56 Ind. Eng. Chem. Res.

1993, 32, 56-61

Relative Rates of Coke Formation from Hydrocarbons in Steam

Cracking of Naphtha. 2. Paraffins, Naphthenes, Mono-, Di-, and
Cycloolefins, and Acetylenes
Frank-Dieter Kopinke* *
Section of Remediation Research, Centre of Environmental Research Leipzig-Halle GmbH, Permoserstrasse
15, D 7050 (0) Leipzig, Germany

Gerhard Zimmermann1
WIP-Research Group “Organic High Temperature Chemistry”, Permoserstrasse 15, D 7050 (0) Leipzig,
Germany
Geerd C. Reyniers and Gilbert F. Froment
Laboratorium voor Petrochemische Techniek, Rijksuniversiteit Gent, Belgium

Relative rate constants of coke formation from saturated hydrocarbons, olefins, and acetylenes during
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steam cracking of naphtha at 810 °C were determined by application of 14C-labeled compounds. The
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range of hydrocarbons investigated comprises 20 representatives of paraffins, from methane to

hexadecane, and of naphthenes, from cyclopentane to hydroanthracene, and 20 olefins from ethene
to styrene, including cyclo- and diolefins, and five acetylenes. Carbonaceous deposits in pyrolysis
reactors from steel and quartz as well as in the transfer line exchanger (TLE) section were determined
separately.

The formation of carbonaceous deposits in olefins pro-
duction by steam cracking of hydrocarbons is a very un-
desirable phenomenon with considerable effects on the
operation of the plant. Therefore, it would be of great help
to have a model for the prediction of the extent of coke
formation. The development of accurate fundamental
models has been hampered by the lack of reliable infor-
mation on coking rates from individual hydrocarbons. An
experimental method for measuring the contribution of
certain carbon atoms of individual hydrocarbons in the
coke formation by application of the radio tracer technique
was described in part 1 of the current series (Kopinke et
al., 1988a).
Beyond the literature survey given in part 1 some recent
papers on coke formation should be mentioned here:
Froment (1990) mainly dealt with the kinetics of coke
formation and the influence of anticoking additives, while
Albright and Marek (1988a) reviewed the characterization
of coke deposited in industrial reactor tubes (Albright,
1988) and in laboratory experiments (Albright and Marek,
1988b).
Kunzru and co-workers published a series of experi-
mental studies directed to the kinetics of coke formation
(Kumar and Kunzru, 1985; Pramanik and Kunzru, 1985;
Kumar and Kunzru, 1987; Sahu and Kunzru, 1988), its
inhibition (Gosh and Kunzru, 1988; Vaish and Kunzru,
1989) , and the gasification of coke deposits (Mandal and
Kunzru, 1986). They concluded that ethene and aromatic
hydrocarbons are the main coke precursors in the pyrolysis
of n-hexane and naphtha, respectively. The rate of coke
formation was found to be proportional to the square of
the concentration of aromatics in the cracked product. All
aromatic hydrocarbons were treated as a lump. Benzene
and toluene were found to affect the coking rate to the
same degree. Zou et al. (1987) found ethene to be the
dominant coke precursor in propane pyrolysis. According
to their model the relative rates of coke formation from
ethene and propene are 264:1 at 850 °C, which is an un-
likely high ratio.
tThe investigations have been performed partially in the former
Department for Basic Organic Materials, Central Institute for
Organic Chemistry, in Leipzig.
Chaverot et al. (1986) assign an important role to ace-
naphthylene as a coke precursor. They used 20 wt %
mixtures of the investigated compounds in the n-decane
feed. This procedure is comparable to that applied in the
present paper, but it does not avoid a significant effect of
the additive on the pyrolysis. In his review on the catalytic
mechanism for the growth of carbon filaments, Baker
(1989) came to the conclusion that the available theories
on this phenomenon fail to account for all aspects of the
experimental results. Carbon filament formation is very
helpful in understanding the influence of reactor materials
on the rate of carbon formation and the morphology of the
deposits, but the actual contribution of this mechanism
to coke formation in industrial steam crackers is still a
matter of debate.
Starting from kinetic equations for the pyrolysis and the
coke formation, Plehiers et al. (1990) successfully predicted
the run length of an industrial ethane cracker.
The fouling of the transfer line exchanger (TLE), which
is important in industrial steam crackers, is not repre-
sented adequately in the recent scientific literature.
Relevant papers were published by Kaiser et al. (1984),
Horak and Baranek (1986), Zander (1989), Hundrots et al.
(1989), and Fernandez-Baujin et al. (1990). Only very few
data are available because of the difficulties involved in
performing laboratory scale experiments which are rep-
resentative of industrial TLE conditions.
For the purpose of a better understanding of the data
discussed in this paper, a brief presentation of our views
on the mechanism of coke formation, explained in more
detail in part 1 already, is given here:
(1) Coke deposits in the cracking coil are mainly formed
by reactions of gas-phase species (radicals and unsaturated
molecules) with the growing coke, which is in reality a
macroradical.
(2) Carbonaceous deposits in the quench zone result
from the physical condensation of high boiling components
of the cracked gas on the cooled walls. These deposits are
subject to further transformations like dehydrogenation
and chemical condensation.
The objective of this study is to come to a comprehensive
insight into structure-reactivity relations for the coking
tendency of hydrocarbons. For this purpose a wide range

