Ind. Eng. Chem. Res.
1988, 27, 755-759 755
McGill, 1987). Other promising materials include silicized
steels (Brown et al., 1982) and steels coated with manga-
nese-rich surfaces (Suzuki et al., 1986).
Many nonmetals in the coke are probably due to im-
purities in the water used to make the steam that is a
diluent for the hydrocarbon feedstock. The presence of
sulfur could be either because of sulfur-containing com-
pounds in the water or sulfur compounds often deliberately
added as deactivators of the stainless steel surfaces. More
data are needed to determine if or how nonmetals affect
coking and decoking.
Information obtained on cokes produced from atactic
polypropylenes clarify some aspects of coke formation in
ethylene furnaces and especially the coke produced from
tarry liquids. Escape of the gases through coke deposits
and surface-catalyzed reactions are apparently two im-
portant factors when high molecular weight liquids are
pyrolyzed.
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Summary
Materials of construction are needed for the coil, transfer
line, and TLX plus possibly the preheater coils that will
minimize surface-catalyzed coke formation and will also
minimize spalling of particles containing nickel, iron, and
Downloaded via ONERA on March 7, 2023 at 09:22:41 (UTC).
chromium. Operating modifications that will likely result
in less coke formation have been suggested.
Acknowledgment
Financial support for this investigation was provided by
Gulf Research Foundation, Alon Processing, Inc., and
Purdue Research Foundation.
Registry No. C2H4, 74-85-1; C2H6, 74-84-0; C3H8, 74-98-6; Fe,
7439-89-6; Cr, 7440-47-3; Ni, 7440-02-0; Si, 7440-21-3; P, 7723-14-0;
Mechanistic Model for Formation of Coke in Pyrolysis Units Producing
Ethylene
Lyle F. Albright* and James C. Marekt
School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907
Coke is formed by three mechanisms during pyrolysis processes used to produce ethylene. The
mechanisms result in metal-catalyzed coke, noncatalytic coke formed from tars, and pyrocarbon coke
that is produced when small precursors react with free radicals on the coke surface. The relative
importance of each of the above mechanisms depends on the operating conditions, hydrocarbon
feedstock, and type of reactor used.
Although much has been reported in the past on coke
formation and on various surface reactions that occur
during the pyrolysis of various hydrocarbons, no known
model has yet been proposed to explain several features
of coke formation in both laboratory and industrial fur-
naces. Albright and Marek (1988a,b) have recently ob-
tained extensive data that are particularly applicable to
pyrolysis units producing ethylene and other unsaturates.
Their results and those in the literature were employed
to develop a mechanistic model in which coke is produced
by three different methods. This model is likely also ap-
f Present address: E. I. du Pont de Nemours &
Co., Inc., Aiken,
SC 29801.
0888-5885/88/2627-0755$01.50/0
S, 7704-34-9; Cl2, 7782-50-5; K, 7440-09-7; Ca, 7440-70-2; poly-
propylene, 9003-07-0.
Literature Cited
Albright, L. F.; McGill, W. A. Oil Gas J. 1987, Aug 31, 46-50.
Albright, L. F.; Tsai, T. C. In Pyrolysis: Theory and Industrial
Practice; Albright, L. F., Crynes, B. L, Corcoran, W. H., Eds.;
Academic: New York, 1983; Chapter 10, pp 233-254.
Baker, R. T. K.; Harris, P. S. In Chemistry and Physics of Carbon;
Walker, P. L., Thrower, P. A., Eds.; Marcel Dekker: New York,
1978; Vol. 1, Chapter 1.
Brown, D. E.; Clark, J. T. K.; Foster, A. I.; McCarroll, J. J.; Sims, M.
L. In Coke Formation on Metal Surfaces; Albright, L. F., Baker,
R. T. K., Eds.; ACS Symposium Series 202; American Chemical
Society: Washington, D.C., 1982; Chapter 5, pp 23-44.
Dunkleman, J. J.; Albright, L. F. In Industrial and Laboratory Py-
rolyses; Albright, L. F., Crynes, B. L., Eds.; ACS Symposium
Series 32, American Chemical Society: Washington, D.C., 1976;
Chapter 14, pp 241-260.
Graff, M. J.; Albright, L. F. Carbon 1982, 20, 319.
Marek, J. C.; Albright, L. F. In Coke Formation on Metal Surfaces;
