1

Catalytic Air Oxidation of Propylene to Acrolein:

Modeling Based on Data from an Industrial
Fixed-Bed Reactor
D. ARNTZ, . , and G. PRESCHER
Degussa AG, Hanau, Federal Republic of Germany
G. EMIG and H . H O F M A N N
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Inst. f. Techn. Chemie I, Universitt Erlangen-Nrnberg, Federal Republic of Germany

From a few w e l l chosen experiments in an i n t e g r a l

r e a c t o r o f t e c h n i c a l dimensions with side-stream
a n a l y s i s both r e a c t i o n schemes and the e f f e c t i v e
heat t r a n s f e r and k i n e t i c parameters o f a r e -
a c t i o n model f o r propylene o x i d a t i o n could be de-
duced, from which v a l u a b l e information f o r both
c a t a l y s t development and o p t i m i z a t i o n o f the r e -
a c t i o n c o n d i t i o n s could be obtained.

The economic s i g n i f i c a n c e (1,2,3) o f the c a t a l y t i c p r o p y l e -

ne o x i d a t i o n n e c e s s i t a t e s a c o n t i n u i n g refinement o f the c a t a -
l y s t . This i n t u r n r e q u i r e s c o n t i n u i n g o p t i m i z a t i o n o f the r e -
a c t i o n c o n d i t i o n s , as these depend upon the c a t a l y s t .
The goal o f t h i s i n v e s t i g a t i o n was the development o f a
s u i t a b l e r e a c t o r model f o r propylene o x i d a t i o n i n an i n d u s t r i a l -
s i z e packed-bed r e a c t o r operated under i n d u s t r i a l l y r e l e v a n t
conditions (4).
From the l i t e r a t u r e i t i s not p o s s i b l e t o deduce a k i n e t i c
scheme s u i t a b l e f o r modeling the r e a c t i o n , s i n c e the majority
of p u b l i c a t i o n s (10-39) do not present an unequivocal p i c t u r e .
Also the fundamental d i f f i c u l t i e s o f e s t i m a t i n g from independent
measurements heat t r a n s f e r parameters f o r a packed-bed r e a c t o r
are w e l l known (5,6,7).
Therefore, an attempt was made t o determine the k i n e t i c
r e a c t i o n scheme and e f f e c t i v e heat t r a n s f e r as w e l l as k i n e t i c
parameters from a l i m i t e d number o f experimental r e s u l t s i n a
s i n g l e - t u b e r e a c t o r o f i n d u s t r i a l dimensions with side-stream
a n a l y s i s . The data e v a l u a t i o n was performed with a pseudohomo-
geneous two-dimensional continuum model without a x i a l d i s p e r s i o n .
The model was t e s t e d f o r i t s s u i t a b i l i t y f o r p r e d i c t i o n .

0097-6156/82/0196-0003$06.00/0
1982 American Chemical Society

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 4 CHEMICAL REACTION ENGINEERING

E x p e r i m e n t a l Set-Up and R e s u l t s

The r e s u l t s w e r e o b t a i n e d i n a c o n t i n u o u s l y o p e r a t e d p o l y t r o p i c p i l o t -
p l a n t r e a c t o r w i t h a f e e d o f a p p r o x i m a t e l y 2-5 m o l e s p r o p y l e n e p e r h o u r . The r e
a c t o r was a s i n g l e t u b e h a v i n g a c a t a l y t i c b e d l e n g t h o f 2.70 m a n d a n i n n e r
d i a m e t e r o f 0 . 0 2 0 5 m. T e m p e r a t u r e was c o n t r o l l e d b y a c i r c u l a t i n g m o l t e n s a l t
b a t h . T h e t e m p e r a t u r e p r o f i l e w i t h i n t h e r e a c t o r was m o n i t o r e d w i t h s i d e - e n t r y
t h e r m o c o u p l e s : e l e v e n i n t h e c e n t e r o f t h e t u b e , t w o i n a n 1/2 r a d i u s p o s i t i o n ,
and t h r e e a t t h e w a l l . F e e d s o f p r o p y l e n e , a i r , i n e r t g a s a n d w a t e r w e r e m o n i t o
red by r o t a m e t e r s and preheated t o s a l t bath temperature. O v e r a l l a c r o l e i n y i e l d s
a v e r a g e d o v e r 48 h o u r s p e r i o d s , were e v a l u a t e d by i s o l a t i n g c r u d e a c r o l e i n by
a b s o r p t i o n with water and subsequent d e s o r p t i o n . Unreacted p r o p y l e n e , c a r b o n o x i -
d e s a n d o x y g e n w e r e m e a s u r e d i n t h e e f f l u e n t g a s ( G . C . ) a n d a c r y l i c a c i d was
a n a l y s e d (G.C.) i n t h e a c r o l e i n - f r e e bottoms. To measure t h e a x i a l c o n c e n t r a t i o n
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p r o f i l e o f t h e r e a c t o r gaseous samples ( 5 p r o b e s a l o n g t h e r e a c t o r ) were a n a l y s e d

