ELSEVIER

Chemical Reaction Fouling: A Review

A. P. Watkinson
Department of Chemical Engineering,
The University of British Columbia,
Vancouver, British Columbia, Canada
D. I. Wilson
Department of Chemical Engineering,
University of Cambridge, Cambridge,
United Kingdom

Recent research on fouling of organic fluids is reviewed. Fouling in

organic mixtures can be caused by numerous reactions, including autoxidation, polymerization and thermal decomposition. Understanding of autoxidation processes and their link to fouling has developed markedly in
the past few years. By contrast, for fouling under non-oxidative conditions,
the chemical and physical processes have not been adequately explored.
Elsevier Science Inc., 1997

Keywords: heat exchanger fouling, hydrocarbons, organic fluids,

autoxidation, deposits
INTRODUCTION
Chemical reaction fouling generally involves the following
multistep process:
Reactants ~ precursors ~
foulant
(soluble)
(insoluble)
Various possible steps in this process are shown in Fig. 1
[1-3]. In the simplest case, the fouling precursors enter
the exchanger with the fluid--for example, from a feed
t a n k - - a n d then form the deposit by reaction on the wall.
Alternately, the reactants enter the exchanger and the
precursors and foulants form in the exchanger, either in
the bulk fluid, in the thermal boundary layer, or on the
wall. Hence, not only reaction, but also transport of reactants, soluble precursors, or insoluble foulant may be
important. Analysis of chemical reaction fouling in a given
system may entail
1. identification of the reactants and precursors;
2. determination of the kinetics of reactions that form
precursors; and
3. determination of whether the solid fouling phase is
initially formed in the bulk, in the thermal boundary
layer, or on the heated surface.
When these factors are known, available mathematical
models can be used to describe the deposition process
quantitatively. In contrast with other types of fouling,
removal processes are usually less significant in organic
systems, whereas aging of deposits is particularly important. Furthermore, in contrast with particulate fouling or
scaling in inorganic systems, identification of the fouling
precursor may be a major task. Sprague [4] discusses the
importance of this identification stage in dealing with
refinery fouling situations. In organic fluid streams such as
petroleum cuts, there may be a large number of possible
reactants, precursors, and reactions forming them. The
temperature field may well dictate which reactions occur

and where in the exchanger they occur. Hence generalized

solutions to chemical reaction fouling problems are unlikely.
Chemical reaction fouling, primarily of organic fluids,
was reviewed by Crittenden [1], and by Watkinson [2, 3].
In addition, a chapter in a recent book by Bott [5] deals
with this subject. Chemical reaction fouling for organic
fluids was attributed to three general classes of reactions:
autoxidation, polymerization, and thermal decomposition
[2]. In plant operations, other factors may be involved.
Murphy and Campbell [6] discuss fouling in refinery heat
exchangers under seven categories, of which the following
four--inorganic salts, sediments, filterable solids, and corrosion products--arise from impurities. Three o t h e r s - oxidative polymerization, asphaltene precipitation, and
coke formation--arise from chemical reactions of constituents of the oil. Reaction of constituents with the heat
transfer surface can give rise to corrosion fouling, which is
outside the scope of this review.
For deaerated systems, polymerization rather than autoxidation fouling may occur at moderate temperatures
where thermal decomposition is unimportant. The relative
rate of fouling under vinyl polymerization and autoxidative conditions depends on the compound involved. In jet
fuel studies [7, 8], significantly lower deposition rates are
reported for deoxygenated conditions; whereas, with
styrene, a common species for reaction fouling studies,
reaction is faster by vinyl polymerization than by autoxidation [9]. Monomers such as methylacrylic acid are stored
under conditions of low but nonzero oxygen saturation to
minimize polymerization by either reaction route [10].
This variation emphasizes a primary difficulty in studies of
chemical reaction fouling--that there rarely exists a single
mechanism common to all species present in a given
hydrocarbon system over the range of operating conditions of interest. The limit of oxygen concentration below
which autoxidation ceases to be dominant has not been

Address correspondence to Professor A. P. Watkinson, Department of Chemical Engineering, The University of British Columbia, Vancouver,
BC V6T 1Z4, Canada.

Experimental Thermaland Fluid Science 1997; 14:361-374

Elsevier Science Inc., 1997
655 Avenue of the Americas, New York, NY 10010

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362

A.P. Watkinson and D. I. Wilson

a)
Bulk Liquid

bulk reaction
precipitation of insoluble B
ed by mass transfer
mass

transfer

surface reaction
A

( adhesion
B

~I~
~'--C

Thermal Boundary
Layer
Heat Transfer Surface

b)
Chemical Reaction

A,

O,

Indene
C,H,

Peroxy
Radicals
RO,-

O,

B,
Heat C,
--- Polyperoxides
- Oxygenated
A
(C,H,OO).
Deposits,

Figure 1. (a) General multistep chemical reaction fouling mechanism. (b) Application of mechanism to
model solutions of indene.
established for most fouling species. Autoxidation was the
mechanism of indene fouling for solutions with calculated
oxygen contents as low as 1.8 ppm [11].
This paper focuses on a survey of the more recent
organic fluid fouling and related literature, based on the
classification in Refs. 2 and 3. Autoxidation fouling is
interpreted by using known chemistry. The residuum processing literature suggests some approaches for dealing
with fouling under nonoxidative conditions, for which the
chemical reactions causing fouling have not been elucidated or incorporated into fouling models.
AUTOXIDATION
The autoxidation of hydrocarbons has been identified as
the main source of unwanted deposits in reviews of fuel
storage stability [12], in the formation of unwanted g u m s
in jet fuel feed lines, and in many cases of heat exchanger
fouling in the temperature range from ambient to 300C
[2]. Deposition in oxygenated hydrocarbon systems above
250-300C is dominated by thermal condensation and
cracking reactions. Autoxidation, or the autocatalytic oxidation of hydrocarbons, consists of a complex set of free
radical reactions, and recent work has been the source of
significant insights into the fouling problem in these systems.
Table 1 is a summary of recent investigations of autoxidation fouling [13-35]. Earlier studies, such as those by
Taylor and coworkers on jet fuel deposition under vaporizing conditions, are discussed in Refs. 2 and 3. Most studies

