence of phase changes with
different p l a s t i c i t y characteristics. Whittaker (2) found
that, depending on the feed, the carbonizing mass retains
p l a s t i c i t y up to 95% of the residence time at the coking
temperature. Quenching experiments, Table I, show that the
carbonization progresses continuously from the entrance of
the feed and that the carbonizing mass would have the
p l a s t i c i t y required for flow at the coking temperature.
Formation of Products. The rate of conversion of feed

into products was determined in terms of the rate of
formation of v o l a t i l e s , gas and l i q u i d products, and by
difference the non-volatiles. The gaseous product includes
C -C hydrocarbons and the liquid C -ioooF.
1 4 5 Gas rates
were obtained from the composition and volume of the gas
generated during each experiment. Similarly, the rate of
l i q u i d product was obtained by determining the weight of
liquid product condensed at room temperature for each coking
experiment.
It was found that, at the temperatures studied,
volatiles formed at a constant rate as long as feed i s
introduced into the coker; upon stopping the feed, however,
the rate drops (Figure 3). Similarly the rate behavior of
gas formation was also observed (Figure 4).

AUDEH AND YAN Coke Formation in Delayed Coking 299

VOLATILE
PRODUCTS
900
800
700
600
400
300
200
100
2 4 6 8 10
INCHES
FEED
Figure 1. Experimental coker drum and typical temperature profile.
125 ppm Ni
4 2 5 ppm V in coke
Top
Low Metals Feed (42 ppm Ni, 126 ppm V)
2 8 % coke
High Metals Feed (130 ppm Ni, 4 2 0 ppm V)

4 6 % coke
Bottom 3 0 0 ppm Ni
8 5 5 ppm V in coke
Figure 2. Consecutive coking of two residues with different metal content. Key:
low metals, 90 cm ; and high metals, 50 cm . Conditions: temperature,
3 3
915F;
pressure, atmospheric; and steam, 2% by weight.

300 COKE FORMATION
Table I
Toluene Solubles Determined for a
Quenched Coking Reaction in a Continuous Coker
Temperature : 91
Pressure : atmospheri
Steam: 2% by weight
Operation time, min: 320
Approximate % of Toluene Approximate

Position Total Soluble "Residence"
a. Coke Plug in Drum, in. "Coke" % wt. Time, min.
Section 1 0-1/4 4 35 3-12
Section 2 1/4-1 1/4 24 5 12-80
Section 3 1 1/4-4 1/2 56 <1

80-320
Section 4 4 1/2 16 <1
b. Solubility of Vacuum Residue and Dry Coke in Toluene
% Wt.
Vacuum Residue 100
Dry Coke <1

15. AUDEH AND Y AN Coke Formation in Delayed Coking 301
WEIGHT OF VOLATILES, GAS LIQUID, COLLECTED VS. TIME
100 200 300 400 500
TIME,MINUTES
Figure J. Coking of a vacuum residue at 1035F.
VOLUME OF GAS COLLECTED AT DIFFERENT TEMPERATURES

12.5
250 500 750 1000 1250 1500

TIME, MINUTES
Figure 4. Coking of a vacuum residue at 1035F (), 915F (), and 835F (&).

302 COKE FORMATION
The above observations suggest that volatiles are

formed at two rates; an i n i t i a l fast rate (R ) and a f i n a l
f
slow rate ( R ) . This indicates that the conversion of feed

s
into coke takes place in two gross steps: F i r s t a fast

conversion of feed into a v o l a t i l e product, gas and l i q u i d ,
and a non-volatile product, semi-coke; secondly, a slower
conversion of the non-volatiles into more v o l a t i l e s and,
ultimately, coke, equations 1 and 2.
Peed > Volatiles + Non-volatiles (Semi-coke) (1)
Non-volatiles îpw ^ Volatiles + Coke (2)
In a delayed coking process only the v o l a t i l e s are

removed while feed i s continuously added to the carbonizing
mass. Both the fas
the incremental fee
already in the coker which i s in the process of coking.
Thus, when the coker i s being fed the amount of v o l a t i l e
products measured i s the sum of the products produced by the
fast reaction and by the slow reaction. After the feed i s
stopped and the rate drops, another constant but slow rate
of product formation i s observed. From the calculated slow
rate of product formation R , the proportion contributed by
s
the slow reaction during conventional operation could be

backed-out and the rate of the fast reaction, alone,
calculated.
Table II shows the product yield for coking a vacuum
residue at 3 temperatures and the percent of gas and liquid
produced by the slow and fast reactions, respectively.
Coking at 835F gives proportionately more l i q u i d in the
t o t a l v o l a t i l e s as a result of the slow reaction than at
915F and 1035F. The data available are insufficient to
determine an overall rate constant for the process, equation
3.
Feed > Volatiles + Coke ( 3)
However, based on the model proposed the relative rates of