(water scrubber and e f f l u e n t gas a n a l y s i s ) . Minor s i d e products as acetaldehyde
and f o r m a l d e h y d e ( G . C , a n a l y s e d i n c r u d e i s o l a t e d a c r o l e i n ) , a c e t i c a c i d ( G . C ,
analysed b e s i d e s a c r y l i c a c i d ) and p o l y a c r o l e i n ( r e s i d u e o f e v a p o r a t i o n ) always
t o t a l e d l e s s t h a n 4 %, b a s e d o n t h e p r o p y l e n e f e d i n ; t h e c o r r e s p o n d i n g s i d e - r e
a c t i o n s were n e g l e c t e d f o r m o d e l i n g .
The s p h e r i c a l c a t a l y s t , b a s e d o n a m u l t i c o m p o n e n t b i s m u t h m o l y b d a t e was
3 3
p r e p a r e d a c c o r d i n g t o ( 8 ) w i t h d = 5.3 . 1 0 " m , = 0.8 . 1 0 - K J / m . s . K a n d
p

3
P = 1145 kg/m f o r t h e c a t a l y t i c b e d . The range o f v a r i a b l e s s t u d i e d i n t h e
g

packed-bed experiments i s given i n Table I . T y p i c a l d e t a i l e d r e s u l t s f o r an ex

perimental run are given i n Table I I .

Modeling

R e a c t o r Model. The d e s i g n o f an i n d u s t r i a l packed-bed r e a c t o r r e q u i r e s a

r e a c t o r m o d e l a s w e l l a s t h e c h e m i c a l a n d t h e h e a t a n d mass t r a n s f e r p a r a m e t e r s
of the c a t a l y s t bed - gas stream system. Since these parameters are model-speci
f i c , i t seemed a d v i s a b l e t o employ a continuum model f o r t h e r e a c t o r c a l c u l a t i o n .
T h i s i s t h e o n l y model t o date f o r which t h e l i t e r a t u r e c o n t a i n s c o n s i s t e n t
d a t a f o r c a l c u l a t i n g h e a t a n d mass t r a n s f e r p a r a m e t e r s ( 5 , 6 , 7 ) . T h i s m o d e l i n i t s

Table I Experiments - Range o f V a r i a b l e s

Run
No. w max C o m p o s i t i o n o f R e a c t o r F e e d ( M o l e F r a c t i o n ) O v e r a l l
propene
propene propane N 2 0 2 H 0
2
c o n v e r s i o n {%)
1 296 301 0.047i 0.0022 0.595 0.158 0.198 45
2 320 335 0.047 6 0 . 0 0 2 4 0 . 5 9 9 0.159 0.192 72
3 311 325 0.088 2 0.0041 0 . 5 7 0 0.151 0.187 42
4 334 358 0.089! 0 . 0 0 3 8 0.569 0.151 0.187 67
5 377 415 0.089 5 0 . 0 0 4 3 0.567 0.150 0.190 85

T =T(salt bath);
w G - 1.16 0.02 ( k g / m * . s ) ;
= 1.63 0.01 ( b a r ) a t r e a c t o r i n l e t ; p r e s s u r e d r o p : A P = 0 . 0 4 9 g - 0 . 0 0 2 ,
* = remains unreacted under a l l o p e r a t i n g c o n d i t i o n s . (bar/m)

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ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 1. ARNTZ ET A L . Catalytic Propylene Oxidation