of jet fuel storage stability have used mass deposition

measurements, whereas heat exchanger studies have featured thermal measurements, using constant heat fluxes to
maintain constant deposit-fluid interface temperatures.
Both thermal and mass deposition measurements have
been employed in the studies of jet fuel deposition. Recently Zabarnick and Grinstead [36] used quartz crystal
resonance techniques in fuel thermal stability tests to
monitor in situ mass deposition against time. Generation
of fouling resistance-time data, which can be used directly in design and operation, was the main advantage of
traditional thermal measurement methods. A significant
feature of recent studies is the use of "model" solutions
consisting of compounds of known reaction chemistry and
tendency to form deposits and relatively inert solvents.
These solutions are used to control reaction chemistry,
minimize variations between experiments, and explore
deposition mechanisms. Another characteristic is the
greater use of analysis techniques to study deposit chemistry and morphology [13, 26, 34], solution chemistry [33],
and oxygen concentrations [24]. Soluble gum and filter
deposition assays used in fuel storage stability tests are
now frequently used in flow system studies.
REACTION CHEMISTRY
Autoxidation can occur without causing fouling; the occurrence of fouling is determined by the reaction chemistry of the hydrocarbons present. The chemistry of hydrocarbon autoxidation has been studied extensively and a

Chemical Reaction Fouling: A Review 363

Table 1. Recent Investigations of Autoxidation Related Fouling

Reference

Test Fluid

[13] Roback et al.

(1983)

RP-1, JP-7 fuels

and propane

[14] Szetela et al.

(1986)

Jet A fuel

[15] Marteney
and
Spadiccini
(1986)
[16, 17] Morris
et al.
(1988, 1989)
[18] Morris and
Mushrush
(1991)
[19] Wilson and
Watkinson
(1992)
[20] Asomaning
and
Watkinson
(1992)
[21] Jones et al.
(1992)

JP-5 fuel and

aromatic blends

[22] Parker et al.

(1992)

JP4, air sat'd

[23] Jones and

Balster
(1992)
[24] Heneghan
et al.
(1993)

Hexadecane
S additives

[25] Chin and

Lefebvre
(1993)

Jet fuels,
additives,
model solutions

Indene in
different solvents
Alkenes in
kerosene

3 Jet A fuels,
hexadecane

3 Jet A fuels
aerated,
deaerated
additives
DF2, kerosene

[26] Zhang et al.

(1993)

Indene in
kerosene

[8, 27] Jones and

Balster
(1993, 1994)
[35] Oufer and
Knudsen
(1993)

Jet-A fuels

Styrene/heptane
sulfur species

Apparatus
(Measurement
Method)

Temperature
Range

Flow
Velocity

OtherAna~ysis
Methods

Tubular heater,
constant heat flux
( A Tw~al,mass
deposition)
Tubular heater,
constant heat flux,
metal wafer inserts
(A Two1, mass
deposition)
Tubular heater,
constant heat flux
(A Tw~al, mass
deposition)
Adapted JFTOT
unit, constant
heat flux
(mass deposition)

150-538C

6-30 m / s

127-357C

0.07 m / s
Re(in) = 60

152-600C

Re = 400,
3000,
21,000

Oxygen analysis

Annular heater,
constant heat flux
(thermal resistance)
Annular heater,
constant heat flux
(thermal resistance)

T~ua = 180240C
Tbulk = 80C
Tsua = 150200C
Tbulk = 80C-

Re = 300012,000

Chemical analysis
of hydroperoxides,
indene, deposit

Reaction flasks
(mass deposition on
discs)
Isothermal heated
tube, optical cell
(absorbance,
scattering)
Reaction flasks
(mass deposition
on discs)
Isothermal tube
(mass deposition)

185C
Tbulk ~ Twan

< 625C

Re = 30011,000

Isothermal tube;
Twall- Tbulk
varied
(mass deposition)
Annular heater,
constant heat flux
(thermal resistance)
Isothermal tube
(mass deposition)

140-350C

Re = 10007000

Tbulk = 80C
T~ua = 137216C
185C
155-255C

Re = 500017,000

Annular
heater

Scanning electron
microscopy
of deposits

190 <Ts~a <

538C

< 502C

Re = 11,000

Gums*

Slow
~"= 4-13.5
min

160-200C

Tsua = 180190C
Tbulk = 100C

Optical analysis

Gums*; TGA/MS**
of deposits

Slow
~-= 1-25
min
0.9-2.4 m / s

Oxygen, methane
analysis
Filtration

Chemical analysis
of indene, ROOH,
deposit, and gum
Oxygen analysis
Gums*

(continued)

364

A . P . Watkinson and D. I. Wilson

Table 1. Recent Investigations of Autoxidation Related Fouling

Apparatus
(Measurement
Method)

Temperature
Range

Flow
Velocity

Other Analysis
Methods

Reference

Test Fluid

[28] Heneghan
et al.
(1995)

Jet A fuels,
Oxygen conc.
varied,
additives
Jet fuels,
additives

Isothermal tube
(mass deposition)

270-335C

r < 6s

Oxygen analysis

Isothermal tube
(mass deposition)

185C

Slow

Oxygen analysis
Gums*

Indene in
kerosene and
lube oil,
oxygen varied
Indene in
kerosene and
lube oil,
antioxidants

Annular heater,
constant heat flux
(thermal resistance)

Tbulk = 85C
Tsurf = 188C

Re = 11,000

Chemical analysis
of indene, ROOH,
deposit, and gum

Annular heater,
constant heat flux
(thermal resistance)

Tbulk =

80-100C
Tsurf = 180240C

Re = 30006500

Chemical analysis
of indene, ROOH,
deposit, and gum

Indene in lube
oil

Tubular heater,
constant heat flux
(mass deposition,
pressure drop, and
thermal resistance)

Tbulk = 100C
Tsurf = 180225C

Re = 300014,000

Scanning electron
microscopy of
deposits
Chemical analysis
of indene, ROOH,
deposit, and gum

[29] Jones and

Balster
(1995)
[30, 31] Jones
et al.
(1995)
[11] Asomaning
et al.
(1995)
[32] Wilson and
Watkinson
(1995)
[33] Wilson et al.
(1995)
[34] Wilson and
Watkinson
(1996)

* Gums: classification of gum and filtration products based on solubilities; r-residence time in tubular section.
** TGA/MS: thermogravimetric analysis/mass spectroscopy.
detailed review is given in Ref. 37. The following abbreviated kinetic scheme shows the complex nature of the
reactions leading to deposit formation.

