Carbon Vol 20, No. 4. pp 319-330.

19R2
Printed in Great Britain.

00086223:8?/04031~12~3.~/0
Pergamon Rest Lid.

COKEDEPOSITIONFROMACETYLENE,BUTADlENEAND
BENZENE DECOMPOSITIONSAT 500-900C
ONSOLIDSURFACES
MICHAELJ. GRAFF? and LYLE F, AL~RIGH~
School of Chemical Engineering, Purdue University, West Lafayette, IN 47907,U.S.A.
(Receiwd IO Ckiuber 1981)
Abstract-Coke formation from decomposition of acetylene, butadiene, and benzene and decoking were investigated on Incoloy 800, aluminized Incoloy 800, and Vycor glass surfaces at SOO-900C.On Incoloy 800, the
coke was greater in quantity and contained iron and nickel particles. On aluminized Incoloy 800, the coke contained
a trace of aluminum, but on Vycor glass, no metal was in the coke. Coking-decoking sequences were highly corrosive
on Incoloy800 surfaces, but they had much less effect on the aluminized Incolny8OOorVycor glass. Filamenteous coke
which is formed catalytically and contains nickel and iron was formed only on Incoloy 800 surfaces. A general
mechanism for formation and deposition of coke is proposed. Filamenteous coke helps collect tar droplets formed by
gas-phase reactions. Such droplets decompose on the surface to produce coke that contains no metal.

Although coke is produced in only relatively small

amounts when hydrocarbons are pyrolyzed to produce
ethylene and valuable by-products or when 1, 2-dichloroethane is dehydrochlorinated to produce vinyl
chloride, coke production results in a significant increase
in operating expenses. Because of coking, the pyrolysis
furnaces have to be shut down periodically to decoke,
the heat transfer coefficients in the furnaces are often
drastically reduced, and coking generally results in corrosion of the stainless steel surfaces on which the coke is
deposited. Significant advantages would occur if coking
could be reduced, and there is a need to better understand the mechanism of coking and of decoking.
Albright, McConnell and Welther[l] demonstrated that
valuable new information can be obtained by comparing
the character of coke formed from acetylene, butadiene,
ethylene and propylene. The former two compounds are
generally considered to be important coke precursors.
They had employed a scanning-electron microscope
equipped with EDAX to analyze the metal content of the
coke. The coke formed on Incoloy 800 surfaces often
contained highly dispersed metal particles making the
coke magnetic in nature. These metal particles contained
nickel, chromium and especially iron that had obviously
been removed in some manner from the surfaces. Baker
ef al. [5,6]
and associates [2-4] and Bernard0
have postutated a mechanism that explains the simultaneous corrosion of the surface and the catalytic
production of a filament-type coke. Of interest, Incoloy
800 surfaces that had first been aluminized were never
found to contain these three transition metals.
The results of Albright, McConnell and Welther[l] are
most interesting but they raise more questions than they
answer. In the present investigation, more information
has been obtained relative to the coke produced from
acetylene, butadiene and benzene. Information has been
obtained on the effect of temperature, partial pressure of
*Presentaddress: Amoco Oil Co., Chicago, Illinois, U.S.A.

coke precursor and time of operation for cokes deposited

on Incoloy 800, aluminized Incoloy 800 and Vycor glass
surfaces.
2.EXPERIMENTAL

The equipment and operating procedures were essentially identical to those employed by Albright, McConnell
and Welther[l]. Coupons that were about 0.5 x 2 x
0.15 cm were positioned inside a Vycor glass tube that
was 2.2cm I.D. and 107cm long. This tube was positioned horizontally in an electrical furnace controlled at
any desired temperature in the 500-900C range. Acetylene, butadiene, helium and oxygen flows were metered as
desired to the inlet of the Vycor glass tube. For benzene
experiments, helium was bubbled through liquid benzene
at room temperature to produce gas mixtures containing
about 12% benzene. Steam was provided by boiling a
flask filled with water. Residence times of the gas stream
in the constant-temperature portion of the Vycor glass
tube were about 20 sec. In most cases, the coupons were
positioned at the beginning of this portion of the reactor
which is designated as the lead position. The rear position, or end of this portion of the reactor, was about
25cm beyond. The aluminized (or aionized) Incoloy
800 coupons were furnished by Alon Processing, Inc. of
Tarentum, Pa. Incoloy 800 coupons had been subjected
at high temperatures to gaseous aluminum; as a result,
some aluminum diffused into the metal resulting in a high
concentration of aluminum of the surface.
Coupons after being removed from the Vycor glass
tube were cooled in an inert atmosphere, and pictures
were then taken using a JSM-U3 scanning-electron
microscope at magnifications varying from 1000 to
20,000. The metal content of the solid surfaces of the
coupon or of the coke produced was measured using an
EDAX, model 707.
3.CO~GANDDECO~NG~~~TS