Table I I Run No. 5 - D e t a i l e d I n f o r m a t i o n

bed l e n g t h temperatureQ) m o l e f r a c t i o n x\ ]
p r o p e n e I C 0 , CO a c r o l e i n a c r y l i c
2
acid;
() C
0 377 0.089 5 0 0 0 .
0.15 415
0.30 413 0.071 6 0.003J 0.0162 0.00054 :
0.45 387
0.60 407 0.056 3 0.005 4 0.030 2 0.0010 8 ]
0.80 406 ;
1.00 385 1
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1.20 397 0.035 2

0.008g 0.049 0 0.00218 1
?
1.40 391
1.70
2.00
390
388 0.021 4 0.013 0 0.059 8 0.0036 6 j
i
2.30 387 t
(
2.60 386
2.70 0.013 6 0.016 2 0.065 3
0.0050 J 0

15 i n c e n t e r o f t u b e , (^ 2 i n 1/2 r p o s i t i o n G = 1.178 ( k g / m * . s )
= 0.051 ( b a r / m )
a r
= 1.633 ( )

two-dimensional form, i n which t h e a x i a l heat c o n d u c t i o n and a x i a l d i s p e r s i o n a r e

n e g l e c t e d , y i e l d s f o r t h e mass b a l a n c e o f t h e c o m p o n e n t s :

3 y
M
j 1 3 , '
3j r~ 3" a ] : V
r ; j=l (1)
3z 1
r ( 2 i e f f

i=l
with t h e boundary conditions:
and f o r t h e e n e r g y b a l a n c e :
3 z=0:yj=yj ; 9=0 (r), 0 0 0*r*l
S-^f k (- H
i
r
) i,eff
3 y

1=1 i 3
O^z^l

3 y
i 3
0 ; B i ( e
0^z="l
^ = 3 T - V
The t r a n s p o r t p a r a m e t e r s i n a j , b j a n d B i a r e e f f e c t i v e p a r a m e t e r s w i t h w h i c h ,
j u s t a s w i t h t h e e f f e c t i v e r a t e r f f , s e v e r a l d i f f e r e n t p h y s i c a l phenomena a r e
e

lumped.
The t w o - d i m e n s i o n a l p s e u d o h o m o g e n o u s r e a c t o r m o d e l ( E q . l ) i s t h e b a s i s f o r
t h e s t a n d a r d i z e d c o m p u t e r p r o g r a m F I B S A S ( 9 ) , w h i c h was u s e d f o r t h e e v a l u a t i o n
and s i m u l a t i o n r e p o r t e d h e r e .

Reaction Schemes and Networks. Within the l a s t few years a

s e r i e s o f review a r t i c l e s have appeared concerning the o x i d a
t i o n o f propylene t o a c r o l e i n (10-16). I t i s g e n e r a l l y assumed
that the f i r s t r e a c t i o n step, the formation o f an adsorbed
a l l y l i c s p e c i e s , i s rate-determining f o r the formation o f aero-

Wei and Georgakis; Chemical Reaction EngineeringBoston

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 6 CHEMICAL REACTION ENGINEERING

l e i n . Side r e a c t i o n s o f t h i s intermediate s p e c i e s as w e l l as d i -
r e c t p a r a l l e l r e a c t i o n s are p o s s i b l e . However, previous mechanistic
i n v e s t i g a t i o n s l e a d n e i t h e r to unequivocal c o n c l u s i o n s over the
r e a c t i o n scheme nor over the r e a c t i o n k i n e t i c s .
A l a r g e number o f i n v e s t i g a t i o n s do not even consider the
formation o f the i n d u s t r i a l l y important a c r y l i c a c i d (Models I -
I I I ) . The most d e t a i l e d Model V, on the other hand, i s too com-
plex f o r a p r a c t i c a l a p p l i c a t i o n . I n v e s t i g a t i o n s o f model s i m p l i -
f i c a t i o n s f o r i n d u s t r i a l l y r e l e v a n t c a t a l y s t s are e i t h e r nonexis-
tent or lead to d i f f e r i n g r e s u l t s (Models I-IV).
A p o i n t common to a l l the models i s that they are based upon
a redox-type mechanism, i n which the r e o x i d a t i o n o f the c a t a l y s t
i s not a l i m i t i n g f a c t o r . Corresponding, none o f them employ the
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model expression o f Mars and van Krevelen (37). On c o n t r a s t newer

works by Keulks (38,39) assume, a t lower r e a c t i o n temperatures, a
l i m i t i n g e f f e c t from the r e o x i d a t i o n which leads to a dependence
on oxygen p a r t i a l pressure f o r the a c r o l e i n formation and to a two
to t h r e e - f o l d higher a c t i v a t i o n energy compared with the r e a c t i o n
at higher temperatures.
Thus a c o n s i d e r a t i o n o f the l i t e r a t u r e data n e c e s s i t a t e s
e s t a b l i s h i n g a network before determining the e f f e c t i v e k i n e t i c
parameters.