Initiation
R H Initiator R"
R O O H --* R O - + H O "
2 R O O H ---, R O 2 + R O " + H 2 0

(la)
(lb)
(lc)

Propagation
R . + 0 2 --) R O 2

RO 2 + RH

abstraction

(2)

R O O H + R - (hydroperoxide)
(3a)

R O 2 + R H addition
......... : R O O R " (--- R' .)(polyperoxide)
(3b)
R O . + R H ~ radicals, products

(7)

Termination
R . + R . --, products

(4)

R" + R O 2 ~ products

(5)

R O 2 + R O 2 ~ products

(6)

Steps (1)-(6) are termed the basic autoxidation scheme

(BAS) in the literature. Initiation in step (la) may be

caused by thermal decomposition of the hydrocarbon, RH,

or by its reaction with chemical initiators, metal ions, or
ultraviolet light. Under conditions of excess oxygen, the
hydrocarbon radical, R . , is rapidly oxidized to the peroxy
radical R O 2 . , by step (2). Propagation occurs through
steps (3a), (3b), and (2), forming hydroperoxides a n d / o r
polyperoxides. Termination is primarily by step (6) when
the peroxy radical is the dominant radical present. When
autoxidation consists of these steps alone, the reaction
rate is given by

d[RH]

d[O2]

dt

at

~ t
(k3a + k3b)[RH] v ~

(8)

which is zeroth order in oxygen if initiation [step (la)]

does not involve oxygen. The products of autoxidation are
thus hydroperoxides, polyperoxides, and the carbonyls and
other oxygenated products generated by step (6). The
thermal decomposition of hydroperoxides produces further radicals [steps (lb and (lc)], and the reaction is thus
autocatalytic. Unimolecular decomposition [step (lb)] is
more important at lower hydroperoxide concentrations,
whereas bimolecular decomposition is more significant at
higher concentrations. Equation (8) shows that the rate of
autoxidation and product distribution will thus change as
the hydroperoxide concentration increases if both decomposition steps can occur. This is one source of complexity
in understanding autoxidation fouling behavior.

Chemical Reaction Fouling: A Review 365

When oxygen is limited, the dominant radical species
changes from the peroxy radical to a mixture of peroxy,
alkoxy ( R O . ) and alkyl (vinyl) radicals (R-). Propagation
steps such as step (7) and termination steps such as steps
(4) and (5) become more significant, with associated
changes in reaction kinetics and product distributions.
These effects are evident in jet fuel deposition studies [27]
featuring the slow flow ( ~ 0.07-1.5 ml/min) of aerated
jet fuel through small-diameter tubes under near isothermal conditions (155-255C). The experimental apparatus
was analogous to a plug flow reactor. The formation of
gums and deposits was shown to be oxygen limited, and
the disappearance of oxygen was found to change from
zeroth-order to first-order kinetic behavior as the reaction
proceeded. Heneghan et al. [28] also reported complex
kinetics in their study of fouling from jet fuels at different
feed oxygen levels.
Heat exchanger fouling was investigated by using model
solutions of indene in kerosene at different oxygen concentrations [11]. The induction period observed before
fouling occurred decreased as the oxygen concentration
increased. Both the initial fouling rate and the kinetic
parameters for the reaction of indene varied with the
saturating oxygen pressure raised to the power 0.6-0.7 at
oxygen saturation pressures below 8.6 kPa. The oxygen
content of the deposits decreased with decreasing dissolved oxygen content of the fouling fluid. This work
confirmed that autoxidation reactions control the generation of fouling precursors.
Oxygen analysis data [29] provided quantitative evidence that a significant proportion of reacted oxygen in jet
fuel autoxfdation was obtained as nonfouling products.
Investigations of fuel storage stability have shown that
fuels that readily undergo autoxidation are not necessarily
those that generate significant amounts of gum or fouling
[38]. Taylor [39] investigated the relation between compound chemistry and fouling behavior by using model
solutions of alkanes, alkenes, and naphthenes in dodecane. Compounds that tend to undergo addition to form
polyperoxides [step (3b)] were found to foul more heavily;
substituted alkenes are particularly prone to oxidative
addition owing to structural effects. This result was confirmed [20] for heat exchangers by using model solutions
of alkenes in kerosene. Indene was found to cause severe
fouling in both these investigations; this compound was
known to undergo addition polymerization to form
polyperoxides [40] and was identified as a major source of
fouling in operating equipment [41]. Fouling in model
solutions of indene, hexadecene, and dicyclopentadiene in
kerosene and lube oil was shown [32, 33] to be caused by
the formation of polyperoxide gums. These gums, being
polar in nature, exhibit solubility limits in aliphatic solvents and precipitate out of solution when the limit has
been reached. Watkinson and coworkers [32, 33] used
recirculating solutions in their heat exchanger studies and
the fouling resistance-time data featured an induction
period where no autoxidation occured, a linear fouling
regime, and a regime where the fouling resistance increased rapidly. Chemical analyses confirmed and the
transition between the two fouling regimes corresponded
to the onset of precipitation of insoluble gum. The insoluble gum formed agglomerates in the bulk liquid that were
rapidly deposited.