Significant changes were noted in the surface composition and appearance of the Incoloy 800 as a result of
319

320

MICHAELJ. GRAFFand LYLE F, ALBRIGHT

coking and subsequent decoking, especially for runs at

900C. To clarify the effect of heating, an Incoloy 800
coupon was heated to 900C in a helium atmosphere. The
chromium content of the surface increased from 22 to
60% after 8 hr heating as indicated by EDAX. Similar
chromium enrichment of the surface also occurred at
900C when acetylene, butadiene or benzene was
employed. The titanium content of the surface of the

coupon also increased to perhaps 2-370 because of heating at 900C.

The appearance of the Incoloy 800 surface changed
significantly during helium treatment at 900C as indicated in Fig. 1; coupons are shown before and after the
heat treatment. The Incoloy 800 coupons as received has
a rather heterogeneous surface. The white areas shown
in the upper left picture were iron-rich particles covering

Fig. 1. Untreatedand helium treated metal coupons.

Cokedepositionfrom chemicalsat 500-900Con solid surfaces

about .5-10% of the surface. EDAX analysis of the
remainder of the surface indicated 45% iron, 33% nickel
and 22% chromium. Heat treatment in the presence of
helium resulted in tiny whiskers, columns or spikes which
are mainly iron or chromium rich particles.
Heat treatment of aluminized Incoloy 800 coupons at
900C in the presence of helium resulted in little change
of either the composition or the appearance of the surface. The surface exhibited chicken wire markings and
contained some almost pure aluminum deposits which
are the white areas of pictures shown in Fig. 1. Part of
the surface aluminum, however, undoubtedly existed as
alumina. The areas between the markings analyzed approximately 46% aluminum, 27% iron, 1% nickel and 9%
chromium. The few pitted areas shown were somewhat
less aluminum rich. With heat treatment, there were
probably fewer pitted areas.
3.1 Coke formation from acetylene
Filmenteous coke was the predominant type of coke
formed in Incoloy 800 surfaces at 500C when either pure
acetylene or helium-acetylene mixtures containing 5%
acetylene were used. Both constant-diameter and braided
(or rope-like) filaments were produced as shown in Fig.
2, and most filaments had diameters of about 0.1-0.2 pm.
A few very long and almost straight filaments with
constant diameters of 0.5-1.0 pm were also noted; three
such filaments are shown in the lower left picture of Fig.
2. The length-to-diameter ratios of the filaments were
often at least 200: 1. The upper right picture of Fig. 2
shows a double helix of filaments; such a double helix
was also noted in another case. The coupon treated with
pure acetylene at 500C was re-examined after several
months, and one filament was then found that appeared
to be hollow or basically a tube. All filaments contained
metal particles as indicated by EDAX analysis. Nickel
and especially iron were predominant in these particles.
For runs at longer times, such as 8 hr, more coke was
noted on the surface and a higher fraction of the coke
appeared to be chunky or amorphous coke such as
shown on the center left section of the lower left picture.
Some globular coke, such as will be described later, was
also noted.
No filamentous coke was ever observed on aluminized
(or alonized) Incoloy 800 or on Vycor surfaces regardless
of the conditions used or the hydrocarbon feed stream
employed. Only amorphous coke was formed from
acetylene in such cases at SOoOC[l].Lesser amounts of
coke were apparently formed on both aluminized and
Vycor glass surfaces based on visual observations. The
coke formed on both aluminized steel and Vycor glass
surfaces never contained detectable amounts of iron or
nickel. Cokes deposited on aluminized steel surfaces
contained however traces of aluminum or alumina.
Figure 3 shows the coke formed at 500C with a feed
stream having an acetylene partial pressure of 0.05 atm.
Only a very few filaments were noted on the coupon
located in the lead position of the Vycor glass tube; these
filaments were, however, very long. One constantdiameter filament and one braided filament appear to be
joined. The other end of the constant-diameter filament