the fast and slow reactions, Rf/R / nay be derived. These
S
e e e
are 5.4, 10.9 and 8.9 for 835 F, 915 F, and 1035 F
respectively, Table I I .
At 1035 F a considerable increase in the y i e l d of gas
was observed. This i s the result of secondary cracking of
l i q u i d product formed during the coking process which
results in a reduced y i e l d of l i q u i d and a higher proportion
of the gas component in the volatiles. From the
relationships between the products i t i s possible to
calculate s e l e c t i v i t i e s for the fast and slow reactions,
Table I I I . A p i c t o r i a l representation of these data i s

15. AUDEH AND Coke Formation in Delayed Coking 303
Table II
Yields of Gas and Liquids Products and
Their Rates of Formation for the Coking
of Vacuum Residue at Different Temperatures
Temperature, F 835 915 1035
Gas Collected, %wt

Reaction 1, fast 1.68 4.06 11.32
Reaction 2, slow 4.32 2.94 7.68
6.00 7.00 19.00
Liquid Collected, %wt

Reaction 1, fast 45.63 56.81 52.66
Reaction 2, Slow 15.37 8.19 6.34
61.00 65.00 59.00
V o l a t i l e s , Collected, %wt
Reaction 1, fast 47.31 60.87 63.98
Reaction 2, Slow 19.69 11.13 14.02
67.00 72.00 78.00
2
Rates of Formation, 10 gm/min
Reaction 1, R f 23.7 30.4 32.0
Reaction 2, R g 4.4 2.8 3.6
Reaction rate ratio, Rf/R 5.4 s 10.9 8.9
,Voaltiles: gas and l i q u i d combined.

304 COKE FORMATION
Selectivities fo Liqui g
of a Vacuum Residue at Different Temperatures
Selectivity, %
Coking "semi-coke"
Temp., F Reaction % wt. gas liquid or coke
Overall 100.0 6.0 61.0 33.0

835 Fast 47.3 3.6 96.4
Slow 52.7 8.2 29.2 62.6
Overall 100.0 7.0 65.0 28.0

915 Fast 60.9 6.7 93.3
Slow 39.1 7.5 20.9 71,6
Overall 100.0 19.0 59.0 22.0

1035 Fast 64.0 17.7 82.3
Slow 36.0 21.3 17.6 61.1

15. AUDEH AND YAN Coke Formation in Delayed Coking 305
shown in Figure 5 and the overall coking yield in Figure 6.

As an example, at 915F, in the f i r s t stage, the feed i s
converted into about 4% gas, 57% liquid (61% v o l a t i l e s ) and
39% s o l i d . In the second stage, the 39% solid formed in the
f i r s t stage i s further converted to about 7% gas, 21% liquid
and 72% coke. These data are summarized as overall coking
yields, 7% gas, 65% l i q u i d and 28% coke.
Overall Coking Model. From the tracer experiments,

quenching and toluene s o l u b i l i t y experiments, rates and
product s e l e c t i v i t i e s , the following model appears to
describe the gross behavior of residue in a dealyed coking
process.
a. Feed and steam enter an empty coke drum and the feed in
part i s deposited on the surface of the drum with the
remainder f a l l i n
decomposes at a fas
a carbonizing mass called semi-coke.
b. As more feed and steam are pumped into the drum,
accumulation of the carbonizing mass continues together
with the generation of volatiles. The steam helps in
stripping heavier liquid product from the carbonizing
mass.
c. Hot feed continues to enter the drum and pushes the
non-volatile carbonizing mass upwards with l i t t l e or no
mixing. Concurrently semi-coke i s further pyrolyzed by
the action of the hot vapors and the steam. This
decomposition takes place at a slower rate than that of
the feed and also gives gaseous, l i q u i d and solid
products.
d. Above the solid carbonizing mass a gradation of vapor
density exists, with the least dense vapors nearest the
top of the drum. Some of the more dense vapors could be
converted to coke. Their contribution i s , however,
probably minimal; most of the vapors leave the coke
drum to form the gaseous product and the coker l i q u i d .

306 COKE FORMATION
"L
70h
60
50 GAS
;-40
LIQUID
>
y 30
_
LU 1st 1st Stage-, 1st Stage
CO
Stage
20
SOLID
10
835 915 1035

TEMPERATURE, F
Figure 5. Product selectivity of the two stages in the coking of a vacuum residue
at different temperatures.