Attempts to model the reaction kinetics in autoxidative

systems [42-44] have not been very successful. Modeling
studies have used simplified kinetic schemes such as a
two-step model:
hydrocarbon + 0 2 ~ soluble precursor, P
insoluble precursor/deposit, (9)
where the soluble precursor, P, was linked to hydroperoxide concentrations [45] or soluble gum concentrations [42].
Norton and Drayer [46] obtained reasonable agreement
between a three-step model and experimental data for the
autoxidation of hexadec-l-ene. These simple models are
not based on the kinetic scheme outlined in Eqs. (1)-(7)
and are thus likely to be limited in application to other
systems.
The tendency of a hydrocarbon fluid to cause fouling
thus depends on its composition. Mayo and Lan [38]
investigated gum formation and oxygen consumption in
aerated mixtures of amines and aromatics in dodecane at
130C and reported large variations in reactivity and yield
with different dopants. Fouling behavior of a mixture of
indene and dicyclopentadiene was very different from that
of the individual components [33]. Co-oxidation of compounds that undergo autoxidation introduces reaction
steps that inhibit step (3b), the addition of oxygen to form
polyperoxides [47]. It is thus unlikely that a priori predictions of fouling behavior based on chemical composition
will be feasible. Wilson and Watkinson [19] also investigated solvent by effects in heat exchanger fouling by using
model solutions with indene as dopant. Solvents such as
tetralin, which were not inert to autoxidation, interrupted
the formation of polyperoxides and thus inhibited fouling.
Fouling was observed in solvents that were relatively inert
to autoxidation. The solubility limit of the polyperoxide
gums was found to depend on the aromaticity and polarity
of the solution.
Solubility plays an important role in fouling, because
deposits often appear to be formed from particulates [26,
48, 49]. Mayo et al. [50] argued that the solubilizing
properties of detergents are the primary source of the
mitigation of fouling by these compounds. Roback et al.
[13], reported dendritic deposit growth in propane fouling
above 316C, whereas kerosene-type fuels generated
spherical agglomerates. Dendritic growths are consistent
with coking mechanisms, which would be expected for
propane at these temperatures. Reported particulate sizes
vary with feedstock and reaction conditions, from 0.015
/xm [49] to 6-20 tzm [32]. Optical methods were used to
analyze particulates formed in jet fuel fouling by Parker et
al. [22], who found that the particulates formed during
once-through reaction of jet fuels at 502C were more
numerous but significantly smaller (diameter < 0.06 tzm)
than those formed during fuel stability tests at ambient
temperature ( > 0.1 txm). Analyses of deposits found in
autoxidative fouling show that the deposit consists of
oxygenated gums or complex mixtures of their products
after aging [32]. Values of thermal conductivities of fouling deposits lie in the range 0.1-0.5 W / ( m K). A value of
0.2 W / ( m K) was reported for indene polyperoxide deposits from mass and thermal resistance data [34].
The effects of heteroatomic species containing sulfur
and nitrogen in jet fuels are determined by their reactivity
(i.e., structure), concentration, and operating conditions
[2, 12]. Research in this area is ongoing [23, 44, 51].

366

A . P . Watkinson and D. I. Wilson

Edwards and Zabarnick [52] investigated the phenomenon whereby several jet fuel fouling studies of slow
flow through a tubular reactor showed a decrease in
deposition at wall or film temperatures of 370C. This
work indicated that the change in deposition was linked
to bulk fluid reaction effects and not to an increase in
the solubility of precursors in the fuel as it became supercritical.
The mode of heat transfer also has an important effect
on the amount of deposition observed in autoxidation
fouling. Increased deposition from hexadecane and
kerosene under vaporizing conditions was reported
[53-55]. Oufer and Knudsen [35] studied fouling from
oxygenated and deaerated model solutions of styrene in
heptane under subcooled boiling conditions. Although
autoxidation was not always the fouling mechanism involved, the reported dependencies on temperature and
flow rate were significantly different from those observed
under conditions of sensible heat transfer. Chin and
Lefebvre [25] reviewed the effect of fuel pressure in jet
fuel fouling. Earlier studies had shown that deposition
decreased with increasing fuel pressure [56], whereas most
other workers reported that pressure had no effect above
a threshold value. These effects were linked to vaporization phenomena.
M E C H A N I S M S A N D M O D E L S OF

AUTOXIDATION FOULING
Autoxidation fouling includes the formation of precursors
and the transport of these precursors to the surface,

where they form deposits. Figure 1 indicates the stages of

fouling from model solutions of indene. The relative importance of each stage varies, and the key to understanding the observed fouling behavior is whether fouling is
governed by generation of precursors in the bulk fluid.
Table 2 is a summary of reported temperature and velocity effects in studies of autoxidation fouling, where deposition is measured per unit surface area. Entries in Table 2
are marked if significant chemical reaction occurred in the
bulk fluid.
When the concentration of precursors in the bulk fluid
is small, deposition is controlled by the transport of reactants to the hot surface, reaction at the surface, and
attachment. This is the case in most heat exchangers
(except reboilers and condensers). Reaction rates increase
with surface temperature, and attachment decreases with
increasing flow velocity. Wilson and Watkinson [34] showed
that autoxidation fouling rates observed in two different
heat exchanger geometries were consistent with a reaction-attachment model based on that of Epstein [57].
Roback et al. [13] observed this type of behavior in testing
jet fuels at high wall temperatures and high flow rates.
The bulk fuel temperature was not reported in their work,
but their account suggests that little bulk reaction would
have occurred. The maxima observed in their data cannot
be explained by simple arguments.
When the concentration of precursors in the bulk fluid
is large, deposition' is controlled by precursor concentration, mass transfer, and attachment. This is the scenario
when gum concentrations reach their solubility limits and
in many of the jet fuel fouling studies in Table 1. A heat

Table 2. Temperature and Velocity Effects on Rate of Autoxidation Fouling

Reference

Test Fluid

Temperature
Effect

Velocity Effect

Comments

[49] Vranos et al.

(1981)
[13] Roback et al.
(1983)

Jet A fuel

E = 42 k J / m o l

rate ot Re 65

Bulk reaction effects

RP-1, JP-7,
propanes
JP-S and aromatic
rich blends

Thermal resistance
maximum at (flow
rate)- 1
Little effect of
flow rate > 250C

Thermal resistance

[15] Marteney and

Spadiccini (1986)

[14] Szetela et al.