0888-5885/93/2632-0056$04.00/0 © 1993 American Chemical Society

 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 57

Temperature (°C 1 Naphtha (

/Steam Table I. Relative Rate Constants of Coke Formation from
-Quartz Reactor Paraffins and Naphthenes in the Cracking Tube and the
77777 TLE
tracer hydrocarbon position of 14C fe(CC) A(TLE-C)
methane u 0.085 0.05
ethane u 0.21 0.14
n-hexane 1 0.64 0.58
n-octane 1 0.61 0.43
n-hexadecane 1 0.61 0.56
3-methylpentane 1 0.67 0.50
2,2,4-trimethylpentane 5 0.72 0.64
n-octane 4 0.85 0.67
2-methylpentane 4 0.79 0.61
2-methylhexane 2 1.1 0.94
cyclopentane u 1.1 1.1
cyclohexane u 1.1 1.0
methylcyclopentane ring 1.55 1.55
1,4-dimethylcyclohexane 7 0.84 0.94
ethylcyclohexane ring 1.2 1.45
ethylcyclohexane 7 1.15 1.15
ethylcyclohexane 8 0.72 0.68
TLE-Coke rc-propylcyclohexane 7 1.1 1.1
decaline 1 1.25 1.35
Length tetradecahydroanthracene 9 2.5 3.6
Cracked Gas The ratio kc./kc¡, represented by (fec.)r, is a rate coefficient
Figure 1. Deposition of coke in the laboratory pyrolysis reactor. for the production of coke out of tlie labeled component
of positionally uC-labeled hydrocarbons from methane to j, relative to that out of the naphtha feed. This ratio equals
1 only when the coke formation out of the tracer and out
chrysene were tested. These are typical feedstock con- of the naphtha proceed at the same specific rate (rc./c,·).
stituents and pyrolysis intermediates and final products.
The results obtained with aromatic hydrocarbons will be (fcc.)r can be considered as a relative specific rate of coke
formation or as a relative rate constant. The term relative
presented in a further paper of this series. rate constant, which is used further on in this paper, does
not claim to express the ratio of rate constants of ele-
Experimental Equipment and Procedure
A detailed description of the experimental equipment mentary reactions, but to reflect the overall result of a
and procedure was given in part 1 of this series and by competition kinetics. It is accessible through ac., the
specific radioactivity of the coke resulting from a pyrolysis
Kopinke (1985). The pyrolysis experiments were con- run and af, the specific radioactivity of the feed consisting
ducted in tubular reactors made from quartz (Figure 1) of naphtha and tracer j.
or Cr-Ni-steel. The feedstock was a straight-run naphtha
with a boiling range of 50-180 °C. The standard reaction Taking the ratios of (1) and (2) leads to
conditions (T = 810 °C; residence time, 0.4 s; total pres- dc,/dcf = kc.Cj/kCic f (3)
sure, 0.1 MPa; dilution ratio H20/naphtha, 0.7 g/g; or also, accounting for the definitions given above,
C2H4/C3H6 weight ratio in the cracked gas, 2.5) are similar kc
to those in industrial pyrolysis reactors. A small amount
(<0.1%) of a tracer hydrocarbon containing a 14C-atom in “'/= ¡ -/ (4)
a given position was added to the naphtha. The ^-con-
or
taining hydrocarbons were either purchased or synthesized =
according to known procedures (Kopinke, 1985). The (kc), kc./kC{ ac./a{. (5)
-