AUDEH AND YAN Coke Formation in Delayed Coking 307
75 r
70
60
50-
.40

LU
30
20 h
10
_U
835 915 1035
TEMPERATURE, F
Figure 6. Overall product yields for coking a vacuum residue at different tempera
tures. Key: G, gas; L, liquid; and C, coke.

308 COKE FORMATION
Literature Cited
1. Singer, L. S., J. Chim. Phys. Special Vol. 1969, A p r i l ,

p. 21.
2. Whittaker, M. P. and Grindstaff, L. I., Carbon 1972, 10,
165.
3. Kabak, H. N., Ivanov, S. K. and Anghelova, G. .,
Dokl. Bolg. Akad. Naukk, 1978, 31, No. 9, 1135,
Levinter, . ., Medvedeva, M. I., Panchenkov, G. .,
and Agpov, G. I., Khimiya i Teknologiya Topliv i Masel,
1966, No. 11, 25.
4. Valyavin, G. G., Fryazinov, V. V., Gimaev, R. .,
Syunyaev, . I., Vyatkin, Yu. L., and Mulyukov, Sh. F.,
Chemistry and Technology of Fuels and Oils, 1979, 15,
No. 7-8, 562.
5. Ozaki, H., Murakami
International Carbo
p. 205.
6. Cantrell, ., O i l and Gas J., 1982, March 22, p. 128.
7. Hayashitani, ., Bennison, D. W., Donnelly, J. . and
Moore, R. G., O i l Sands, 1977, 233.
8. Werstler, C. E., Niederstadt, R. J., and Lutz, . .,
O i l and Gas J., 1954, August 9, p. 98.
9. Berry, A. and Edgewood-Johnstone, R., I. . Chem. 1944,
1140.
R E C E I V E D June 28, 1982.

INDEX
A Benzene, chemisorbed on nickel 101/

Benzene on iron, heats of adsorption .. 104
Abrasion 61, 63 Benzene pyrolysis
Acetone, carbon deposition, carbon deposit morphology 112
sulfiding effects 226/ conditions 112
Acetone, heterogeneous surface carbon formation, mech
decomposition 223-238 anism 109-120
Acetone decomposition Beta carbon film 272
mechanism 236 Bifunctional catalyst 249
by niobium, stainless steel, sulfur Bismuth 60
effects 230
on triiron tetraoxide, sulfur effects. Butene 23
on triiron tetraoxide, thiophene
effects 231/
reaction features 236 C
Acetone deposition on stainless
C A E M S e e Controlled atmosphere
steel, sulfiding 227
electron microscopy
Acetylene 123
Carbide nucleation 219
Alkali metal carbonates 76
Carbide particle growth, mech
Alkaline earth oxides 76
anism 219
Alonized Incoloy 800 125
Carbon, filamentous 2, 177
Alumina, differential thermal
growth mechanism 2, 7/
analysis 250/
Carbon, filamentous growth,
Aluminized Incoloy 800 153
hydrogen effect 100
advantages 174
Carbon, scanning Auger map 201
coke deposit morphology 138
Carbon, transport 5
coke deposits 168/, 170/
Carbon buildup 2
coking results 125, 126
Carbon deposit
coking/decoking sequence 143
characterization 8
hydrogen sulfide treatment 155
crystalline particles 207
oxygen treatment 155
particulate development 207
steam treatment 155
Carbon deposit morphology 193-221
Aluminized Incoloy 800 coupons
metal structure influences 217
Carbon deposition
inorganic gaseous treatment
catalyst 191
157/-158/, 161/
cementite formation 185
metal oxide formation 164
gas residence time effect 96/
reaction order 133
mechanisms 194
surface composition 160
presence of carbide 185
Aluminized surfaces 151
rate 119
Aluminum 125
solution-precipitation processes .193-221
Amorphous carbon 2
supports 194
Amorphous carbon film 258, 261
Carbon deposition from acetone,
Argon 60
sulfiding effect 228/
Auger electrons 11
Carbon deposition on
copper 109-120, 115/
Carbon deposition on iron
activation energy 103
Barium oxide 76 Arrhenius plot 94/
Benzene, carbon formation, hydrogen mechanism 103-105
effect 89-106 rate comparison 105/
311