Albright, L. F., Baker, R. T. K., Eds.; ACS Symposium 202, Am-
erican Chemical Society: Washington, D.C., 1982a; Chapter 7, pp
123-150.
Marek, J. C.; Albright, L. F. In Coke Formation on Metal Surfaces;
Albright, L. F., Baker, R. T. K., Eds.; ACS Symposium Series 202;
American Chemical Society: Washington, D.C., 1982b; Chapter
8, pp 151-176.
Suzuki, G.; Uchida, M.; Ohsaki, K.; Onodera, T.; Unemura, T.;
Sundaram, K. M. “Development of Coke Deposition Retarding
Bimetallic Tubes for Ethylene Cracking Furnaces”. Paper pres-
ented at the National Meeting of American Institute of Chemical
Engineers, New Orleans, April 6-10, 1986.
Tsai, T. C.; Albright, L. F. In Industrial and Laboratory Pyrolyses;
Albright, L. F., Crynes, B. L., Eds.; ACS Symposium Series 32;
American Chemical Society: Washington, D.C., 1976; Chapter 16,
pp 274-195.
Received for review September 19, 1986
Revised manuscript received December 8, 1987
Accepted December 21, 1987
plicable to other high-temperature processes including the
dehydrochlorination of 1,2-dichloroethane to produce vinyl
chloride.
Three Coking Mechanisms
The three mechanisms by which cokes are produced in
the coil, transfer line, and transfer-line exchanger (TLX)
of an ethylene furnace are reviewed next.
Mechanism 1 involves metal-catalyzed reactions in
which metal carbides are intermediate compounds and for
which iron and nickel are catalysts (Baker and Harris,
1978; Trimm, 1983). The resulting filamenteous coke often
contains 1-2 wt % metal; the metal is positioned primarily
at the tips of the filaments. Other catalytic cokes have
© 1988 American Chemical Society
756 Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988
been designated as arrowhead or needle cokes (Albright
et al., 1979); such cokes may, however, be mixtures of
filamenteous coke and noncatalytic coke produced by
mechanisms 2 and 3, to be discussed later. Filamenteous
coke is produced at temperatures from about 400 °C up
to at least 1050 °C (Albright and Marek, 1988a), and it is
often the predominant coke formed on clean stainless steel
surfaces. It does not form, however, on noncatalytic sur-
faces such as glass or aluminized steel surfaces, as prepared
by Alon Processing, Inc. Filament thickening that causes
an increase in the diameter of the filaments occurs by
mechanism 3.
Mechanism 2 has been described by Lahaye et al.
(1977). Aromatics (Ar-H) are probably the most important
intermediates; some aromatics are produced by trimeri-
zation and other reactions involving acetylene. Starting
with simple aromatics, the following sequence of conden-
sation and dehydrogenation reactions occurs in the gas
phase to produce tar droplets and soot particles:
-h2
nAr-H--
nucleation
polynuclear aromatics (tars) —
---;—
and condensation
-H2 -h2
tar droplets- semitar droplets-«·
coke particles (soot)
Bennett (1981) using an electron microscope has seen
the droplets hit solid surfaces. The droplets either rebound
from the surface or adhere to it. The tar or semicoke
adhering to the surface decomposes to form hydrogen and
coke containing numerous surface radicals (Baker, 1985).
Tars with low viscosities wet the solid surfaces and spread
out on it; a relatively featureless coke results. Semitar
droplets with high viscosities, however, retain their
sphericity and often cluster.
This coke is metal-free if quartz or Vycor glass surfaces
and a metal-free feedstock are used. In industrial furnaces,
however, metal particles or compounds spall from the tube
walls; some of these particles collect in the tar droplets that
eventually are converted to coke. Mechanism 2 is generally
relatively unimportant at temperatures of 700 °C or less.
The exact temperatures depend to some extent on the
hydrocarbons being pyrolyzed. Spherical coke particles
on the surface grow in size, however, by mechanism 3.
Mechanism 3 involves as a first step the reactions of
microspecies with the free radicals on the coke surfaces.
These microspecies with molecular weights of usually 100
or less are often acetylene (Harris and Weiner, 1984),
probably ethylene or other olefins, butadiene, and free