specific radioactivity of the pyrolysis feedstock was in the
range of 10-1000 kBq/g. After a pyrolysis run of 1 h the
reactor was purged with nitrogen and the coke was burnt
off with air and determined quantitatively as C02. Special
attention was paid to a separate determination of the
carbonaceous deposits in the reactor (“coil-coke”) and in
the cooling and condensation section, between 400 and 200
°C corresponding to the TLE in an industrial unit
(“TLE-coke”). Very little coke was deposited in the zone
between 650 and 400 °C. Liquid and gaseous pyrolysis
products were analyzed by radio gas chromatography. The
radioactivity of C02 (as a solution of phenylethylamine
carbonate) was measured by liquid scintillation counting.
Results and Discussion
1. Relative Rate Constants for Coke Formation. If
the coke formation out of the tracer j, labeled with 14C,
and that out of the naphtha may be considered to proceed
according to first-order kinetics, the rates in a given point
in the reactor can be written
rCi
=
kCjCj
rc,
=
kc,Cf
The reproducibility of the relative specific radioactivity,
ac /«f, was comprised between 5 and 10%, except for
methane and acetylene on alloyed steel surfaces, which
were less satisfactory.
Tables I and present relative rate constants fe(CC) and
fe(TLE-C) for the formation of coil- and TLE-coke from
45 compounds containing in each one a labeled carbon
atom. These values arise from the contribution of the
labeled carbon atom of the feed hydrocarbon, but also from
all the labeled pyrolysis products. The k(CC)- and k-
(TLE-C)-values are integral values, derived from the coke
deposits over the total length of the tubular reactor or
cooling zone by combustion.
The absolute value of the coking rate in the reactor is
strongly influenced by the reactor material. It amounted
to roughly 0.1 mg of C/(cm2-h) on a quartz surface and to
0.1-2.5 mg of C/(cm2-h) on a steel surface. The wide range
of coking rates on steel surfaces observed under identical
pyrolysis conditions reflects the influence of the material
and of the history of the material on its catalytic activity.
(1) It is well-known that the absolute coking rate on a steel
surface exhibits a high initial value and then declines with
(2) time (e.g. Kopinke et al. (1981) and Sundaram et al.
58 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993

Table II. Relative Rate Constants for Coke Formation from erogeneous decomposition at the surface or, more likely,
Olefins and Acetylenes by reactions of gas-phase methyl radicals. The apparent
position A(TLE- A(CC,)/ conversion of [14C]methane, measured by the radioactivity
tracer hydrocarbon of 14C *(CC) C) fc(CC2) content in all the pyrolysis products, does not reflect the
ethene 0.73 0.35 0.97 intermediate formation of methyl radicals, because of the
propene 1 1.03 0.85 O dominance of their identity reaction back to methane. The
1.09 0.90 0.86
surprisingly high reactivity of methane can be related to
propene 2
propene 1, 3 0.83 0.67 0.93
pent-l-ene 1 1.30 0.83 0
its activation by the large pool of radicals generated in the
pent-l-ene 5 0.68 0.50 0.85 naphtha pyrolysis. Tesner came to a similar conclusion
hept-l-ene 1 1.07 0.86 0.84 for the formation of pyrocarbon from benzene (Arefewa
2,2,4-trimethylpent-4-ene 5, 8 1.46 0.86 a
and Tesner, 1987). The presence of gas-phase radicals
n-octenes6 4 1.6 1.3 0.88
2 2.1 1.75 0.79
increased the rate of coke formation from benzene by 1-2
2-methylhexenes6
cyclopentene6 u 2.1 2.55 0.76 orders of magnitude.
cyclohexene6 u 1.66 1.25 a Ethane is much more reactive than methane. Its con-
methylenecyclohexane 7 1.44 1.5 0.69 version amounted to 45%, the yield of ethene to 38%
butadiene 1 1.68 1.35 0.64
2.4 2.9 0.71
under the standard pyrolysis conditions. Consequently,
cyclopentadiene U
methylcyclopentadienes methyl 1.00 0.85 0.65 the contribution to coke formation of ethane can be mainly
ethylcyclopentadienes methyl 0.96 0.83 0.71 due to its pyrolysis products. The k(TLE-C)-value of 0.14
cyclohexa-1,3-diene u 0.84 1.0 0.71 is in good agreement with a predicted value, taking into
methylcyclohexa-1,3-dienes methyl 0.92 1.2 0.83
8 1.62 1.55 0.87
account the potential of ethene only (A(TLE-C) = 0.35),
styrene
ethyne4 5.2 (7-20) 3.0 0.40 which yields a value of (0.38)(0.35) = 0.133 for ethane.
propyne 3 2.0 (2.5-5) 1.25 0.28 For paraffins beyond pentane there is no influence of
but-l-yne 1, 2
-