321

seems to be connected to surface. The coupon located in

the rear position of the constant-temperature zone was
apparently almost coke free.
Coke formed from acetylene at 900C appeared to be a
mass of rather spherical droplets that had partially fused
together as shown in Fig. 3. This type of coke is called
globular in this investigation whereas it was called
knobby by Albright, McConnell and Welther[l]. The
globular coke varied in shape from rather perfect
spheres, partly fused together, to droplets that were
fused to a much greater extent. The general characteristics of cokes deposited at 900C on Incoloy 800,
aluminized Incoloy 800 and Vycor glass surfaces were
similar in all cases but with perhaps some differences in
the diameter of the droplets. In some portions of an
aluminized coupon, it was possible to see the metal
surface below or through the coke; apparently less coke
was deposited on these surfaces as compared to Incoloy
800 coupons. When the globular cokes deposited in Incoloy 800 coupons were scrapped with a knife blade,
there were essentially two layers of coke. The layer
closest to the metal surface was highly adherent to the
metal, but the top layer was rather easily removed. The
top layer of coke formed on all coupons contained no
detectable iron, nickel or other metals. The amount of
coke increased with time of operation and with higher
partial pressures of acetylene. At 900C and with acetylene at atmospheric pressures, the Vycor glass tube
plugged after about 1 hr. With a partial pressure of
0.05 atm, only a relatively small thickness of coke was
noted after 16hr of operation. It is estimated, based on
this finding, that the rate of globular coke deposition at
900C is second order or higher based on the acetylene
partial pressure. Such a finding seems consistent with the
fact that condensation reactions of acetylene to produce
heavier hydrocarbons are probably mainly second-order
reactions.
3.2 Coke formation from butadiene
Coke was produced from butadiene at temperatures of
500, 700 and 900C and at partial pressures of 0.05 and
1.0 atm.
Temperature had a major effect on the morphology of
the deposited coke. Figure 4 shows the results for Incoloy 800 coupons subjected for 8 and 16 hr to a heliumbutadiene mixture containing 5% butadiene. At 5OOC,a
thin brown but smooth film of coke was formed. At
700C more coke was present on the coupon and appeared to be a cloudy film. At 9OOC,profuse needle coke
was present; in some cases the coke gave the appearance of finely cut ribbons which seemed to
originate at iron- or chromium-enriched particles on the
surfaces of the coupons. The lower right picture of Fig. 4
shows a column-like filament growing out of a
chromium-enriched particle on the surface. This column
was formed on the coupon positioned at the rear position
of the constant-temperature zone, and it was similar in
appearance to formations noted on the Incoloy 800 coupon heated to 900C in the presence of helium. Both
coupons also had concentrations of about 3% titanium on
their surfaces.

322

MICHAEL
I. GRAFFand LYLEF. ALBRIGHT

Fig. 2. Pure CzHz over Incoloy 800 at 500C.

At 900C and for 1 hr runs, globular and/or spaghettilike cokes were formed on al1 three surfaces. The
spaghetti-like characteristics were particularly noted on
the Incoloy 800 coupons as compared to aluminized
Incoloy coupons as indicated by Fig. 5. The globular and
spaghetti cokes were fused together in many cases. The
precursor for these cokes is thought to be tar droplets
that flowed rather readily before being converted to coke

as will be discussed later. On aluminized Incoloy 800, the

diameter of the coke spheres increased with time, as
shown for exampie in the lower right hand picture of Fig.
5.
For 900C runs using fncoloy 800 coupons, the outer
layers of coke after 8 and 16hr were primarily needle or
cut ribbon-type cokes. Some chunks of amo~hous coke
were also observed after 16 hr. Less coke formed on the

Coke deposition from chemicals at 500-900Con solid surfaces

(1 micron = f--w)

323

(1 micron = e---4

Fig. 3. 5% C2H2over Incoloy 800for 8 hr.