312 COKE FORMATION
Carbon deposition on ironContinued Carbon formation on nickel

rate expression 103 mechanism 100-103
S E M photograph 97/ rate comparison 105/
Carbon deposition on iron foils rate expression 100-103
benzene concentration effects 93-95 Carbon gasification rates 276, 278-279/
deposit structure 95, 96/ apparent activation energies 280
gas flow rate effect 95 interaction of graphite 280
hydrogen effect 95 Carbon monoxide
temperature effect 93-95 disproportionation, iron-
Carbon deposition on iron-oxide catalyzed 5
foils 17/ exposure to nickel catalysts 267
Carbon deposition on nickel radiation-induced degradation 223
activation energy 102 Carbon mound growth 201, 203/,
carbon monoxide exposure 267, 268/ 206/, 207
by carbon monoxide exposure 269/ development 219
by ethylene 258-267 growth kinetics 207
forms 253 particulates 210/
hydrogen effect 96/ Carbon oxidation
morphology 27
reaction network 27
reaction order 101/ oxygen transfer mechanism 83
S E M photograph 97/ temperature effect 63
steam gasification 267 water vapor partial pressure effect. 63
x-ray diffraction 98/ Carbon oxide, formation 50, 56
Carbon deposition on nickel foils Carbon precipitate, lateral spreading 204/
benzene concentration effects 93 Carbon precipitation 201, 202/, 217
deposit structure 95, 96/ Carbon reprecipitation 205/
hydrogen effect 95 Carbonaceous deposits
temperature effects 93 CAEM 14
Carbon deposition on silica-alumina, formation 9/
rate constants 288/ Mossbauer spectroscopy 14
Carbon deposition rate Carbonyl sulfide 232/, 235
gas residence time effect 114/ Carbon-water vapor reaction, acti-
hydrogen partial pressure effect 114/ vation energy 83
temperature effect 112/ Catalyst, carbon diffusion 2
Carbon deposits via decomposition of Catalytic reforming of naphtha,
ethylene, electron mirco- purpose 239
graphs 266/ Cementite 184/, 191
Carbon diffusion, activation Cesium 76
energies 4/ Channeling 76
Carbon dioxide 223 Chemical vapor deposition 27
Carbon dissolution 205/ of silica 27
Carbon fibers 177 Chemisorbed carbon 276
Carbon filament 3/ Chromium 24, 57, 84, 125, 173
formation 6/ Chromium(III) oxide
growth mechanism 90 carbon deposition 227
problems with growth 273 sulfiding effects 229/
spiral 6/ gas phase poisons 227, 223, 234
Carbon film, amorphous 258, 261 sulfiding 227
Carbon formation sulfur poisoning 233
catalyst 184/ surface area 225/
filamentous, macro-scale forma- Clean fuels, production 283
tion 16 Cobalt 76
filamentous, over iron surfaces 1-20 Coke
hydrogen:naphtha ratio effects 250/ effect on hydrogenolysis 249
iron and nickel-catalyzed 89-106 filamentous, growth and initiation
pressure effects 250/ mechanism 177-191
solid phase catalyst 180 metals in, concentration profile 298

INDEX 313
CokeContinued Coke formationContinued

reaction with steam on solids 283-293 quenching studies 297, 298
Coke content, measurement 240 reactor material effect 48
Coke deposit 39/, 41/ role of the surface 172
bulk metals concentrations 24 surface comparison 133
filamentous 42/ surface effects 45
oxidation rates 85/ surface passivation 26
removal 141-143 tracer studies 297, 298
structure effect 64/ Coke formation in delayed coking .295-307
Coke deposit oxidation 67/-68/ Coke formation from ethylene 127
enhancement by inorganic Coke formation from methane 223
catalysts 59-87 Coke formation over naphtha
in water vapor 61 reforming catalyst 239-252
Coke deposition catalyst behavior, H : naphtha
2
coke structure 38 molar ratio effect 246/, 248/

effect of cracking times 38 H : hydrocarbon ratio effect
2 245
measurement 34 pressure effects 241/, 242-244
procedure 285 standard test 241/
Coke deposition on alumina, stea
gasification 293
Coke deposition on impregnated impregnated metal effects 290
silica-alumina, kinetics of reaction rate 286/
steam gasification 289/ reaction rate constant 283
Coke deposition on montmorillonite, Coke gasification rate
kinetics of steam gasification 293/ deposited metal oxides effect 288
Coke deposition on P t / A l 0
2 3 251 impregnated metals effect 288-291
Coke deposition on silica-alumina substrate effect 291-293
activation energy 286 Coke oxidation
gasification kinetics 286 alkali metal salt effect 78/
kinetics of steam gasification 287/ argon effect 62/
Coke deposition on stainless steel .123-148 barium oxide effect 79/
Coke deposition on Vycor surfaces cobalt effect 81/
123-148 conditions 77/
Coke effects 23 experimental measurement 73
Coke formation inorganic contaminants 73
iron effect 80/
acetylene 127
nickel effect 81/
after coking/decoking 144
strontium oxide effect 79/
from carbon monoxide 223
transition metal effectiveness 84
catalysts 26, 30, 56
water vapor effect 65/-66/
decoking effect 34
Coke reaction with steam, im
edge phenomena effect 138
pregnated metal effects 290
factors affecting the rate 151
Coke reaction with steam, reaction
geometrical effect 138, 140-141
rates 286/
heterogeneities effect 138
Coke reforming, catalyst behavior
H : hydrocarbon ratio effect
2 239-252
and pressure effects 243/
hydrogen partial pressure effect .... 127
Coke skin, hard 40/
inhibition 23-42
Coke types 127
-iron-cementite equilibria 180
Coked catalysts 284
iron-iron oxide-iron carbide-gas
Coker drum 298/
equilibria 182/
tt-iron-wustite equilibria 180 Coking 33/
nature 245 Coking, delayed
preoxidized quartz reactor 54/ See also Delayed coking
preoxidized steel reactor 53/ coke formation 295-307
prereduced steel reactor 52/, 53/ Coking, microbalance system 32/
pressure effect 239-252 Coking/decoking sequences, coke
procedure 285 formation after 144
quenched coking 300/ Coking model, overall 305