radicals such as methyl, ethyl, phenyl, or benzyl radicals.
Acetylene reacts with surface radicals to form aromatic-
type rings; dehydrogenation of these rings results in more
coke and more surface radicals that permit further reac-
tions with microspecies. With ethylene, a free-radical
polymerization sequence or a modification of it can be
postulated. Dente et al. (1983) and Trimm (1983) sug-
gested a polymerization technique but gave no details on
the probable chemistry. Mechanism 3 explains the
thickening of filaments and the growth of spherical coke
particles on the surfaces.
Figure 1 indicates a version of mechanism 3 in which
methyl radicals react to form attached methyl groups. On
the surface, C-H bonds are broken, re-forming surface
radicals and producing hydrogen radicals or molecules. A
chain reaction is in essence occurring, and the coke is
formed one carbon atom at a time. Phenyl radicals
(formed from benzene), benzyl radicals (formed from
toluene), and ethyl radicals probably also react with surface
radicals by a similar chain mechanism. With the larger
Microspecies such as alkyl or phenyl radicals react with
with surface radicals (S·) to start chain mechanism.
Example with methyl radicals
1.
H
i i
2.
H
S-C-H
S-C· + H·
I,
H H
3- H .
fjj
H
S"C· + 'C-H —^ S-C-C-H
a H
4. and 5.) Reactions similar to 2 and 3 continue the chain
6 All C-H bonds are eventually broken.
Figure 1. Postulated chemical steps when methyl radicals react
with surface free radicals (one version of mechanism 3 coking reac-
tions).
radicals, morethan one carbon atom is added to the sur-
face each time radical reacts. Surface free radicals likely
a
couple readily with gaseous free radicals; the coke which
is quite graphitic is a highly delocalized aromatic system,
and resonance stabilization aids the coupling step.
Since the microspecies have low molecular weights, they
diffuse rapidly in the high-temperature gases (Cleland and
Wilhelm, 1956). Hence, the microspecies have fairly
uniform concentrations at all radial positions in a tubular
reactor and on all sides of spherical or filamenteous coke;
such a conclusion is especially true in a laboratory unit
operated with relatively low flow velocities. As a result,
both filamenteous and spherical coke grow in size rather
uniformly in all radial directions. Such a finding was
reported by both Tibbetts (1984) and Albright and Marek
(1988a).
Explanation of Laboratory Coking Results
Laboratory, as well as industrial coking, results can be
explained in considerable detail by considering mecha-
nisms 1, 2, and 3. When noncatalytic surfaces are used,
as can easily be done in laboratory units, only mechanisms
2 and 3 need to be considered.
The results of Albright and Marek (1988a) are used as
an example for explaining laboratory results; their results
are particularly suitable since they investigated a wide
range of operating conditions and since some variables of
importance were investigated for the first time. Their
results indicate that coking rates and coke morphology
varied significantly as the residence time of the reaction
mixture at high temperatures increased. Plots of the rate
of coke formation versus residence time indicated one or,
even in one occasion, two maxima. In interpreting such
results for acetylene runs, the coke precursors of impor-
tance for each of the three mechanisms must be consid-
ered. Acetylene is a highly effective precursor for both
mechanisms 1 and 3. The maximum rate of coke forma-
tion on stainless steel coupons and the coke morphology
at low residence times (and a high concentrations of
acetylene) were obviously caused by coke formed mainly
by mechanisms 1 and 3.
Acetylene, however, also reacts in the gas phase to
produce various coke precursors, and Figure 2 is a quali-
tative prediction of the concentrations of such precursors
as a function of time. Low molecular weight microspecies
such as benzene are the initial precursors produced, and
later reactions result in polycyclic aromatics, tar droplets,
 Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988 757