aluminized Incoloy 800 or Vycor glass surfaces as compared to the Incoloy 800 surface; portions of the aluminized metal could sometimes be seen for coupons
investigated at 900C. More coke was formed in all cases
when pure butadiene was employed as compared to a
mixture containing 5% butadiene.
For runs at SOOC,the exit gases from the Vycor tube

were mainly butadiene, but some liquid product was

collected in an ice trap. Based on gas chromatography,
this liquid was mainly Cs hydrocarbons with lesser
amounts of C6 and C4 hydrocarbons. The Gs and Gs
are probably mainly aromatics based on the more
detailed analyses by Albright and Yu[7] for comparable
experiments. At 9OOC,most of the butadiene reacted in

MICHAELJ. GRAFFand LYLE F. ALBRIGHT

Fig. 4. 5% C& over Incoloy 800 (1 pm = ---I.

the Vycor glass reactor, and considerable hydrogen and

methane were noted in the exit gas stream. Essentially
no liquid product was obtained, however, for 16 hr of
operation when a feed mixture containing 5% butadiene
was employed.
For all runs considerable tars were deposited in especially in the cool exit end of the Vycor glass tube. For a
run at SOT using pure butadiene, liquid deposits formed
in the tube where the temperatures are 170C or lower.

For a 7OOT run, brown liquid droplets formed in the exit

end of the tube where temperatures varied from about
600 to 3OOT. For a 900C run, brown tar collected in the
exit end where the temperatures dropped from 800 to
170C.
3.3 Coke ~o~~~~oR from benzene
For a benzene run at 5OOC,an Incoloy 800 coupon
was tarnished with a spotted, light-brown residue after

Coke deposition from chemicals at NC-900C on solid surfaces

16hr. With the scanning-electron microscope, the base

metal was still cleariy visible through the coke which
appeared amorphous in character. At 7OOC,more coke
formed in the lncoloy 800 coupon which appeared to
have a filmy clouded surface. Figure 6 shows pictures
taken of both the Incoloy 800 and aluminized Incoloy
800 surfaces. An amorphous coke with the beginnings of
globular coke were noted on both surfaces. In one area

325

of the aluminized surface, there were large columns or

chunks of coke (see lower right picture of Fig. 6); such
deposits were not observed on any other coupons.
At 900C, globular coke was observed on both Incoloy
800 and aluminized Incoloy 800 surfaces as shown in Fig.
7; the top two pictures are for runs of 1 hr whereas the
bottom two pictures are for runs of 8 hr. Three features
are of interest. First, considerable more coke occurred in

326

MICHAEL
J. GRAFFand LYLEF. ALBRIGHT

Fig. 6. 12% C6H6at 700Cfor 16hr (IO Fm = -).

all ca!res on the Incoloy 800 coupons as compared to the

alumiisized Incoloy coupons; the aluminized surface can
be seten even after 8 hr operation. Second, the diameter
of the: coke spheres increased in the 1-8 hr time period.
Third , the spheres of coke on the aluminized surfaces
were sometimes transparent to the SEM beam as shown
in the lower right picture of Fig. 7.

3.4 Decoking of metal coupons

Two decoking experiments were made using Inr:oloy
800 coupons on which coke had been deposited . To
deposit the coke, the coupons were exposed to a mi:vture
of 5% acetylene in helium for 8 hr at 900X Decc&king
was accomplished for one coupon by contacting it with
pure steam at 700C for 24 hr; the other coupon was

Coke depositionfrom chemicals at 5WWC

contacted with pure oxygen at 800C for 24 hr. Photographs of the resulting surfaces are shown in Fig. 8.
After steam, the surface indicated numerous iron-rich
particles, but several protruding chromium-rich spikes
were also noted. These spikes appeared white in the
pictures, and were estimated to be as great as 1.5-2.0 pm
in length. One prominent spike is shown in the two
pictures for steam butnoff shown in Fig. 8; in each case
CAR Vol. 20, No. 4-E

on solid surfaces

327

this spike is slightly to the left of the center of the

picture. EDAX analyses of one spike indicate the following approximate compositions: 62% chromium, 22%
iron and 16% nickel. The composition of the remaining
surface except for iron-rich regions was about 42%
chromium, 36% iron and 22% nickel. There was
obviously both a significant change in surface composition and also in roughness of the decoked Incoloy

328

MICHAEL
J. GRAFFand LYLE F. ALBRIGHT

Fig. 8. Carbon burn-off for 24 hr at 7WC of an Incoloy 800 surface, originally treated with 5% C2H2at 900Cfor
8 hr.