D e r i v a t i o n o f Reaction Schemes Based on Experimental R e s u l t s .

Although numerous methods f o r e v a l u a t i n g r e a c t i o n s schemes have
been developed (40-44), most o f them (40-42) s t a r t with a hypothe-
t i c a l mechanism which i s , by means o f experiments, e i t h e r c o n f i r -
med or r e j e c t e d . A newly developed method f o r the systematic e l u -
c i d a t i o n o f r e a c t i o n schemes o f complex systems r e q u i r e s no chemi-
c a l c o n s i d e r a t i o n s , but concentration-time measurements and sy-
s t e m - a n a l y t i c a l c o n s i d e r a t i o n s (45). The method i s based on the
i n i t i a l slope o f the concentration-time p r o f i l e s and when ne-
cessary the higher d e r i v a t i v e s o f these curves a t t = 0. Reaction
steps i n which products are formed d i r e c t l y from r e a c t a n t s can be
i d e n t i f i e d i n a concentration-time p l o t by a p o s i t i v e g r a d i e n t
dc- a t t = 0 (zero order d e l a y ) .
J
dt
I t can be seen from a t y p i c a l , p r a c t i c a l l y isothermal con-
c e n t r a t i o n p r o f i l e (Figure 1) t h a t a t t = 0 a l l products e x h i b i t
a non-zero s l o p e . This i m p l i e s that a l l o f them must be formed
d i r e c t l y from the r e a c t a n t s propylene and oxygen, which e l i m i n a -
tes the r e a c t i o n schemes I and IV (Table I I I ). Therefore the
f o l l o w i n g s t o i c h i o m e t r i c equations were used i n the a n a l y s i s ;
f o r equation (4) the approximately constant r a t i o o f CO and CO^
which was a c t u a l l y measured was a p p l i e d .
k
i
Pe + 0 2 * > Ac + H 0 2 (2)
Pe + 1.5 0 2 ^> As + H 0 2 (3)
Pe + 4 1/6 0 2 *3 y 2/3 CO + 2 1/3 C0 + 3 H 0
2 2 (4)

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 1. ARNTZ ET A L . Catalytic Propylene Oxidation 7

Table III R e a c t i o n Models

I (17-20) P e Ac > C 0 , C 0 ; 2 I I (21-25)

III (26-30) Pe vC0,C0 ; o I V (31) Pe > co,co 2

Fo,Ad
Ac acrolein
Ad acetaldehyde
V (32-36) Pe - M s C0,C0 2 As acrylic acid
9 Fo formaldehyde
\ y
Fo.Ad Pe propylene
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Further systematic a p p l i c a t i o n o f the new method l e d t o the con

c l u s i o n that the r e a c t i o n scheme was s t i l l incomplete but that
such r i g o r o u s model b u i l d i n g demands independent v a r i a t i o n s o f
a l l r e a c t a n t c o n c e n t r a t i o n s , which was beyond the scope o f t h i s
investigation.

(5)

The r e a c t i o n scheme was t h e r e f o r e completed using a d d i t i o n a l i n

formation from the concentration-time-diagram. In experiments
with a high degree o f conversion (Table I I ) the y i e l d o f a c r o l e i n
i s obviously l i m i t e d with i n c r e a s i n g residence time. At the same
time the a c r y l i c a c i d c o n c e n t r a t i o n i s s t i l l i n c r e a s i n g a t the
end o f the r e a c t o r , suggesting a concecutive o x i d a t i o n o f a c r o l e i n
to a c r y l i c a c i d as an a d d i t i o n a l r e a c t i o n .