(6.0) 3.8 a the chain length on the coking tendency of a certain carbon
pent-l-yne 5 0.75 (0.72) 0.53 0.66
atom in the molecule (compare, e.g., the terminal C-atoms
hex-l-yne 3 3.0 (2.0) 1.9 0.53
in n-hexane and in n-hexadecane).
“
Data are available only for experiments in a steel reactor, without The contribution of different types of carbon atoms to
axial resolution of deposits. 6 Mixtures of isomers synthesized by acid coke formation increases in the order primary < secondary
catalyzed dehydration were used. The dominant isomers are n-oct-4- < tertiary. This holds for both coil- and TLE-coke. It
ene and -5-ene, 2-methylhex-l-ene and -2-ene, [l-14C]cyclopentene, and
[l-14C]cyclohexene. c&(CC)-values of acetylenes pertain to coke de- suggests tiie following ^-values for paraffins with C-number
posits on quartz; values in parentheses refer to coke on steel surfaces. > 6:

for primary C-atoms

(1981)). Despite this, no significant dependence of relative
rate constants on the run length of a pyrolysis experiment
lasting from 0.25 to 5 h was observed.
As described already in detail and interpreted in
mechanistic terms in part 1, the relative rate constants are
identical (with a few exceptions) for coke formation on
quartz and steel surfaces and also for different surface to
volume ratios. This lends some confidence to the con-
clusion that the relative rate constants determined in
bench scale experiments by means of the tracer technique
are valid for the coke formation in industrial cracking
units, provided it is not controlled by hydrodynamic ef-
fects. These may play a role in the TLE fouling, however.
2. Results for Paraffins. A separate determination
of coke deposited in the first and in the second half of the
cracking tube yielded fc(CCj) and k(CC¿) values which were
identical, within the experimental error (±5%) for pa-
raffins and naphthenes. Exceptions were ethane (k-
(CCil/fctCC!) = 1.14) and the tertiary carbon atom in
2-methylhexane (*(CC2)/A(CC1) = 1.24), which lead,
therefore, to a slightly higher contribution in the coke
deposited in the second half of the reactor.
A direct participation of paraffins with more than two
carbon atoms to TLE-coking is very unlikely, because of
their almost complete conversion under the conditions of
severe cracking. Consequently, the TLE-coke is formed
exclusively from cracked products, including those re-
sulting from the labeled tracers.
From Table I it follows that methane is a very poor coke
precursor. Nevertheless, its contribution in the coil-coke
formation can hardly be accounted for by contributions
of its pyrolysis products only. Its conversion at 810 °C
amounts to 5% and at 750 °C to less than 2%. This is
significantly lower than the corresponding &(CC)-values:
0.085 and 0.125, respectively. Therefore, it can be con-
cluded that methane is involved in the coil-coke formation
not only by its unsaturated reaction products, but, ac-
cording to Blackwood et al. (1967), also via a direct het-
0.65
k(CC) =
fe(TLE-C) = 0.54
for secondary C-atoms
*(CC) 0.82
=
fe(TLE-C) =
0.64
for tertiary C-atoms
k(CC) =
1.10 fe(TLE-C) =
0.94
This set of reactive rate constants, which has an accuracy
of better than ±0.1, permits the coking tendency of any
paraffin molecule to be predicted by a simple incremental
calculation. The spread of relative rate constants in the
group of paraffins is rather narrow. Obviously, the degree
of branching in paraffin molecules is of minor importance
(compare, e.g., the terminal C-atoms in n-octane and in
isooctane). The transformation of a normal paraffin into
an isoparaffin corresponds to the disproportionation of two
secondary carbon atoms into one primary and one tertiary
carbon atom. This transformation is almost neutral with
respect to the coking potential of the involved carbon
atoms.
3. Results for Naphthenes. The coking rate of
naphthenes with one or two rings is about 50% higher than
that of paraffins. There are no significant differences
between five- and six-membered rings. There is none
between alkylated and nonsubstituted rings. C-atoms in
the «-position with respect to the ring have a higher k-
value than the same type of C-atoms in paraffins, whereas
C-atoms more distant from the naphthene ring are com-
parable with those in paraffins.
Decaline and decahydroanthracene are the only repre-
sentatives of polycyclic naphthenes investigated here. The
coking tendency of bicyclic naphthenes seems to be very
close to that of monocyclic naphthenes, but molecules with
more than two condensed rings tend to have a considerably
higher coking rate. The A-values of paraffins and
naphthenes for coke formation in the coil and in the TLE
are very close. This does not seem to justify a separate
handling of both types of coke, but the utility of a separate