800 surface as compared to the surface before coking

and decoking.
With oxygen decoking, the surface was also roughened
significantly. The background metal indicated approximately 50% chromium, 30% iron and 20% nickel;
the spikes indicated about 62% chromium, 26% iron and
12% nickel.
One steam burnoff was made at 800C of coke on an

aluminized Incoloy 800 coupon. The coke had been

deposited at 900C in 16 hr using a gas mixture containing
5% butadiene in helium. After 24 hr of steam decoking,
the surface still showed some chicken wire markings,
but dark but smooth blemishes were now visible. EDAX
analysis indicated a much higher nickel content on the
surface than in the original aluminized coupons. White
deposits of aluminum (or alumina) were still present over

Coke depositionfrom chemicals at 500-900Con solid surfaces

a portion of the surface. The pitted areas had however

almost disappeared. Of interest, a burnoff at 700C by
Albright, McConnell and Welther [ l] indicated essentially
no changes of the aluminized Incoloy 800 surface. Probably the advantages of an aluminized surface will be
retained much longer if temperatures for decoking are
700C or lower.

329

react to form first various condensation products leading

to production of fairly heavy materials such as tars.
Albright and Yu[7] have published some information on
the initial condensation products. Some tars condense
forming droplets that are suspended in tthe gas phase.
Three routes are available for the production of coke
from these heavy hydrocarbons or tars. In two methods,
the liquid droplets grow in size because of coalescnce
and further condensation of tars. Eventually these droplets impinge and collect on solid surfaces such as
pyrolysis coils or transfer line exchangers. On the hot
surfaces, dehydrogenation occurs with the production of
coke that is essentially pure carbon. When the tar droplets collect on the surface, the droplets can wet the
surface and coalesce with other droplets or the droplets
can fail to coalesce. The degrees to which these two
phenomena occur depends on several factors including
the following:
(a) The viscosity of the droplets which depends on the
temperature and the chemical composition of the liquid.
Higher molecular weight compounds tend to be more
viscous. As dehydrogenation occurs and the tar approaches coke, the viscosity also increases.
(b) The wetting ability between liquid droplets and the
solid surface; this ability depends on the composition
and roughness of the solid surface. Droplets also collect
more readily on lower temperature surfaces.
(c) The velocity of the gas stream near the droplet. In
the present investigation, slow velocities occurred
whereas in commercial units extremely high velocities
are prevalent. In the latter case, there is a greater tendency for spreading of the droplets and for shearing of
filament coke.
(d) The rate of cracking or of dehydrogenation in the
liquid or tar on the surface. At high temperatures, the
liquid tar droplets on the surface would be dehydrogenated more rapidly; hence the original shape of the

4. DISCUS!SIONOFRESULTS
Coking mechanisms have been clarified to a significant
extent for pyrolysis processes and for dehydrochlorination of 1,Zdichloroethane since acetylene, butadiene and benzene are always formed to some extent
in both processes. Figure 9 is a summary of major
mechanisms by which coke are formed. Some of the
coke is formed by catalytic reactions in which stainless
steels such as Incoloy 800 participate and are as a result
corroded. Adsorption of the precursor on the surface is
undoubtedly a first step in the coking mechanism. Details
on the production of filamentous cokes have been reported earlier by Baker et al.[2-4] and by Bernard0 et
al.[5,6]. Excellent examples of filamentous cokes are
shown in Figs. 2 and 3. Coke formed from butadiene to
yield cut-ribbon coke is another example of coke formed
by surface catalytic reactions; the lower left hand picture
of Fig. 4 shows an example of this coke. Cokes formed
by catalytic reactions are apparently the predominant
types of coke formed at lower temperatures and perhaps
especially during the early stage of a pyrolysis run when
the metal surfaces are fairly clean. Yet evidence has
been obtained that during pyrolysis of ethane some
filamentous coke containing metal particles was
produced at 800C[8] and that coke containing metal
particles promotes additional coke formation[9].
Coke can also be produced by a sequence of reactions
of which the initial reactions are in the gas phase.
Hydrocarbons such as acetylene, butadiene and benzene

C2HZ

and other

&He

and

other

acetylenes
dloleflns

Chemvx

condensatton

Wetting

of

Non-w;tt,nq

Fig. 9. Mechanism for production of coke.