(1986)

Jet A fuel

Maximum in
thermal resistance
as Tsurf increases
E = 42 k J / m o l
T~u~f < 250C;
E = 167 k J / m o l
Tsu~f > 250C
E = 200 k J / m o l
(est.)

[25] Chin and Lefebvre

(1993)

DF2, kerosene

Increase with
increasing Tbulk
and Tsurf - Tbulk

Rate

[8] Jones and Balster

(1993)
[26] Zhang et al. (1993)
[28] Heneghan et al.
(1995)
[33] Wilson et al.
(1995)
[34] Wilson and
Watkinson (1996)

Jet A fuel

Rate ct (flow rate)

Rate cx R e - l 4
Rate ct (flow rate)

Fouling resistance
Bulk reaction effects

Indene in lube oil

E = 150 k J / m o l
(oxygen kinetics)
E = 39 k J / m o l
E = 128 k J / m o l
(oxygen kinetics)
E = 82-85 k J / m o l

Bulk reaction effects at

high fluid
temperatures
Non-Arrhenius
temperature
dependency
Bulk reaction effects
suspected
Bulk reaction effects

Fouling resistance

Indene in lube oil

E = 76.4 k J / m o l

Rate cx Re -n
2>n>l
Rate ct Re -n
2>n>l

Indene in kerosene
Jet A fuels

ot R e '65

JFFOT breakthrough
temperature = 252C
Bulk reaction effects

Fouling resistance

Chemical Reaction Fouling: A Review 367

exchanger or jet fuel system operating in this mode can be
considered a tubular reactor; bulk reaction kinetics thus
determine the distribution of deposits in the device. The
jet fuel studies of slow flow rates in Table 2 show increasing, or weakly increasing, deposition rates with flow rate
as the effects of mass transfer and attachment tend to
cancel out for the very small particulates formed in jet
fuel autoxidation.
An example of bulk reaction control is shown in Fig. 2
[8], which shows one set of deposition profiles for a jet fuel
passing through a near-isothermal tube at 185C. Figure 2
also shows the oxygen concentration in the bulk liquid.
The mass of deposit increases along the tube as the bulk
reaction generates more precursors, until the oxygen is
exhausted. The concentration of bulk precursors then
decreases owing to further reaction and deposition, giving
a decreasing deposit profile. Katta et al. [42] modeled this
system as a reactor but found that they were limited by an
incomplete understanding of the reaction kinetics. They
did not include any attachment considerations or fouling
effects. Jones and Balster [8] were not able to explain
their deposition results for different tube sizes by using a
reactor model, because they did not consider attachment.
Care must thus be exercised in extracting reaction kinetics
from such data, because mass transfer and attachment
effects can significantly affect deposition behavior.
The transition between surface and bulk reaction control is evident in jet fuel fouling studies [14, 15] at constant heat fluxes, which maintained constant bulk fluid
temperatures. The data are more difficult to interpret

owing to the changing surface temperature profiles in the

apparatus. Szetela et al. [14] found that deposition rates
increased exponentially with initial wall temperature until
the wall temperature approached the thermal stability
limit of the fuel. Plots of deposit rate against wall temperature (or axial position) showed a maximum, corresponding to precursor exhaustion, when the bulk fluid exit
temperature was greater than 420 K. The data prior to a
maximum showed a reasonable correlation between deposition rate and surface temperature, which is consistent
with surface reaction/attachment control. They found
that the location of a maximum did not correlate with wall
temperature and suggested that this phenomenon was
related to the residence time of the fuel.
The transition between bulk fluid reaction control and
surface-thermal boundary layer control has been discussed in other types of fouling. Fryer [58] described
similar features in comparing silica fouling in geothermal
brines and in food fouling, particularly in the fouling of
milk heat exchangers at temperatures < 100C. At these
temperatures, milk fouling is caused by the denaturation
of milk proteins (mainly fl-lactoglobulin) followed by protein aggregation and deposition. Protein denaturation occurs rapidly above a critical temperature (70-75C), so
surface and bulk control can occur in different parts of
the same heat exchanger if the bulk fluid temperature
exceeds the critical value. Simulations of milk fouling
based on both bulk and surface processes show reasonable
agreement with experimental data and predict features
analogous to the maximum in deposition in Fig. 2 [59].
F O U L I N G IN D E O X Y G E N A T E D SYSTEMS

185C
+ 1.8s
[] 1.0

80

&

O 0.125

0.75
O.S

0.10

DISSOLVED OXYGEN (%)

uJ

60

o_

t,.)

~,

N
o
a

,,o
40

J-

eeeo IE.~'lb
~ D -..x
l,m e o e e

20

0
0 ~

STRESS

DURATION

10

12

(rain)

Figure 2. Deposition rate at 185C on 0.125-in tubing at

various flow rates (cm3/min) for fuel initially saturated with
air at room temperature. Superimposed is dissolved oxygen
versus stress duration. From Jones and Balster [8].

Because the importance of oxygen has long been recognized in a qualitative manner, most processing of organic
fluids is done with maximal exclusion of oxygen. Under
such conditions, reactions leading to fouling are primarily
thermal decomposition (thermolysis, pyrolysis, cracking,
etc.) or vinyl-type polymerization. Styrene polymerization,
which has often been used as a model chemical system
[48], continues to be studied (Table 3). Oufer and Knudsen [35, 51] reported experimental data and a model for
polymerization fouling under flow boiling conditions. Epstein [57] used the styrene polymerization data of Crittenden [48] to verify a mathematical model for chemical
reaction fouling. Thus, for both polymerization and autoxidation, recent work related the reaction to the fouling.
For thermal decomposition, this link is yet to be established.
Table 3 also lists recent studies on fouling of crude oils
and other undefined petroleum mixtures [60-65]. For
crude oils, fouling can be caused by contaminants such as
inorganic chemicals, sediments, and corrosion products or
by constituents of the oil itself. In none of these papers
are the chemical reactions (other than autoxidation) that
lead to the fouling deposit discussed. In some cases,
reactions and kinetic rate constants are mentioned, but no
details of the types of reactions are given.
The effect of feedstock composition is perhaps the most
significant of all the variables in chemical reaction fouling.
Studies by Dickakian [60, 61, 67], are reportedly based on
hundreds of different petroleum streams; however, results
are not published in a form that other researchers can
readily duplicate and are not generally in the public