314 COKE FORMATION
Coking rate measurements 30 deposit structure effect 61, 63

Coking of residue, metal content Ethylene steam cracker Continued
effect 299/ gasification 86
Coking of vacuum residue 301/ gas flow rate effect 61
product selectivity 306/ hydrogen effect 69
product yields 307/ inhibition of coke formation 23-42
selectivities for gas and liquid inorganic contaminants 73
products 304/ oxidation of deposit 59-87
yields of gas and liquid products ... 303/ oxidized deposit, surface
Condensation mechanism 110, 112 topography 82/
Controlled atmosphere electron plant materials investigation 24-26
microscopy 13, 26, 194 presence of metals 26
description 8 sample containment 61
Copper 84 silica coated tubes 34-38
carbon deposition 115/ surface contamination 60
carbon formation 109-120 surface passivation 26, 27
effect on coke gasification 288 See also Surface passivation
Copper foils, preparation Ill temperature effect 63
Core type particles 215
Coupons, metal alloy 12
Cracking, coking deposition 23 Extrusion filaments 5
Cracking temperature, gas com
position effects 36/
Cr 0 See Chromium(III) oxide
2 3
F
C V D S e e Chemical vapor deposition
Fe CSee Iron carbide and Cementite
3
D Fe 0 See Triiron tetraoxide

3 4 225
Ferromagnetic metals, carbon
Decoking 23, 143 formation 1
Delayed coking 296 Filament growth, activation energies .. 4/
coke formation 295-307 Filamentary growth 219, 220
feed 296 Filamentous carbon 2, 177, 193
process 302 delta states 261
Delayed coking process, gross extrusion mode growth 7/
behavior of residue 305 formation 2
1,2-Dichloroethane 123 formation studies 11
Differential thermal analysis of growth center 178
alumina 250/ growth inhibition 2, 5
growth mechanism, extrusion
mode 5,7/

spiral filaments 5
Electron microscopy, carbon deposit Filamentous carbon formation
characterization 257 CAEM 13
ESCSee Ethylene steam crackers macro-scale formation 16
ESCASee X-ray photoelectron Mossbauer spectroscopy 10
spectroscopy over iron surfaces 1-20
Ethane, reaction with iron 19 temperature effects 13
Ethylene 23, 123 Filamentous coke
Ethylene steam cracker catalyst 191
butane effect 69 growth
carbon deposits 224 apparatus 179/
coke formation 59-87 composition 186/
coke inhibition 34-38 reactor support 181/
coke structure 86 growth and initiation
coke surface contamination 86 mechanism 177-191
coke yields 37/ surface effects 185 191
deposit oxidation conditions 75/ Foil pretreatment 48