Heat T r a n s f e r Parameters. Attempts i n t h i s i n v e s t i g a t i o n t o

use heat t r a n s f e r parameters ( ^ h ) c a l c u l a t e d from c o r r e l a
t i o n s based on data without r e a c t i o n ,7) l e d t o the r e s u l t t h a t
the energy balance o f the r e a c t o r a t the measured temperatures was
not s a t i s f i e d . On the other hand, the simultaneous e s t i m a t i o n o f
heat t r a n s f e r and k i n e t i c parameters by r e g r e s s i o n a n a l y s i s o f
p o l y t r o p i c measurements allows these parameters t o i n f l u e n c e each
other. I t was observed that the parameters c a l c u l a t e d by these two
methods were q u i t e d i f f e r e n t (5,46). Therefore i n t h i s r e p o r t the
heat t r a n s f e r parameters were determined from experimental r e
s u l t s by a t h i r d method with a minimum o f a d d i t i o n a l assumptions:
The e n e r g y b a l a n c e e q u a t i o n was s o l v e d f o r t h e m o s t e x o t h e r m i c c a s e ( R u n 5 ) ,
( T a b l e s I and I I ) t o g e t h e r w i t h t h e mass b a l a n c e e q u a t i o n ( 1 ) . T h u s , t h e r ^
were d e d u c e d f r o m a w e l l - f i t t e d b u t w i t h r e s p e c t t o t h e k i n e t i c e x p r e s s i o n '
s t i l l a r b i t r a r y d e s c r i p t i o n of the experimental c o n c e n t r a t i o n p r o f i l e along the
r e a c t o r . S i n c e t h e ^ a r e known, i t r e m a i n s t o c h o o s e h and X f f s o t h a t t h e
w e

e x p e r i m e n t a l l y measured temperature g r a d i e n t | i s c o r r e c t l y d e s c r i b e d . For t h i s ,

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 8 CHEMICAL REACTION ENGINEERING
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mole nj
100 mole Pe

Figure 1. Experimental results from Run 3, Table 1.

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 1. ARNTZ ET A L . Catalytic Propylene Oxidation 9

two a s s u m p t i o n s w e r e made: 1. t h e m o d e l e x p r e s s i o n g i v e n i n ( 7 ) ( w i t h o u t t h e l o n
g i t u d i n a l c o r r e c t i o n ( 9 ) i s c o r r e c t ) ; 2 . B i o t i s c o n s t a n t ( t h e same c o r r e c t i o n
f a c t o r f o r h and * f f )
w e

These heat t r a n s f e r parameters were used f o r a l l experiments

(Table IV); they are d i s t i n c t l y higher than those which can be
c a l c u l a t e d from ( 7 ) f o r the case without r e a c t i o n . T h i s agrees
with i n v e s t i g a t i o n s o f the o x i d a t i o n o f CO ( 5 ) .

Table IV experimentally determined R e f e r e n c e (2)

0
(KJ/m.s.K) 1.25 1 ( H 0.82 10-
err, r
h (KJ/m
w
2
.s . K) 0.412 0.27
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E f f e c t i v e K i n e t i c Parameters. F o r the r a t e e f f o f the

i t h r e a c t i o n the p o t e n t i a l law '

r. = A. exp(-Ei/RT)T Pj
ij
(6)
was chosen. An i n i t i a l s e t o f parameters ( , E l f n j ) was de
x

termined f o r each t r i a l s e p a r a t e l y (Runs 1 - 5 ) , (Table I ) by

simultaneous f i t t i n g o f measured c o n c e n t r a t i o n and temperature
p r o f i l e s along the r e a c t o r . I n i t i a l gross f i t t i n g was accompli
shed by o p t i c a l o p t i m i z a t i o n ( 4 7 ) t h r o u g h v a r i a t i o n o f A E i , n i j . l f

I t p r o v e d e f f e c t u a l t o s e t s m a l l v a l u e s f o r i{ ( 4 0 - 7 0 x l 0 J / k m o l e )
6
and n i j
( 0 . 3 - 0 . 5 ) a n d a c h i e v e t h e f i r s t f i t b y v a r y i n g A j . A b e t t e r f i t was a c h i e v e d b y
v a r i a t i o n o f E j a n d n j : , w h e r e b y A j was r e c a l c u l a t e d f o r e a c h s u b s e q u e n t com
putation according to ( 7 ) .