368

A.P. Watkinson and D. I. Wilson

Table 3. Recent Investigations of Fouling in Nonoxygenated Systems

Reference

Test Fluid

Apparatus

Tempera ture
Range (C)

Velocity
(m / s)

Other

[60] Dickakian
(1989)

Crude oils

Annular TFT*

Tb 275

[61] Dickakian
(1990)

FCC streams,
oils,
asphaltenes
Crude oil

TFT unit

Ts 510-593
T b 350-382

Refinery preheat
train

T~ 165-260
Tb to 250

1.1-2.1

[63] Crittenden
et al. (1993)
[64] Haquet et al.
(1995)

Crude oil and

residue
Crude/
residue

Tubular heater

~ 197-218
Tb 140
T b 230-270

0.5
(Re 6800)

[65] Shibuya et al.

(1995)
[66] Bach et al.
(1995)

Gas oils

Tb 40-320

0.2-0.7

[35, 51] Oufer

and Knudsen
(1993, 1994)

Styrene/heptane

[62] Crittenden
et al. (1992)

Isobutane in N 2
P = 0.1 MPa

Refinery
exchanger and
inserts
S and T, plate
exchanger**
Coupon in
quench stream
(mass deposition)
Annular

Scanning electron
microscopy,
deposit aging
Deposit
analysis,
P 35-58 atm
Deposit
thickness and
analysis
P 15 bar,
Inserts
Turbotal insert

24-day tests

Tb 350-500

Surface effects

T~ 180-190
T b 100

0.9-2.4

Subcooled
boiling,
sulfur species

* TFT: thermal fouling test unit (details in ref. [60]).

** S and T: shell and tube

domain. Variations in fouling of crude oils are said to be

caused by changes in composition and are related to
asphaltene/oil incompatibility [67]. For FCC slurry, asphaltenes and coke particles are the main causes of organic fouling [61]. Crittenden's work [62] provides valuable
data on fouling of crude oil in an industrial unit. Although
the range of conditions explored is necessarily limited by
processing constraints, consistent velocity and temperature effects are reported. Decreases in tube-side velocity
and increases in temperature led to increased fouling.
Inorganics make up some 15-39% of the deposits, whereas
coke represents 25-37 wt.%, which suggests that a combination of the mechanisms reported by Murphy and Campbell [6] are responsible.
Ebert and Panchal [68] present a novel semiempirical
analysis that suggests that a combination of low temperature and high shear stress will produce a threshold condition such that the fouling fate will be essentially zero.
Data from a previous crude oil coking study were regressed in the form

0 05

Velocity-

1.2

ft/s

Veloclt 7 " 2.5

0.04

0.03
14

0.02

//."

~t

= o.oi
g
Ib4

.t"i,-

0.00

200

250

. . . .

300
FILm

. . . .

. . . .

3.50

400

. . . .

450

. . . .

500

Temperatu.re,

(10)

Figure 3. Comparison of experimental and fitted fouling rates

of crude oil by Ebert and Panchal [68].

Hence, if ~- is sufficiently large, the deposition rate is zero.

This equation was applied to conditions that gave linear
fouling rate with time and should not be confused with the
usual fouling rate being equal to the difference between
deposition and removal terms. The right hand side terms
are empirical expressions for two components of the deposition term. This analysis gives a good fit to the data (Fig.
3) and leads to a simple diagram to identify fouling and
nonfouling conditions (Fig. 4). The approach appears to
be very useful for designers, although the chemical reac-

tions are not identified as such and the formulation lacks

a rigorous explanation by the authors.
Haquet et al. [64] describe the use of Turbotal internal
devices to limit fouling of crude oils. They attribute their
effect to cleaning of the surface and the renewal of the
thermal boundary layer, which reduces the difference in
temperature between the wall and the bulk fluid, thus
minimizing fouling. In terms of the approach of Ebert and
Panchal [68], both the increased shear at the wall and

d R f / d t = a Re/3- e x p ( - E / R T f ) - Y~'.

Chemical Reaction Fouling: A Review 369

5OO

Foullng

2 0 0

1 0 0

'

10

'

20

'

50

Wall Shear Stress,

'

40
N / m

50
2

Figure 4. Threshold-film temperature concept of Ebert and

Panchal [68].
reduction of the film temperature should have positive
effects. Crittenden et al. [63, 69] report data for a crude
oil containing added waxy residue and review the use of
wire matrix inserts. It is claimed that more than a simple
reduction in wall temperature is responsible for reducing
fouling. Shibuya et al. [65] report gas oil fouling in plate
and in shell and tube heat exchangers. Addition of cracked
stocks was found to increase fouling in a gas oil. Under
both once-through and recirculated flow conditions, maximum fouling appeared to occur at an intermediate temperature of about 200C. At both 180C and 260C, fouling was reduced. A marked increase in fouling was noted
when the gas oil was presaturated with oxygen. It was
noted that recirculation of fluids, a common laboratory
procedure for fouling studies, gave increased fouling and
hence was judged to be more severe than once-through
processing. Fouling was much reduced in the plate exchangers, although the lack of pressure drop data precluded a conclusion of how this effect was influenced by
increased shear stress.
Under nonoxidative conditions, the organic part of fouling in crude oils and other noncracked refinery cuts is
claimed to be due largely to precipitation of asphaltenic
constituents [6, 67, 70]. Asphaltenes are a solubility class,
generally defined as being the benzene soluble-heptane
insoluble fraction of a petroleum stream. Strausz et al.
[71] presented a hypothetical structure of asphaltenes
(Fig. 5) containing aromatic clusters and side chains, which
was consistent with recent research. Fouling is triggered
by precipitation of the asphaltenes due to an incompatibility between asphaltenes and the remainder of the oil [67].
The precipitated asphaltenes adhere to the hot surface of
the exchanger and then carbonize into coke. The physical
and chemical steps that lead to the incompatibility have
not been discussed in the fouling literature, although
generalized reaction schemes have been presented [70]:
oils ~ resins ~ asphaltenes ~ coke
(11)
Recent literature on processing of residuum and heavy
oils (see, e.g., Ref. 72) discusses reactions that lead to
coke formation in such processes as visbreaking and hydrotreating and perhaps can be applied to fouling of fired

Figure 5. Hypothetical asphaltene, structure by Strausz et al.