H
1 2 3

1. Formation of filamentous coke on "clean"

stainless steel surface early in run.

2. Thickening of filaments and collection of car

or semi-tar droplets. Incomplete fill-in
near me tal surface.

3. Fill-in mechanism creates essentially non-porous

coke away from the raecal surface, but some
porosity is retained near the metal.

4. Region of dynamic coke growth, which moves to

Figure 2. Postulated concentrations of coke precursors in gas phase
for acetylene pyrolysis at ~1000 °C and up to 10-15-s residence
time.
semitar droplets, and coke or soot particles. Maxima in
the rates of coking at intermediate residence times are
explained by these heavier coke precursors and the major
importance of mechanism 2.
Toluene and all reaction products formed from it are
however not highly effective coke precursors for mecha-
nism 1; hence, mechanism 1 is of relatively minor impor-
tance when toluene is used. Toluene, however, produces
higher molecular weight precursors such as tar; mechanism
2 is hence of primary importance especially at intermediate
or higher residence times. Based on experimental results,
mechanism 3 apears also to be of major importance when
toluene is used as a feedstock. This finding suggests that
benzyl and/or phenyl radicals are important and effective
precursors.
Prior to coke formation on a solid surface, coke pre-
cursors must either react on or collect on the solid surfaces
in the reactor. These precursors must therefore be
transferred to the solid surfaces; both the geometry of the
reaction system and gravity were found to have an im-
portant effect on the transfer steps of the higher molecular
weight precursors (Albright and Marck, 1988a). By use
of tar droplets as an example in a coil reactor, improved
transfer to the surface causes coke formed by mechanism
2 to occur over a longer length of the coil and/or at pos-
itions in the reactor that are further upstream. Although
the flow velocity of the gas stream in the reactor has not
been extensively investigated as an operating variable in
coking experiments, the velocity likely has a major effect
on the transfer steps of the heavier coke precursors. To
obtain extremely high velocities in a laboratory unit that
are similar to those in industrial units will not be easy.
The degree of graphicity of a coke likely depends on
several factors which include at least the following:
1. Relative Importance of Mechanisms 1,2, and 3 in the
Coking Process. Cokes formed by mechanism 1 and by
mechanism 3 (Tibbetts, 1983a,b) are quite graphitic,
whereas those formed by mechanism 2 are presumably
mostly amorphous.
2. Type of Precursor. In the case of mechanism 3, the
nature of the microspecies is likely very important; phenyl,
benzyl, or other aromatic radicals may produce a more
graphitic coke than alkyl radicals. Acetylene likely also
produces a graphitic coke.
3. Surface of Metal, Coke, etc., on Which Coke Is De-
posited. Considering mechanism 3, a more graphitic coke
the right with time, creating additional thickness
of non-porous coke. Spheres grow from adsorption
and reaction of mlcrosoecies.
Figure 3. Growth of coke deposits on stainless steel surfaces as a
function of time.
may be produced when the outer layers of the coke are
highly graphitic as compared to those that are amorphous
or microscopically rough.
4. Non-Hydrocarbon Gases in Reaction Mixtures.
Hydrogen and steam, for example, may indirectly affect
the graphicity of the coke. Both gases react with coke at
high temperatures to gasify it. Amorphous coke may react
more rapidly than graphitic coke; in such a case, the level
of graphicity of the residual coke would be increased.
Explanation of Industrial Coking Results
A much improved understanding is now possible of the
mechanisms by which cokes form in industrial furnaces
as a function of run time. The results obtained by Albright
and Marek (1988b) are particularly useful. The formation
of coke on the stainless steel surface of an ethylene coil
is divided into at least two time periods, as depicted by
Figure 3.
In a plant run that is often 4-8 weeks in length, filam-
enteous and other metal-catalyzed cokes form in high
concentrations during the initial stages of the run (when
decoked or clean stainless steel surfaces such as HK-40 or
Incoloy 800 are present); mechanism 1 is then especially
important. The filaments are excellent collection sites for
tar or semitar droplets. Industrial cokes near the stainless
steel surfaces frequently contain 1-2 wt % metals. A few
industrial cokes have, however, been found with lower
concentrations of metal in this region. When the metal
content is high, the numerous filaments that form prevent
the tar droplets from completely filling in the voids around
the base of the filaments. Simultaneously the filaments
thicken via mechanism 3. As tar droplets collect on the
tops of the filaments, solid coke layers begin to form.
When that occurs, tar droplets and microspecies cannot
penetrate and complete the filling-in operation, and a
porous layer of coke results near the metal surface.
Filling in the void spaces occurs by means of both
mechanism 2 and 3, and a relatively solid coke matrix is
produced when fewer filaments are present. With time,
the solid coke increases in thickness. Most of the metal
to catalyze the production of more filaments (by means
of mechanism l) is transferred from the inlet or interme-
diate section of the coil in the ethylene furnace (Albright
758 Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988
MECHANISM 1
Figure 4. Approximate relative importance of mechanisms 1, 2,
3 for industrial and laboratory cokes.
and Marek, 1988b). The amounts of metals entrained and
transferred in the gas stream affect the number of fila-