INDEX 315
G Incoloy 800Continued
aluminized, hydrogen sulfide
Gasification, influence of inorganic treatment 155
contaminants 73 aluminized, oxygen treatment .... 155
Gas-phase carbon formation 110 aluminized, steam treatment 155
Gas-phase reactions, homogenous 124 hydrogen sulfide treatment 155
Gas-phase poisons oxygen treatment 155
carbonly sulfide 235 steam treatment 155
hydrogen sulfide 235 inorganic gaseous treatments .156/, 159/
sulfur dioxide 235 metal oxide formation 164
thiophene 233 polished aluminized, coke deposits .. 171/
Gold 225 polished, inorganic gaseous
Graphite 280 treatment 156/
crystal 10 reaction order 133
iron deposition 10 surface composition 160
nickel-catalyzed gasification, surface composition after treatment 162/
rates 281 titanium content 164
spectroscopic 284 Incoloy 800, aluminized 153
Graphite platelet deposit 5
Graphitic laminar films
coke deposits 168/, 170/
H coking/decoking sequence 143
Hard coke skin 40/ inorganic gaseous
Heavy oil, catalytic processing 284 treatment 157/-158/, 161/
Helium 153 metal oxide formation 164
Heterogeneous metal-catalyzed surface composition 160
reactions 124 Incoloy 800 chromium contact 164
High activity substrates 291 Incoloy 800 tube, uncoated 40/
High alloy steel 24 Inorganic contaminants 73
Homogenous gas-phase reactions 124 Ion etching 197, 213/
H SSee Hydrogen sulfide
2 Iron 24, 56, 125, 173, 194
Hydrocarbon-metal reaction, carbon effect on coke gasification 288
atom formation 90 metallic 19
Hydrocarbon surface film, polymeric . 273 Iron, carbon formation 1
Hydrocarbon synthesis, on nickel activation energy 103
surfaces 277f mechanism 103-105
Hydrocracking, comparison with rate expression 103
hydrogenolysis 249 Iron carbide 10, 14, 16
Hydrogen:hydrocarbon ratio effect 239-252 Iron carbide as catalyst 19
Hydrogen sulfide .151, 164, 228, 232/, 235 Iron-carbon phase diagram 198/
effect on acetone decomposition .... 230/ -Iron-cementite equilibria,
effect on chromium(III) oxide 229/ coke formation 180
Hydrogenolysis, coke effects 249 Iron contamination 207
Hydrogenolysis, comparison Iron foil
with hydrocracking 249 metallic, Mssbauer spectra 15/
structure 200/
surface preparation 199/
I Iron foils, carbon deposition
Impregnated silica-alumina, coke benzene concentration effect 93-95
deposits on, kinetics of deposit structure 95, 96/
steam gasification 289/ gas flow rate effect 95
In situ scanning electron hydrogen effect 95
microscopy, benefits 194 temperature effect 93-95
Incoloy 800 24, 25/, 152 Iron levels, etching effects 211
coking results 125, 126 Iron oxide 10, 18/, 76

316 COKE FORMATION
Iron oxideContinued
identification 11
Naphtha 23
production 16
catalytic reforming, purpose 239
samples 11
properties 240
Iron surface, pretreatment
Naphtha reforming catalyst 239-252
with steam 16
Naphtha reforming catalyst, coke
-Iron-wustite equilibria,
formation over
coke formation 180
catalyst behavior, H 2 : naphtha
molar ratio effect 247/, 248/
pressure effect 241/, 242-244
Ketone decomposition, poisoning 224 standard test 241/
Nickel-catalyzed gasification of
graphite, rates 281
L Nickel 56, 76, 173, 194
Lead 76 carbon deposits on, via ethylene 258-267
Lithium 76 carbon formation
Low activity substrates 291 mechanism 100-103
M Nickel catalyst 257

Manganese 57, 84 carbon deposits on
Mass transfer limitations 90 carbon monoxide exposure 267
Metal-catalyzed reactions, ethylene exposure 270
heterogeneous 124 morphology 270
Metal alloy coupons 124 steam gasification 267
coke deposits 164 properties 257/
coke thickness 167 surface carbon reactivity 253-281
coking rates 165/ temperature-programmed
filamentous coke formation 169 surface reaction 253-281
morphology change 155 deactivation 281
polishing 152 Nickel foils, carbon deposition
pretreatment effect 164 benzene concentration effects 93
surface composition 162 deposit structure 95, 96/
surface morphology 153 gas flow rate effect 95
Metal foil, surface preparation 197 hydrogen effect 95
Metallic iron 19 temperature effects 93
Mssbauer spectra 15/ Nickel reactor, preoxidation effects .... 50
Metals in coke, concentration Nickel-niobium stabilized stainless
profile 298 steel 223
Metal-support interaction 90 Nickel sulfides 151
Methane, filament growth 220 Niobium stainless steel, acetone
Methane radiation-induced decomposition by, sulfur effects .. 230/
degradation 223 Niobium stainless steel, sulfur
Microbalance 47/ poisoning 233, 235
Microbalance reactor 91,92/
Molybdenum 48
Monticular growthSee Mound Octane number 240
growth
Olefin, sources 45
Montmorillonite, coke deposits on, Overall coking model 305
kinetics of steam gasification 293/ Oxidation-reduction cycle 83
Mssbauer spectroscopy 10 Oxygen 153
Mssbauer spectroscopy experiments, Oxygen transfer mechanisms 83
carbonaceous deposits 14
Mound growth 193
carbon 201,203/, 206/, 207

development 219 Particulate deposit 212/
growth kinetics 207 core particles 211
particulates 210/ crystalline particles 207
Mounting systems 195 filamentary deposits 211