Formatton
of coke I
qos phase.
then collection
on surface

330

MICHAELJ. GRAFF and LYLE F. ALBRIGHT

droplets would be retained to a greater extent. Figures 3

and 9 show examples in which globular coke retains, to a
considerable extent, the spherical shape of the droplets.
At lower temperatures, there would generally be more
time (or a greater tendency) for the droplets to wet and
spread out on the surface. This postulate explains the
results obtained with butadiene at 500-9OOC.Black mirror finishes such as noted at fairly low temperatures for
coke formed from butadiene by Yu and Albright [7] can
also be explained.
Some coke is also formed by a sequence of reactions
that occur entirely in the gas phase. Dehydrogenation
and coking reactions occur in the gas phase before liquid
droplets of any appreciable size are formed. Such coke
in sub-microscopic sizes, however, collects on solid surfaces to form initially so-called gas-phase or cotton-like
coke[l]. Filamentous coke on the surface aids in collecting both gas-phase cokes and tar droplets because of a
filtering action. Roughened surfaces also serve as collection points. Both filamentous coke and roughened SWfaces explain why more coke was noted on Incoioy 800
surfaces as ~ompated to aluminized Incoloy 800 surfaces. It also explains why the top layer of globular or
amorphous coke is rather easily removed by scraping
whereas the bottom layer is more adherent.
Gas-phase coke or tar droplets would of course contain
no metal particles. Further confirmation that the top
layer was gas-phase coke is the evidence based on
EDAX analysis that it contained no metal. The bottom
layer on Incoloy 800 coupons was, however, a mixture of
filamentous and globular cokes; this mixture of course
contains some metal particles because of the filamentous
coke. The increased diameter of globular coke formed
during longer length runs and for coupons positioned at
greater distances in the Vycor tube can be accounted for
by increased agglomeration of the tar droplets either on
the surface or in the gas phase.
Coking and decoking results of this investigation have
further demonstrated that rather severe corrosion occurs
on stainless steels such as Incoloy 800 during pyrolysis.
Relatively little quantitative or mechanistic information
can be found in the literature on decoking; clearly a need
for such information exists. Additional information is
also needed on how surface reactions depend on the

specific stainless steel used. This investigation has, for

example, further confirmed that aluminized Incoloy 800
surfaces (and also Vycor glass surfaces) result in complete or essentially complete elimination of all catalytically formed coke and in a significant reduction in surface
corrosion because of coking and decoking. It was

encouraging to learn recently that aluminum was retained

on alonized surfaces for a coil operated for over a year
in a pyrolysis furnace. No specific evidence is
yet available, however, whether the beneficial improvements obtained with aluminized surfaces are maintained
over extended periods of operation. Hopefully such tests
can be obtained in the near future since the benefits to be
obtained with improved materials of construction for
both pyrolysis coils and transfer line exchangers may be
substanti~. Of interest, metal surfaces coated with
microscopic thick layers of silica have also been found
effective in significantly reducing coke formation or
collection[lO].
Quantitative information on weight changes of coupons because of coking, decoking, and various gas
treatments will shortly be reported by the Purdue group.
These measurements will provide further information
relative to coke formation and deposition and to decoking on various metal surfaces.
Ac~ow~edgemen~~-A~~owledgement is made to the donors of
the Petrole~ Research Fund, administered by the Americas
Chemical Society, for partial support of the research. Alon
Processing, Inc. of Tarentum, PA also provided support. Dr. Carl
King of E. I. duPont DeNemours and Co., Inc. suggested the
arrangement for Fig. 9.
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1. L. F. Albrigbt, C. F. McConnell and K. Welther, Thermal

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and T. R. Eddinger), Advances in Chemistry Series, No. 183,
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_ Washington. D.C.
ii979).
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Cata~ysjsSO,36 (1973).
3. R. T. K. Baker and R. J. Waite, I. Cu~~~y~~s
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5. C. A. Bernard0 and L. S. Lobo, i. Cufa~ysi~37,267 (1975).
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M. L. Sims, The ~nhibifio~of Coke Fo~atioa in Ethylene
Steam Cracking. National Meeting of American Chemical
Society, New York (1981).