ments produced and hence the importance of mechanism
1 as the solid coke layer grows in thickness.
The hydrocarbon feedstocks used in pyrolysis units and
the operating conditions affect the types and the concen-
trations of coke precursors; hence they affect the relative
importance of the three mechanisms and the rates of
coking. The precursors formed from ethane and naphtha
feedstocks are for example obviously quite different.
Various naphthas also often produce quite different pre-
cursors.
In a TLX, the sudden decrease in gas temperatures
results in condensations and the production of considerably
more tar droplets. In addition, radical destruction by
recombination is favored over production of radicals.
Hence, the relative importance of the three coking mech-
anisms shifts when the gases enter the TLX’s, and mech-
anism 2 becomes more important. In the coil, mechanism
3 is likely most responsible for the fill-in operations.
Photomicrographs of cokes from coils and TLX’s support
these conclusions.
Figure 4 is a prediction of the relative importance of
mechanisms 1, 2, and 3 during the production of coke in
the coils and TLX’s of a typical ethylene unit. As already
indicated, mechanism 1 is of more importance immediately
after decoking when both the coils and TLX’s have just
been cleaned and are essentially coke free. The predictions
of course also vary with operating conditions and hydro-
carbon feedstocks. As also shown, mechanism 1 is of little
or no importance when glass surfaces or aluminized steel
surfaces are used; both glass-coated and aluminized sur-
faces have been used in recent pilot plant and/or industrial
plant runs. Some iron or nickel may, however, be present
in such runs due to imperfections in the coatings, diffusion
through the coatings, or impurities in the feed. Mechanism
3 is favored by higher temperatures and with higher con-
centrations of acetylene in the gas stream. At these con-
ditions, considerable amounts of very thick filaments were
produced (Albright and Marek, 1988a).
The mechanism proposed here is undoubtedly also ap-
plicable to coke production in industrial dehydrochlo-
rination units used to produce vinyl chloride. Many of the
coke precursors mentioned above are also formed in these
vinyl chloride units, e.g., acetylene, benzene, and butadiene.
Recommendations
Although the proposed mechanism contributes signifi-
cantly to an understanding of coke formation in ethylene
units, additional information is needed to clarify the fol-
lowing factors:
1. Role of steam and factors affecting coke gasification
(or formation of carbon oxides) during pyrolysis. Dun-
kleman and Albright (1976) and Siklos et al. (1986) re-
ported that carbon oxides are formed almost exclusively
because of metal-catalyzed reactions on the walls of a coil;
few carbon oxides formed when coke was deposited
or no
on glass reactors. The relative rates of gasification of
graphitic and amorphous cokes should be clarified.
2. Source of metal and predominant method of metal
transfer in the coil, transfer line, and TLX. Vaporization
of metal sulfides is sometimes important (Marek and
Albright, 1982).
3. Roles of nonmetals such as sodium, potassium, cal-
cium, phosphorus, chlorine, and sulfur in coking and de-
coking. Some nonmetals promote decoking steps (Trimm,
and
1977).
Importance of hydrogen chloride and chlorine in the
4.
gas phase of vinyl chloride units. As metal chlorides form,
surface compositions and roughness are affected. Ferric
chloride is, for example, quite volatile. The roles of hy-
drogen chloride and metal chlorides should be investigated
with respect to coke formation, gasification, and the ki-
netics of dehydrochlorination. Bernstein and Albright
(1972) showed, for example, that chlorine sometimes
promotes free-radical reactions on the surfaces.
Acknowledgment
Financial support for this investigation was provided by
Gulf Research Foundation, Alon Processing, Inc., and
Purdue Research Foundation.
Registry No. C2H4, 74-85-1.
Literature Cited
Albright, L. F.; Marek, J. C. Ind. Eng. Chem. Res. 1988a, first in a
series of three in this issue.
Albright, L. F.; Marek, J. C. Ind. Eng. Chem. Res. 1988b, second in
a series of three in this issue.
Albright, L. F.; McConnell, C. F.; Welther, K. In Thermal Hydro-
carbon Chemistry·, Oblad, A. G., Davis, H. G., Eddinger, R. T.
Eds.; Advances in Chemistry Series 183; American Chemical So-
ciety: Washington, D.C., 1979; pp 175-191.
Baker, R. T. K., personal communications, 1985.
Baker, R. T. K.; Harris, P. S. In Chemistry and Physics of Carbon·,
Walker, P. L., Thrower, P. A., eds.; Marcel Dekker: New York,
1978; Vol. 1, Chapter 1.
Bennett, M. J., personal communication, March 1981.
Bernstein, L. S.; Albright, L. F. AIChE J. 1972, 18, 141.
Cleland, F. A.; Wilhelm, R. H. AIChE J. 1956, 1, 489.
Dente, M.; Ranzi, E.; Barendregt, S., Jr.; Tsai, F. W. “Ethylene
Cracker Transferline Exchanger Fouling". Presented at the Na-
tional Meeting American Institute of Chemical Engineers, Hous-
ton, TX, March 1983.
Dunkleman, J. J.; Albright, L. F. In Industrial and Laboratory Py-
rolyses·, Albright, L. F., Crynes, B. L., Eds.; ACS Symposium
Series 32; American Chemical Society: Washington, D.C., 1976;
Chapter 14, pp 241-260.
Harris, S. J.; Weiner, A. M. Combust. Sci. Technol. 1984, 38, 75.
Lahaye, J.; Badie, P.; Ducret, J. Carbon 1977, 15, 87.
Marek, J. C.; Albright, L. F. In Coke Formation on Metal Surfaces·,
Albright, L. F., Baker, R. T. K., Eds.; ACS Symposium Series 202;
American Chemical Society: Washington, D.C., 1982; Chapter 7,
pp 123-150.
Siklos, P.; Izsaki, Z.; Varga, T. A.; Kalman, J. Erdol Kohle-Erdgas
Petrochem. Brenstoff-Chem. 1986, 39, 243.
 Ind. Eng. Chem. Res. 1988, 27, 759-764 759