INDEX 317
Particulate depositContinued Scanning electron microscopy, carbon

shell particles 211 deposit morphology 193-221
Particulate growth 219, 220 Semi-coke 302
Petroleum chemicals operation 23 Shell thickness 211
Phase diagram 180 Shell type particles 215/
iron-carbon 198/ Silica-alumina, coke deposits on
Platelet carbon 272 activation energy 286
Platinum 5 gasification kinetics 286
Platinum-alumina catalyst, kinetics of steam gasification 287/
coke deposition 251 Silica-alumina, impregnated, coke
Poisons 224 deposits on, kinetics of
Polished aluminized Incoloy 800, steam gasification 289/
coke deposits 171/ Silica-rich surfaces 151
Polished Incoloy 800, inorganic Silica coating 34
gaseous treatment 156/ of steel alloys 27-33
Polymeric hydrocarbon surface film .. 273 Silica films 30
Pore blockage 90 Silicon-rich surfaces 151
Potassium 76 Silver 84
Preoxidation 30
Prereduction 4
Presulfiding treatments 26 Spectroscopic graphite 284
Product formation, rate of coke deposition 123-148
conversion from feed 298 nickel-niobium stabilized 223
Propane steam cracking 45-57 niobium, sulfur poisoning 233, 235
apparatus 47/ removal of coke deposits 123-148
coke formation 49/, 53/ Stainless steel surfaces 151
preoxidized quartz reactor 54/ Steam 59
preoxidized steel reactor 53/54/ Steam cracking
prereduced steel reactor 51/52/ coke yields 37/
prereduced vs. preoxidized 51/ coking deposition 23
quartz reactor with steel 49/ ethylene, inhibiting coke
Propylene 23 formation 23-42
Pseudocrystallites 290 Steam cracking of propane,
Pyrolysis, effect of inorganic gases .151-175 surface effect 45-57
Pyrolysis, surface phenomena Steam reaction with coke
during 151-175 impregnated metal effects 290
Pyrolysis reactor, oxidation 151 reaction rates 286/
Pyrolytic carbon 272 on solids 283-293
Steam reforming, carbon oxide
formation 56
Q
Steel, high alloy 24
Quartz reactor, coke formation 48 Steel, silica-coated 31/
Quenched coking 300/ Steel alloy, silica coating 27-33
Steel alloy, steam treated 28/
R Steel coupons, silica coating,
apparatus 29/
Radiant coils 24 Steel foils, preoxidation 48
Reforming reaction network on Steel reactor
nickel surfaces 277/ carbon oxide formation 50
Rough surfaces 147 preoxidation effects 50
Roughness 155 quartz liner effects 50
minimization in analysis 197 Strontium oxide 76
Rubidium 76
Substrate, high activity 291
Substrate, low activity 291
S Sufide surface layer 224
Salts 61 Sulfided stainless steel, carbon
Scanning Auger map, carbon 201 deposition 227
Scanning electron micrograph, silica Sulfided surfaces, coke formation 169
coated steel 31/ Sulfiding 227

318 COKE FORMATION
Sulfur dioxide 232/, 235 Transmission electron microscopy,

effect on acetone decomposition .... 230/ benefits 194
Sulfur poisoning 223-238 Triiron tetraoxide
thiophene 233 acetone decomposition on
Surface carbon, reactivity on sulfur effects 232/
nickel catalyst 253-281 thiophene effects 231/
Surface carbon, temperature- carbon deposition 227
programmed surface reaction.253-281 from acetone 228/
Surface carbon formation, gas phase poisons 227, 233, 234
mechanism 109-120 sulfiding 227
Surface contamination, with sulfur poisoning 233, 235
inorganic salts 60 surface area 225/
Surface corrosion 147 Tubular reactor, quartz 46
Surface metal carburization 147 Tubular reactor, stainless steel 46
Surface passivation
high temperature team V
pretreatments 26
preoxidation 26 Vacuum residue, coking
presulfiding treatments 2
Surface phenomena during
pyrolysis 151-175 selectivities for gas and liquid
Surface roughness 155 products 304/
Surface sulfiding 151 yields of gas and liquid products .... 303/
Vanadium, effect on coke gasification 288
Vinyl chloride 123
Volatile formation 302
Temperature run-away 284 Volatiles 296
Temperature-programmed surface Vycor 152
reaction 253-281 Vycor glass, coking results 125, 126
carbon deposits by Vycor glass, rate of carbon formation 138
ethylene 259/, 263/, 264/, 270 Vycor reactor 124
carbon monoxide exposure 267/ Vycor surfaces, coke deposition
ethylene exposure 267/ and removal 123-148
microreactor system 254 Vycor tubes, filamentous
system 255/ coke formation 169
Tetraethoxysilane 34
Thermal annealing 197
Thiophene 225, 229/, 230/
Titanium 24, 125, 140 X-ray photoelectron spectroscopy,
Toluene solubles 300/ steam treated steel alloys 27
TPSRSee Temperature-programmed
surface reaction
Tracer studies 298
Transition metals 177 Zirconium 60
Jacket design by Martha Sewall.