consideration of reactor and TLE becomes clearly evident
for the more reactive hydrocarbons like acetylenes and
aromatics.
4. Results for Olefins. Table II presents relative rate
constants for a wide variety of carbon atoms in more than
20 mono-, di-, and cyclo-olefins. A separate determination
of deposits in the first and in the second half of the
cracking coil, available from the steel tube segment in the
tubular quartz reactor, revealed a significant dependence
of the relative rate constants on the axial position, as ev-
idenced by the ratio k(CC2)/k(CC!) (column five in Table
II). Unlike saturated hydrocarbons, all the olefins and
acetylenes contribute more to coke deposits in the first part
of the cracking coil. This is the more pronounced the
higher the reactivity of the component. Indeed, ethene,
which has the lowest coke potential of all olefins, con-
tributes almost uniformly to coke deposits along the re-
actor, whereas the coke formation from ethyne, the most
active coke precursor, in the first half is 2.5 that in the
second half of the cracking zone. Typical values of the
ratios k(CC2)/k(CC1) are 0.85 for acyclic monoolefins and
0.70 for cyclo- and diolefins. Labeled carbon atoms in
saturated hydrocarbons behave like the majority of the
unlabeled feedstock over the entire reactor, while labeled
carbon atoms in unsaturated target molecules benefit from
their greater reactivity from the very beginning of the
cracking. This advantage, however, is lost with increasing
conversion in the reactor.
Under Experimental Section, relative rate constants for
coke formation were said not to depend on the reactor
material. The first representatives of acetylenes, ethyne
and propyne, however, deviate from this rule: their coking
rates are higher on steel surfaces, probably because of
significant contribution of the metal catalyzed coking.
Therefore, Table II contains two sets of k(CC)-values: one
referring to coke formation on a quartz surface and a
second, in parentheses, on a steel surface.
Cyclopentadiene and its derivatives, as well as cyclo-
pentene, which is dehydrogenated to cyclopentadiene, coke
faster on quartz. Speculation on a specific catalytic effect
of the quartz surface seems not reasonable. Hence, the
fc(CC)-values given in Table II for these compounds are
averages.
The main product of steam cracking, ethene, has the
smallest coking tendency among unsaturated nonaromatic
hydrocarbons. Nonetheless, because of its high concen-
tration it is one of the major sources of coil-coke. Propene
exhibits similar properties with respect to coke formation
in the reactor but a considerably higher potential to pro-
duce TLE-coke, probably because it generates allylic
radicals, which are recognized as precursors of heavier
products. A slight difference between sp2-hybridized C-
atoms and the methyl C-atom in the coke production in-
dicates that part of the propene contributes as an entity,
wheras another portion contributes only after its scission
from the molecule.
The majority of the olefins and acetylenes studied here
carry the labeled atom in the unsaturated part of the
molecule, including allyl and propargyl C-atoms. Carbon
atoms in aliphatic chains of those molecules coke ap-
proximately like aliphatic C-atoms, irrespective of their
parent molecule, when the distance to the multiple bond
exceeds two single C-C bonds. This can be seen from a
comparison of k-values for the primary aliphatic C-atoms
in paraffins, olefins, and acetylenes given in Table III. No
effect of the original hydrocarbon structure on the coking
rates of the terminal C-atoms in the second cracking zone
and in the cooling section can be detected. This is a
Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993 59
Table III. Relative Rate Constants for Coke Formation
from Primary Aliphatic C-Atoms in Pentane, Pentene, and
Pentyne
tracer hydrocarbon hcco A(CC2) fe(TLE-C)
n-alkanes 0.64 0.64 0.57
pent-l-ene 0.74 0.62 0.50
pent-l-yne 0.90 0.60 0.53
consequence of the fragmentation of aliphatic chains in
the gas phase. The slightly high k(CC)-values for pentene
and pentyne in the first cracking zone do not necessarily
reflect an incorporation of the entire olefin or acetylene
molecule into the coke matrix. They can be attributed to
a higher gas-phase decomposition rate of the unsaturated