The k i n e t i c parameters obtained from t h i s o p t i c a l o p t i m i z a

t i o n are used as s t a r t i n g values f o r the FIBSAS o p t i m i z a t i o n sub
r o u t i n e SIMPLEX. The procedure d e s c r i b e d above was a p p l i e d t o a l l
t r i a l s (Runs 1 - 5 ) , whereby some o f the parameters obtained f o r
the d i f f e r e n t t r i a l runs s t i l l showed s i g n i f i c a n t v a r i a t i o n . A
set o f parameters v a l i d f o r a l l runs was obtained from the l i n e a r
regression ( 8 ) :

I n r . = I n A. - ( E . / R T ) . . I n p . ( 8 )
j 1J j
and p. i n ( 8 ) a r e experimental values; the other parameters
a r i s e from the former f i t t i n g s f o r Runs 1 - 5 . In each step o f
approximation the best f i t i s f i r s t achieved f o r i = l and then,
one a f t e r another, f o r i = 2 - 4 .
The r e s u l t o f t h i s e s t i m a t i o n o f k i n e t i c parameters i s
shown i n Table V and F i g u r e s 2 - 4 .

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ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 10 CHEMICAL RE ACTION ENGINEERING

Table V Results for Effective Kinetic Parameters

., . _ . _
/ r- / i l 2 3
r A e RT
i , e f f " i * *P<-V > P P e \ P c A

A. E.
1 1 .
i [Z n..) "il n
i2 i3 0

K m o l e / n r . s . P a s c a l J i j J/Kmole
1 16.7 -* 5
47.4 106 0.44 0.93 0
2 1.3 10~ 6
42.8 10 6
0.54 0.54 0
3 1.28x 10" 3
52.8 10 6
0.66 0 0
4 77.1 10~ 3
93.2 10 6
0 0 1
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Discussion

The model d e s c r i b e s , w i t h i n the l i m i t s o f measuring e r r o r ,

the experimental temperature and c o n c e n t r a t i o n p r o f i l e s q u i t e
w e l l over a wide temperature range (more than 100 C) and propy
lene conversion range (Table I ) , (Figures 2 - 4 ) . But the r e
a c t i o n orders f o r propylene and oxygen have only a l i m i t e d r e
l i a b i l i t y s i n c e e s p e c i a l l y the oxygen c o n c e n t r a t i o n along the
r e a c t o r v a r i e d only w i t h i n narrow l i m i t s . A d d i t i o n a l l y , pressure
and flow r a t e were, f o r the most p a r t , h e l d constant (Table I ) .
The model was then used to p r e d i c t measured r e s u l t s f o r a
wide range o f experimental c o n d i t i o n s (T = 343-360 , ( x ) = p

0.07-0.09, ( x ) = 0.13-0.15 , ( x Q ) = 0 . I 8 5 " 0-003, 5 H 2 0

W

1
G = 1.17 - 1.70 kg.m^s" ) as w e l l as f o r a c a t a l y s t d i f f e r e n t
from t h a t used i n Runs 1-5 . The new c a t a l y s t was based upon
the same chemical system but contained more a c t i v e m a t e r i a l ( 8 ) .
It was s u r p r i s i n g t h a t only the pre-exponential f a c t o r s A^
had to be newly estimated (Table VI) whereby the conversion
f a c t o r s f o r A f o r the three p a r a l l e l r e a c t i o n s s t a r t i n g from
x

propylene ( i = l - 3 , Table VI) proved to be about the same. From

these r e l a t i o n s h i p s u s e f u l i n f o r m a t i o n f o r f u t u r e c a t a l y s t p r e
p a r a t i o n may be drawn ("learning model").

Table VI A . f o r new r u n s (different catalyst)

i n . . A. (5 new r u n s )
1 A. 3
(Kmole/m s . P a s c a l J
) A* ( r u n 1 - 5 )
1 J

1 1

1 j 30.4 " 6
1.8 2

2 2.26 10~ 6
1.7 4

3! 2.03 10" 3
1.5g
4 272.5 10" 3
3.53

The agreement o f the p r e d i c t i v e c a l c u l a t i o n s with the measu

red r e s u l t s i s q u i t e good f o r those new runs ( " p r e d i c t i v e model")

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 1. ARNTZ ET AL. Catalytic Propylene Oxidation 11
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Figure 2. Experimental results from Run 2, Table L Key: X , temperature mea

sured; > propylene; , acrolein; A * acrylic acid; and , CO and C0 . Z

Figure 3. Experimental results from Run 4, Table I. Symbols are the same as in
Figure 2.