[71]. A, B, and C represent larger aromatic clusters; the rest
of the structural units are based on experimental data.
heaters and extrapolated to the lower temperatures of
preheat trains. Wiehe [73] has developed a model of
residuum thermolysis based on the formation of asphaltene cores, A*, stripped of their stabilizing side chains. He
assumes that asphaltene cores can be formed either by
reaction of asphaltenes originally in the feedstock, A , or
by conversion of other solvent fractions, H , in a parallel
set of reactions:
A +~A* +nil* + (1-m-n)V
H + ~ aA* + (1 - a)V
(12)
The soluble asphaltene cores eventually reach their solubility limit, A*ax, and then the excess undergoes a very
rapid reaction to precipitate liquid coke (toluene insolubles):
[A* - A*ax] ~ (1 - y ) T I + y H *
(13)
This reaction is essentially a phase separation process,
controlled by equilibrium. This model provides an explanation for the observations that it is not asphaltene content alone that dictates fouling and suggests a mechanism
for the incompatibility phenomenon in heating petroleum
streams. The similarity to the solubility limit in autoxidation fouling [32], is evident. The extent to which the
precipitation process rather than the reaction process
controls this type of fouling under moderate temperatures
( < 350C), where severe coking does not occur, is yet to
be clarified. Furthermore, the same mechanistic issues
discussed under autoxidation fouling--namely, conditions
for bulk, boundary layer, or wall deposition--have yet to
be established. This is an area of active research [74].
As described above for autoxidation fouling, the use of
model compounds could well simplify the complex chemical situation in heavy hydrocarbon mixtures and illustrate
the connections between the reaction and the fouling
process. Model compounds have been used extensively to
explore reaction pathways of asphaltenes; see, for exam-

370 A.P. Watkinson and D. I. Wilson

ple, Ref. 75. Fouling studies using this approach would be
valuable.
Fouling in higher-temperature pyrolysis systems is attracting increased attention. Bach et al. [66] provide a
survey of recent work in the light hydrocarbon pyrolysis
area and outline additional mechanisms for deposit formation in transfer line exchangers. Mass deposition onto
coupons placed downstream from the cracking zone of a
laboratory isobutane cracking apparatus was followed with
time. Fouling rates at 500C were found strongly dependent on the material of the coupon, being negligible for
quartz, low for incoloy and inconel, and significant for
15Mo3 steel. This was taken as evidence for the catalytic
role of the surface in deposition during cooling in dry
cracked gas atmospheres. Building on earlier work by
Froment and others, Huntrods et al. [76] simulated an
ethane pyrolysis quench system and compared the results
with performance over time of an industrial transfer line
exchanger. Two mechanisms of coke formation were considered important: (1) formation of polymers from precursors such as dienes and acetylene and (2) surface-catalyzed reaction between carbon and the metallic tube
surface.
DEPOSIT AGING
Some effects of deposit aging have been determined for
oxygenated gum deposits [32]. Thermogravimetric analysis
(TGA) and pyrolysis studies showed that composition of
deposits found on heat exchanger surfaces could be generated by the thermal degradation of the polyperoxide gums
precipitated from the bulk solution. The effect of deposit
aging on reaction chemistry has also been discussed in jet
fuel fouling. Jones and Balster [29] attributed the changes
in deposition profiles and reduction in deposition rates
between their 6-h and 72-h tests to changes in reaction
kinetics. They did not consider the changes in the temperature profile in the fluid caused by extended fouling.
Marteney and Spadiccini [15] did not find any appreciable
variation in deposition rate with test duration. Others [14,
24], however, observed an increase in average deposition
rate when the test duration was increased. Further work is
required in this area.
Dickakian [60] has shown how the fraction of coke in a
deposit from crude oil increases over time, whereas the
fraction of asphaltenes decreases. An initial deposit contained 30% asphaltenes and no coke. After 3 h of heating
and further fouling, the coke content of the deposit was
60% and the asphaltene content about 14%. The thermal
resistance of the deposit will change owing both to the
chemical reactions and to the further deposition. This
aging reaction must be understood if the mechanisms of
fouling are to be inferred from deposits taken from industrial exchangers that may have been on stream for many
months. As described above, a start has been made in the
analysis of aging reactions from autoxidation fouling.
MITIGATION
Control of fouling by manipulation of process variables
such as temperature and velocity or by the use of inserts is
discussed above. Modifications of process chemistry or
physicochemical properties of precursors through additives provide an additional mitigation strategy. Each ap-