Tibbetts, G. G. GMR-4518 Report, Oct 21, 1983a; General Motors bright, L. F., Crynes, B. L., Corcoran, W. H., Eds.; Academic: New
Research Laboratories, Warren, MI. York, 1983; Chapter 9, pp 203-232.
Tibbetts, G. G. Appl. Phys. Lett. 1983b, 42(8), 666.
Tibbetts, G. G., personal communications, 1984. Received for review September 19, 1986
Trimm, D. L. Catal. Rev.-Sci. Eng. 1977, 16, 155. Revised manuscript received September 21, 1987
Trimm, D. L. In Pyrolysis: Theory and Industrial Practice·, Al- Accepted December 11, 1987

Thermal Decomposition of Cyclohexane at Approximately 810 °C

F. Billaud,* *t P. Chaverot,1 M. Berthelin,1 and E. Freund8
Département de Chimie Physique des Reactions, UA 328, CNRS, INPL-ENSIC, 1 rue Grandville,
54042 Nancy, France, Direction de Recherches, Recherche et Développement, Instituí Franqais du Pétrole,
Centre d’Etudes et de Développement Industriéis, Solaize, BP 3, 69390 Vernaison, France, and Direction de
Recherche Physico-Chimie Appliqueé et Analyses, Instituí Franqais du Pétrole, 1 et 4 Avenue de Bois Préau,
BP 311, 92506 Rueil-Malmaison, France