molecules relative to the paraffin, thus giving rise to a
faster supply of labeled coke precursors during the initial
cracking period.
The relative rate constants of coke formation for sp2-
hybridized C-atoms in acylic monoolefins (>C4) increase
in the sequence primary < secondary < tertiary ones (k-
(CC), 1.3 < 1.6 < 2.1; k(TLE-C), 0.83 < 1.3 < 1.75), which
parallels the scale of reactivities of C-atoms in paraffins.
Besides 10 acyclic monoolefins, Table II contains 10
more olefins with special structures. Butadiene behaves
in a way similar to the monoolefins. The higher integral
reactivity of its terminal C-atom in comparison to mono-
olefins arises mainly from the first cracking zone (k-
(CC2)/k(CCi) = 0.64). Even styrene, that can be consid-
ered as an activated olefin, falls in the same class of coke
precursors. It is considered here as an olefin because of
the position of the labeled C-atom in the vinyl group.
Nevertheless, both olefins yield substantial amounts of
fuel, resulting in k (TLE-C) -values, which are higher than
those for primary C-atoms in non-activated olefins (1.35
and 1.55 versus 0.8). Cyclopentadiene holds a top position
as coke presursor. The range of relative rate constants
starting from ethene at one end and cyclopentadiene at
the other end of the scale vary by a factor of 3 and 8 for
coil- and TLE-coke, respectively. The coking rates of
monoolefins with a six-membered ring like cyclohexene and
methylenecyclohexane are close to those of acyclic olefins,
like n-octenes. Cyclopentene behaves very much like cy-
clopentadiene, given by its fast dehydrogenation via radical
reactions or/and by molecular 1,4-elimination.
Alkyl substituents on the cyclopentadiene ring are
partially split off. This could explain why their coking
contributions are smaller than those of unsubstituted cy-
clopentadiene itself. The scission of the labeled carbon
atoms, however, is significantly different (50 and 85% of
the methyl C-atom in methyl- and ethylcyclopentadiene,
respectively), whereas the Á-values are nearly identical.
The relatively low coking tendency of cyclodiolefins with
more than five C-atoms could result from their fast con-
version into benzene and its derivatives (Kopinke et al.,
1987), which have a poor coking potential: fe(CC) = 0.30
and k (TLE-C) = 0.325 for benzene, e.g. This would be the
case for cyclohexadiene and methylcyclohexadienes as well.
It will be discussed further.
Figure 2 shows a possible correlation between the con-
tribution to the formation of coil-coke of labeled carbon
atoms positioned in paraffins, naphthenes, and olefins and
their contribution to the formation of aromatic pyrolysis
products. The data are all taken from the naphtha
cracking under standard conditions (810 °C). Acetylenes
do not agree with this correlation. Paraffins other than
methane and ethane are represented as average values for
primary, secondary, and tertiary C-atoms. The points
related to hydrocarbons, which can form aromatics by
intramolecular reactions (Kopinke et al., 1988b), all fall
60 Ind. Eng. Chem. Res., Vol. 32, No. 1, 1993
20 40 60 80
Aromatics [%] *"
Figure 2. Correlation between relative rate constants of formation
of coil-coke from olefins (O), naphthenes ( ), and paraffins ( ) on
quartz and the contribution to aromatic pyrolysis products of labeled
C-atoms in tracer hydrocarbons.
below the correlation and are not shown in Figure 2, except
that for cyclohexadiene. An interpretation of Figure 2
requires some additional comments on the formation of
aromatic hydrocarbons under cracking conditions. Even
though the detailed mechanism is still a matter of specu-
lation, one can distinguish between two routes: (i) the
formation of aromatic structures from small unsaturated
units with less than six carbon atoms and (ii) the rear-
rangement and dehydrogenation of units, which contain
at least six carbon atoms and have a hydrygen deficit m
in C„H2(n+1-m) of more than 1.
The first route is dominant in the formation of aromatic
structures from paraffins, monocyclic naphthenes, and
lower olefins; the second, for polycyclic olefins (Zimmer-
mann et al., 1985), cycloolefins, and cyclodiolefins con-
taining already a number of carbon atoms—the
“ensemble”—sufficient to form an aromatic ring without
requiring intermolecular synthesis steps. The correlation