proach entails costs that must be offset by potential savmgs. Costs of fouling have been reviewed by Bott [5].
Numerous types of antifoulant additives have been described [4, 77]: antioxidants, metal deactivators (MDAs),
dispersants, detergents, size limiters, and coke suppressants. Antioxidants interrupt the formation of fouling precursors either by converting hydroperoxides into stable
products or by scavenging peroxy radicals. Metal deactivators reduce the initiation properties of metal ions, whereas
detergents and dispersants prevent fouling precursors from
generating permanent deposits. There is a considerable
body of literature concerning the mitigation of autoxidation during fuel storage but little characteristic of the
higher temperatures found in many heat exchangers and
jet fuel feed systems. Additives that perform well in lowtemperature tests do not automatically function well at
higher temperatures.
Studies of the effects of a commercial antioxidant, BHT
(dibutylhydroxytoluene), on heat exchanger fouling from
model solutions of indene [33] showed that the antioxidant
inhibited the onset of autoxidation. There was no appreciable change in fouling mechanism or rate after the
antioxidant had been exhausted. Similar delays in the
onset of fouling in jet fuels were reported [29] when an
antioxidant (BHT) and an MDA were used. Other types of
jet fuel additives did not change the rate of reaction of
oxygen significantly but reduced deposition considerably
[24, 29]. These results are consistent with the different
additive mechanisms.
Increased rather than reduced deposition was observed
at high BHT concentration [33]. The increase in fouling
was attributed to reaction of the additive at the surface.
The surface temperature in this work (240C) was markedly
higher than the "ceiling" temperature for BHT antioxidation. Similar problems were found with a proprietary
phenol additive in jet fuel fouling [28]. Antioxidants, which
modify the reaction by sacrificial action, should not be
used beyond their known effectiveness limits. The polar
nature of antioxidants can lead to insoluble oxidation
products. Zabarnick and Grinstead [36] reported similar
results for BHT and other additives in fuel stability tests
at 140C. They also noted that different trends in additive
performance were evident in flowing tests at higher temperatures. The effectiveness of four different additives
(antioxidant, MDA, dispersant, detergent-dispersant mixture) was examined for three different jet fuels [31]. The
antioxidant, BHT, and MDA were not effective at the
temperatures used, which were above the antioxidant ceiling temperature. These compounds delayed the onset of
fouling by inhibiting the bulk reaction, as reported in Ref.
33. Heneghan et al. [28], however, found that metal deactivators gave promising reduction in deposition from other
jet fuels. Jones and Balster [29] found that dispersants,
which reduce particulate agglomeration in the bulk fluid,
gave the greatest reduction in deposition. The discussion
of fouling mechanisms suggests that dispersants would be
less effective in cases where deposition was controlled by
surface reaction and attachment. Mitigation of organic
fouling thus requires a reliable understanding of the fouling mechanism involved. Selection of additives is likely to
remain feedstock specific but should consider both the
feedstock composition and whether bulk or surface reaction/attachment effects are important. Testing of additive
packages is likely to remain an integral part of additive

Chemical Reaction Fouling: A Review 371

o.gn

,,,-,.,.. ~"

0.15

:..~,,,,-,,,,,.'.,:,~,..g~'~,,,,1,,.j,.

O.lO
I$11LTM

E o.05
v

iff

0.1~
40.05

t i m e (hrs)
oon

o,o

'"

..

0.05
ooo

os

-o.o51

41P

~o

t i m e (hrs)

O.~n

,, ,.,,,-,,~,,,.,.;,.~,~. ,,..,_,,,,,,,.,,'"'.,,'"-,, ,~'="

o.ls

=rg

0.10

,=

="

=;k"

'=

=r~=' % d , = r ~ = =

P ET-4250

~o.05 jZ,"

= Base 1

50
-0.05
t i m e (hrs)

selection. Tam [78] illustrated the effect of some commercial antifoulants on the deposition from a fuel oil doped
with a heavy oil rich in asphaltenes. It is clear from Fig. 6
that such commercial antifoulants can be effective, reducing fouling from a significant rate to essentially zero.
However, the mechanism by which the antifoulants work
requires further research.

C O N C L U D I N G REMARKS
The classification of organic fluid fouling into situations
caused primarily by autoxidation, polymerization, and
thermal decomposition clearly has its value; however, the
complex case of asphaltene fouling does not yet fit well
within this structure. Much progress has been made in
autoxidation fouling, in part because of the supporting
studies on fuel stability and jet fuel utilization. Polymerization fouling has been narrowly focused on styrene
reactions, and trends should be verified in other systems.

II
I

Figure 6. Effect of commercial antifoulants on fouling from heavy oil-fuel

oil blend. Antifoulant concentration, 100
ppm; oil velocity, 0.6 m/s; Tb, 85C;
Ts, o, 245C. From Tam [78].

Improved semiempirical mathematical models are becoming available. With regard to thermal decomposition-induced fouling, the process has been formulated as an
incompatibility or a phase separation problem, but little
progress has been made in fouling studies to determine
reaction and solubility limits. For higher-temperature conditions, the research related to the chemistry of petroleum
residue processing appears to offer some explanations of
observed fouling behavior. This extensive research could
be profitably extended to provide a route to better understanding of chemical reaction fouling in organic fluids at
moderate temperatures. The use of inserts and of chemical additives remains a major focus of the control of
fouling in industrial situations; an understanding of both
mitigation methods would benefit from further fundamental research.
Ongoing support to A.P.W. by the Natural Sciences and Engineering
Research Council of Canada is appreciated.

372

A . P . Watkinson and D. I. Wilson

NOMENCLATURE
s t o i c h i o m e t r i c p a r a m e t e r s in r e a c t i o n s (12) and
(13)
A + a s p h a l t e n e c o n t e n t o f feed, w t . %
A* a s p h a l t e n e c o r e c o n c e n t r a t i o n , w t . %
E activation energy, k J / m o l
H + p e n t a n e soluble f r a c t i o n of feed, w t . %
H* side chains s t r i p p e d f r o m asphaltenes, w t . %
ki r e a c t i o n rate constant, step i
R init initiation rate
[RH] c o n c e n t r a t i o n of h y d r o c a r b o n , R H , m o l / L
R.
h y d r o c a r b o n radical
ROOH
hydroperoxide
Re fouling resistance, m 2 K / ( k W )
Tsurf t e m p e r a t u r e at surface or d e p o s i t - f l u i d
interface, C, K
Tbulk t e m p e r a t u r e o f bulk fluid, C, K
Tf film t e m p e r a t u r e , C, K
TI t o l u e n e insoluble fraction, w t . %
t time, h
V volatile fraction w t . %

a, m, n, y

Greek Symbols
o~,/3, 3, p a r a m e t e r s in Eq. (10)
T s h e a r stress

REFERENCES
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Chemical Reaction Fouling: A Review

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Received April 17, 1996; revised September 22, 1996