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 1 2
CHEMICAL REACTION ENGINEERING
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Figure 4. Experimental results from Run 5, Table I. Symbols are the same as in
Figure 2.

Figure 5. Data plotted of a predicted run. Symbols are the same as in Figure 2.

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 1. ARNTZ ET A L . Catalytic Propylene Oxidation 13

as i l l u s t r a t e d i n Figure 5 ( d i f f e r e n t c a t a l y s t ; reduced bed

length; (XQ ) = 0.127; ( X H O ) = 004; G = 1.67 k g . m ^ s " ) .
2 2 0
1

The p r e d i c t i o n o f the new runs succeeded, even though, be

s i d e s the c a t a l y s t , the r e a c t o r feed and flow r a t e were s i g n i f i
c a n t l y d i f f e r e n t from those o f the experimental r e s u l t s (Tables I
and II) from which the model was d e r i v e d .
C l e a r l y , the s i m p l i f i c a t i o n o f the r e a c t i o n scheme t o the
four r e a c t i o n s found i n network (5) i s only v a l i d f o r the tempe
r a t u r e and c o n c e n t r a t i o n range which was i n v e s t i g a t e d . E s p e c i a l l y
at higher temperatures, a d d i t i o n a l secondary r e a c t i o n s , p a r t i c u
l a r l y the o x i d a t i o n o f a c r o l e i n t o CO and CO2, must be e x p l i c i t l y
considered.
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Legend of Symbols

4.(q /P ).(L/d ).(d /d ).(Pe )-

b 0 t p t Pj,P= p a r t i a l p r e s s u r e ; p r e s s .
m Pascal
L M /G 0 P*m = u . d p / D f f , P e e l e t No. ( m a s s , r a d i a l )
0 r? e

preexponential factor P e - G . C p . d p A f f , P e c l e t No.(heat,radial)

h
r f e
1
4.(L/d ).(d /d ).(Pe )-
t p t h r 2r'/d^, reduced r a d i a l coordinate
b 2 L/(G.c .T ) p 0 r' = radial coordinate m
Bi df h /2V,eff
w B i t number r i f f = e f f . rate of i th reaction
f e

Cp = mass s p e c i f i c h e a t a t c o n s t a n t time s
1
pressure K J k g " "* temperature
CJ = molar c o n c e n t r a t i o n kmole linear velocity ms - 1

dp,d|.= d i a m e t e r ( p a r t i c l e , t u b e ) mole f r a c t i o n
^r,eff effective radial dispersion pseudo-mole f r a c t i o n y j = n j / 5 n j 0

coefficient mV z'/L reduced a x i a l coordinate

E = a c t i v a t i o n energy J mole""* = a x i a l c o o r d i n a t e m
G = mass s p e c i f i c f l o w r a t e k g n r ^ s " * V , e f f e f f e c t i v e r a d i a l t h e r m a l c o n d u c t i
= reaction enthalpy J mole"* v i t y o f t h e c a t a l . b e d K J . n r V .K" 1 1

h
w = wall heat t r a n s f e r stoichiometric coefficient
1
coefficient KJ.nrV ^| Y i j

v o l u m e t r i c mass kg m - 3

ki reaction rate constant o f i th : reduced temperature T / T 0

reaction
L = lenght of reactor superscript:
M = mean m o l a r mass kg k m o l e - 1 i , (i+1) step o f i t e r a t i o n
= amount o f s u b s t a n c e mole
= reaction order
subscripts:
g = gasphase s = s o l i d phase
i = f o r t h e it h r e a c t i o n t = tube
j = f o r t h e jt h s p e c i e s w = wall
= particle 0 = conditions at reactor inlet

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2. Weigert,W. "Ullmanns Encyklopdie d. technischen Chemie"; Verlag Chemie,
Weinheim, 1974; Vol. 7, p. 74.

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 14 CHEMICAL REACTION ENGINEERING

3. Weigert, W.M; Maschke, H. Chew. Zeitung, 1974, 98 ( 2 ) , 61

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RECEIVED April 27, 1982.

Wei and Georgakis; Chemical Reaction EngineeringBoston

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.