illustrated in Figure 2 points toward aromatics as the main
coke presursors. The same picture, however, would be
obtained if the formation of coke and aromatic hydro-
carbons require the same type of non-aromatic presursors,
i.e., involve the same type of reactivity in radical reaction
steps. Obviously, this type of reactivity is not that ex-
hibited by ensemble molecules, as is evidenced by a com-
parison between cyclopentadiene and cyclohexadiene. The
latter produces mainly benzene (55%). Hence, it is not
the bare aromatic ring that leads to a high coking rate.
From the present results it cannot be unambiguously
concluded whether the different type of intermediates or
the different composition of the aromatic fraction formed
via routes i and ii is prevailing in the coking rates. Aro-
matic hydrocarbons may play a dual role: as real coke
precursors and as a probe for short living, highly reactive
intermediates producing coke in their turn.
A linear extrapolation of the correlation for olefins in
Figure 2 yields a finite intercept on the ordinate, pointing
toward a direct route from olefins to coke, unaffected by
aromatics or their precursors. The corresponding curve
for saturated hydrocarbons goes through the origin.
5. Results for Acetylenes. The data on relative rate
constants of acetylenes, shown in Table II, reflect a sig-
nificant contribution of a catalytic mechanism, with a top
position for the unsubstituted ethyne.
A very high enrichment of acetylenic carbon atoms—up
to a factor of 100—was observed in deposits near the en-
trance of the steel reactor. Even on a surface free of
metals, ethyne has a rate constant 10 times higher than
that of ethene in the first cracking zone. In general, the
contribution of acetylenes to coke deposits is higher in the
reactor than in the cooling section.
In spite of their high relative rate constants the im-
portance of acetylenes with respect to coke formation in
steam crackers is limited by their rather low concentration.
Conclusions
From the results presented in this paper it follows that
a reduction of the paraffin content in favor of naphthenes
significantly reduces the run length, in particular when the
naphthenic fraction contains polycyclic ring structures. On
the other hand, monocyclic naphthenes in a high boiling
feedstock like hydrowax behave very much like paraffins,
because of the dominance of paraffinic side chains in those
molecules. For a homologous series of components the
boiling range and the molecular weight have no direct
influence on the tendency to form carbonaceous deposits.
In practice, however, the coking potential of high boiling
feedstocks is essentially controlled by their aromatic
fraction. A small content of olefins (<5%) in a steam
cracker feedstock can be tolerated with respect to the
fouling in the reactor and in the TLE.
Aromatic hydrocarbons play an important role in the
coke formation, more than saturated hydrocarbons and
olefins. Detailed studies on their coking tendencies will
be the subject of a further publication.
Nomenclature
Cf surface concentration of unlabeled carbon, g of C/m2
=
surface concentration of labeled carbon, g of C/m2
=
Cj
cf = volume concentration of unlabeled carbon from feed
hydrocarbons, g of C/L
Cj volume concentration of labeled carbon atoms from model
=
hydrocarbon j, g of C/L
kc, rate constant of coke formation from unlabeled carbon
=
atoms, m/s
kc. = rate constant of coke formation from labeled carbon
atoms, m/s
(kc)T
=
relative rate coefficient of coke formation
fc(CC) = (kc)T for coke formation in the coil
fc(TLE-C) = (kc )r for coke formation in the TLE
fc(CCf) = (kc )r for coke formation in the first section of the
coil
(kc )r for coke formation in the second section of the
=
fe(CC2)
coil
rc = rate of coke formation from unlabeled carbon atoms, g
of C/(m2 s)
rc = rate of coke formation from labeled carbon atoms, g of
JC/(m2 s)
T =
pyrolysis temperature, °C
Subscripts
C = carbon
f =
feed
i =
general index, can be f or j
j =
labeled hydrocarbon, labeled carbon atoms
r = relative
Greek Symbols
aCj
=
specific radioactivity of coke, kBq/(kg of carbon in the
coke)
af = specific radioactivity of feed, kBq/(kg of carbon in the
feed)
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Received for review July 13, 1992
Accepted October 19, 1992