In order to determine the behavior of cycloparaffins in steam cracking reactions, a study of the thermal
decomposition of cyclohexane in the presence of n-decane has been carried out at ca. 810 °C by using
the technique of plug flow reactor. Cyclohexane chiefly decomposes into ethylene, hydrogen, 1,3-
butadiene, and small amounts of cyclohexene. We propose a primary mechanism of the decomposition
of cyclohexane initiated by n-decane. This mechanism leads to three main primary stoichiometries
which account for the whole range of reaction products.

1. Introduction: Aims and State-of-the-Art
Mushrush and Hazlett (1984) have pyrolyzed model
compounds representative of shale crude to confirm that
molecules containing long unbranched alkyl groups may
be the source of n-alkanes in jet fuels derived from this
source.
We have used a rather similar approach in the present
paper to describe and explain olefin production during the
steam cracking of petroleum cuts liable to contain large
amounts of naphthenic compounds in relation to linear
alkanes. We began by investigating the n-decane-cyclo-
hexane mixture. This model can simulate the behavior of
cycloparaffins in naphtha.
A better understanding of the initial decomposition
processes of cyclohexane is thus very important for im-
proving our understanding of the cracking and oxidation
of cycloparaffins. Decompositions of naphthenic com-
pounds have not been analyzed with as much precision as
those of paraffins.
Although a number of studies of cyclohexane or sub-
stituted cyclohexane pyrolyses have been reported, these
were mainly concerned with product distributions and
yields at high conversion and with possible contributions
of surface effects (Fabuss et al., 1964a,b; Romavacek et al.,
1972; Levish et al., 1969; Zdonik et al., 1967; Frey, 1949;
Garnett et al., 1976); Gordon (1962) and Stein and Ra-
bino vitch (1975) detected the isomerization of the cyclo-
hexyl radical into methylcyclopentyl radicals in low-tem-
perature experiments. Above 400 °C, cyclic radicals begin
to split up (Gordon, 1962; Stein and Rabinovitch, 1975;
Arai et al., 1960).
Mechanistic modeling has been useful in studying the
kinetics of pyrolytic reactions at low conversion (Tanaka
et al., 1975; Powers and Corcoran, 1974; Murata and Saito,
1975). Few attempts have been reported at high conver-
tCNRS.
* Institut
Franjáis du Pétrole, Vernaison.
§
Institute Franjáis du Pétrole, Rueil-Malmaison.
sion levels similar to those of industrial cracking (Sun-
daram and Froment, 1978; Aribike et al., 1981). This stems
from the large number of molecular species and free rad-
icals with their associated reactions. The number of these
reactive species drastically increases with conversion and
leads to excessive computation time.
Most of these studies have a particular emphasis on
kinetics within the Rice (1931, 1933), Rice and Herzfeld
(1934), and Rice and Kossiakoff (1943) theory parameters.
Tsang (1978a,b) investigated the decomposition mech-
anism and initial velocities of cyclohexane from single-
pulse stock tube experiments and demonstrated that the
main initial process is the isomerization of cyclohexane into
1-hexene followed by the decomposition of 1-hexene.
The initiation of chains during the dissociation of pure
cyclohexane is difficult. The breaking of the C-H bonds
requires an energy expenditure of 95.2 kcal/mol (Kon-
dratiev, 1974), whereas breaking along the C-C bonds
occurs at much lower velocity. This breaking requires only
77 kcal/mol and does not lead to the formation of any
monoradicals.
The isomerization of the biradical that is formed
/CH2s
CH CH2
•CH,(CH2).CH2· ==
—-
| CH2=CH(CH2)3CH3
|
ch2ch ch2
through the intermediary of an activated complex with six
centers considerably facilitates the initiation of chains
following the formation of a weakened C-C bond in 1-
hexene. The breaking of this bond leads to a resonant allyl
form (C3H5·):
C3H6 + H*
CH2=CH(CH2)3CH3 —
*ch2ch2ch3 + ch2=chch2*
c2h4 + ch3*

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