Indexing and production by Deborah Corson and Anne Bigler
Elements typeset by Service Composition Co., Baltimore, MD

Printed and bound by Maple Press Co., York, PA


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Coke Formation

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Basedona symposium jointly sponsored

ACS SYMPOSIUM SERIES 202

In Coke Formation on Metal Surfaces; Albright, L., et al.;

In Coke Formation on Metal Surfaces; Albright, L., et al.;

David L. Allara Marvin Margoshes

Robert Baker Robert Ory

Donald D . Dollberg Leon Petrakis

Robert E. Feeney Theodore Provder

Brian M . Harney Charles N. Satterfield

W . Jeffrey Howe Dennis Schuetzle

James D . Idol, Jr. Davis L. Temple, Jr.

Herbert D . Kaesz Gunter Zweig

In Coke Formation on Metal Surfaces; Albright, L., et al.;

In Coke Formation on Metal Surfaces; Albright, L., et al.;

C/OKE FORMATION is AN UNDESIRABLE SIDE E F F E C T of many chemical

In Coke Formation on Metal Surfaces; Albright, L., et al.;

It i s w e l l known that the surface s t a t e of a

oxygen, was about the same as that of the metal

carbon filament formation.

The accumulation of carbon on metal surfaces when heated i n

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Carbon d e p o s i t s normally have a complex s t r u c t u r e containing

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Figure 1. Transmission electron micrograph of filaments showing the catalyst

Figure 2. Schematic of the proposed mechanism of carbon filament formation.

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Comparison of Measured A c t i v a t i o n Energies f o r

Filament Growth with Those f o r Carbon

CATALYST ACTIVATION ENERGY FOR

CATALYZED FILAMENT DIFFUSION

NICKEL 34.7 (5) 33.0-34.8 (15)

ot-IRON 16.1 (6) 10.5-16.5 (16)

NICKEL-IRON 33.6 (8) 34.0 (17)

COBALT 33.0-33.3 (6) 34.7 (18)

VANADIUM 27.6 (21) 27.8 (19)

MOLYBDENUM 38.8 (21) 41.0 (20)

CHROMIUM 27.1 (6) 26.5 (22)

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Other mechanisms have been proposed f o r filamentous carbon

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Figure 3. Spiral filaments produced

In Coke Formation on Metal Surfaces; Albright, L., et al.;

Figure 4. Schematic of growth mechanism of filamentous carbon on iron carbide.

In Coke Formation on Metal Surfaces; Albright, L., et al.;

forms of carbon d e s c r i b e d here and i t i s u n l i k e l y that i t would be

C o n t r o l l e d Atmosphere Transmission E l e c t r o n Microscopy.

In Coke Formation on Metal Surfaces; Albright, L., et al.;

In Coke Formation on Metal Surfaces; Albright, L., et al.;

such sequences. Unfortunately the m o d i f i c a t i o n s which have to be

Mossbauer Spectroscopy. The Mossbauer spectroscopy c e l l used

In Coke Formation on Metal Surfaces; Albright, L., et al.;

The sample was a 0.0127 mm t h i c k i r o n f o i l , of 99.99% p u r i t y ,

Macro-Scale Experiments. For studying filamentous carbon

In Coke Formation on Metal Surfaces; Albright, L., et al.;

In Coke Formation on Metal Surfaces; Albright, L., et al.;

S c i e n t i f i c Co.) and was pressed i n t o s e l f - s u p p o r t i n g wafers,

the tube s t i l l maintained at 700C, ethane was admitted at a flow

complete r e d u c t i o n to the m e t a l l i c s t a t e . A f t e r evacuation of the

pressure of 2.0 T o r r . Upon subsequent r e h e a t i n g , f i l a m e n t s were

at 600C f o r 1 hour, c o n d i t i o n s where the metal i s expected to

acetylene, filamentous carbon formation was not detected u n t i l

In Coke Formation on Metal Surfaces; Albright, L., et al.;