Kinetics of the Fischer-Tropsch Reaction on a Precipitated Promoted

Iron Catalyst. 1. Experimental Procedure and Results

Egbert S. Loxt and Gilbert F. Froment*

Laboratorium voor Petrochemische Techniek, Rijksuniversiteit, Krijgslaan 281, B-9000 Gent, Belgium

The Fischer-Tropsch reaction on a commercial promoted precipitated iron catalyst was studied in
a tubular reactor under non-deactivating conditions of temperatures between 523 and 623 K, pressures
between 0.6 and 2.1 MPa, hydrogen to carbon monoxide feed ratios between 3.0 and 6.0 mol/mol,
and W/F°co values between 9.2 and 63.0 kg-s/mol. The selectivity for carbon dioxide, methane,
and hydrocarbons of different functionality with 2-15 carbon atoms in the molecule was obtained
as a function of the carbon monoxide conversion, the reactor temperature, and the total pressure.
The initial rate of formation of these products was measured as a function of the total pressure and
the partial pressures of hydrogen and carbon monoxide at the reactor inlet. These experiments,
combined with the information gained from the catalyst characterization, indicated that carbon
dioxide is formed by the water gas shift reaction. Methane, n-paraffins, and 1-olefins with two and
more carbon atoms in the molecule are all primary products of the Fischer-Tropsch reaction. The
composition of the hydrocarbon product fraction, as a function of the number of carbon atoms in
the hydrocarbon molecule, could be described by the Schulz-Flory distribution, although it is shown
that the latter only approximately holds for the efflüent of an integral reactor.

1. Introduction of the following empirical power law type rate equation:

The reaction between carbon monoxide and hydrogen
on heterogeneous catalysts yielding hydrocarbons, carbon
dioxide, and water has led to intensive research ever since
it was discovered by Fischer and Tropsch in 1923. Con-
siderable efforts have been devoted to the understanding
of the mechanism of this reaction and, more recently, to
the development of more selective catalysts. The major
part of the kinetic studies did not go beyond rate ex-
pressions of the empirical power law type rate for the
reaction rate of carbon monoxide:
=
Rco ^coPH2nPcom
(Vannice, 1976; Dry, 1981; Feimer et al., 1981; for a review
see also Huff and Satterfield (1984)).
Bub and Baerns (1980) and Grenoble et al. (1981) also
expressed the rate of formation of carbon dioxide in terms
Author to whom correspondence should be addressed.
* Various other mechanisms have been assumed. The main
f
Present address: Inorganic Chemical Product Division, De-
gussa A.G., P.O. Box 1345, D6450 Hanau-1, Germany.
=
(2)
*co2 *cOiPcouPH2oy
In most cases the hydrocarbons were lumped according to
the number of carbon atoms in the molecule. Sometimes
all the hydrocarbons were simply treated as one lump or
split into a paraffin lump and an olefin lump (Zein el Deen
et al., 1979; Bub and Baerns, 1980; Dictor and Bell, 1986;
Gaube et al., 1982).
Some authors derived Langmuir-Hinshelwood-Houg-
en-Watson (LHHW) rate equations. Dixit and Tavlarides
(1983) based their kinetic equations on the “carbide”
(1) mechanism, which basically states that the hydrocarbon
intermediates on the catalyst surface are formed by po-
lymerization of monomers consisting of carbon and hy-
drogen. The rate-determining step (RDS) was assumed
to be the hydrogenation of a carbon intermediate, C-l:
C-l + x(H-l) CHX-1 + x-1
—
(3)
difference between these mechanisms is the nature of the
monomer. Besides monomers consisting of carbon and

0888-5885/93/2632-0061$04.00/0 &copy; 1993 American Chemical Society