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Coke Formation Mechanisms and Coke

Inhibiting Methods in Pyrolysis Furnaces

Article in Journal of chemical engineering of Japan October 2002

DOI: 10.1252/jcej.35.923

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Journal of Chemical Engineering of Japan, Vol. 35, No. 10, pp. 923-937, 2002 Journal Review

Coke Formation Mechanisms and Coke Inhibiting Methods in

Pyrolysis Furnaces
JAFAR TOWFIGHI, MOJTABA SADRAMELI
AND ALlGHOLl NIAEI
Chemical Engineering Department, Tarbiat Modares University,
P.O. Box 14155-4838, Tehran, Iran

Keywords: Coke Formation, Coke Inhibition, Hydrocarbons Pyrolysis, Cracking Coil, Kinetics

Research has been carried out to understand the mechanisms under which coke formation occurs and
to search for solutions to reduce or eliminate coke deposition. Significant efforts bave been exerted over
the past twenty years in developing coke-inhibiting methods. Coke inhibitors, i.e., chemical additives, or
special coating of metal surfaces which suppress coke formation. Coke inhibitors/surface coating work
by passivating catalytically active metal sites through cbemical bonding interactions, and/or forming a
thin layer to physically isolate the metal sites from coke precursors in a process stream, and/or interfer
ing with those radical reactions leading to coke formation by blocking active radical sites on surfaces.
Tbis review paper investigates the effect of the most important methods such as new chemical additives,
tube material construction, pretreatment of surface on the coke formation of pyrolysis furnaces.

Introduction tial pressure of hydrocarbon, temperature, conversion,

The thermal cracking of hydrocarbons ranging
from ethane to gas oil is the most important source of
olefins and aromatics. the main feedstocks of the pet
rochemical industries. The operation is carried out in
gas fired furnaces containing e.g., 4-8 vertical coils in
paralle I and having a production capacity of the order
of 100,000-1,000.000 tons/year ethylene, The hydro
carbon is diluted with steam (e.g .. 0.3-0.4 kg steam/kg
hydrocarbon in ethane and propane cracking, 0.6-0.7
for naphtha) to minimize undesired side reactions and
preheated to around 600-650C in the convection sec
tion of the furnace.
The thermal cracking of hydrocarbons is always
accompanied by coke formation. The coke deposits on
the walls of the coil and affects the operation of py
rol:- ~i, coils with pressure drop increase, heat transfer
re!juction. hot spot and corrosion by carbonization.
These phenomena have penalties such as reduced run
length. ~electi\'ity reduction. production losses, high
maintenance cost and increased utility cost. For above
reasons the c(1ke has to be periodically removed. Ob
viously. such information is of extreme importance for
the operation. design and optimization of cracking fur
naces and further to e\aluate recently introduced anti
coking additives or special coating of the tubes. Many
factors affect coke formation such as feedstocks, par-
Received on November 13,2001 Corre,pondence concerning
this article should be addressed to J. Trm fighi IE-mail address:
Towfighi@modares.ac.ir).
reactor construction material and residence time. This
review paper investigates the mechanisms of coke for
mation and the effect of the most important coke in
hibiting methods such as chemi:cal additives, pretreat
ment of surface, tube material construction and feed
composition in pyrolysis furnaces.
1. Pyrolysis and Coke Formation
1.1 Pyrolysis kinetics
The reaction mechanism of thermal cracking of
hydrocarbons is generally accepted as free-radical
chain reactions. Ethane cracking represents the sim
plest application of the free-radical mechanism, The
reaction scheme with heavier feeds is much more com
plex than that of gaseous feedstocks, due to the fact
that hundreds of reactants (feed components) react in
parallel and some of those components are formed as
reaction products during the reaction. As conversion
and concentrations of olefins and other products in
crease, secondary reactions become more significant.
Cyclodiolefins and aromatics are produced at increased
partial pressure of olefins and diolefins, which is a
favorable condition for condensation reactions.
Many investigators have measured the product
yield in hydrocarbon pyrolysis, and detailed mecha
nistic kinetic models have been published for gaseous
feed (Murata and Saito, 1975; Sundaram and Froment,
1978; Tomlin et al., 1995), but very few detailed ki
netic models have been published for heavy feed. Dente
et al. (1979) developed a simulation program (SPYRO)
based on the fundamental free radical reaction, for the

COPFight 2002 The Society of Chemical Engineers, Japan 923


L Coke Precursor
Metal particle on
* Grain boundaries
~.~.~~.--- \
I 2-Sitc adsorption '>
I ,"i-Strrface reactions \
carbon forma:ion ..
Fig. 1 Steps of formation of filamentous coke with catalytic mechanism
pyrolysis of hydrocarbon feed. The radical reaction
mechanisms of pyrolysis of normal and branched par
affins (Murata and Saito, 1973; Dente and Ranzi, 1983;
Ranzi etal., 1983. 1997). heavy liquid feeds (Depeyre
et at., 1989: Dente et al., 2001), naphtha (100 et al.,
200 I), substituted aromatic hydrocarbons (Chen and
Froment, 1991a, 1991b) have been investigated.
Recently a complete reaction, rigorous kinetic
model, for the decomposition of the hydrocarbon feed
(ethane to naphtha) has been prepared by Towfighi and
Karimzadeh (1993) and Towfighi et al. (1993, 1998b,
2002a). This reaction network contains more than 1000
reactions for 91 species such as initiation reactions,
H -abstractions, radical additions, decomposition reac
tions, isomerization reactions, termination reactions,
and Diels-Alder cyclizations.
Many authors however, have developed molecu
lar kinetic models for pyrolysis of hydrocarbons. The
pyrolysis of ethane, propane, butane (Sundaram and
Fromen!, 1977a, 1977b; Bozga et al., 1988; Towfighi
et al., 1994b, 1998a; Owtadi and TowfighL 2000),
naphtha (Kumar and Kunzru, 1985a; Parameswaran et
al., 1988; Niaei and Towfighi, 1993; Towfighi and
Shokuhi, 1994; Towfighi et al., 1994a; Towfighi and
Sharfi, 2000; Sadrameli et al., 2000; Sadrameli and
Towfighi, 2(00), cyclohexane (Pant and Kunzru, 1997),
gas oil (Zou et al., 1993; Depeyre et al., 1989) have
been in~estigated and published.
1.2 Mechanisms of coke formation
The three mechanisms by which cokes produced
in the coil and transfer line exchanger (TLE) of a crack
ing furnace are reviewed as follows:
1.2.1 Catalytic coking mechanism Industrial
cracking coils frequently contain different weight
percentage of chromium, nickel and iron. As shown in
Fig. 1, during the startup of a furnace, the reacting gas
mixture is in contact \\lith the bare reactor walls.
Initially a hydrocarbon molecule is chemisorbed on a
metal crystallite on the surface and by a surface reaction
convert to coke. Carbon atoms thus dissolve in and
diffuse through the metal panicle. The carbon
924
o Active Sites;
Metal particle on
Metal crystalline
Metal oxides or
5-Carbon Diffusion
6-Nucleution and
accumulation in the particle causes a pressure buildup
at the dislocations and the grain boundaries, which may
exceed the tensile strength of the metal. The metal
partic Ie is then Iifted from the surface and carbon
crystallizes at the end of the particle. A growing carbon
stem thus develops which carries the crystallite at its
top. The precipitation of carbon can give rise to
structural deficiencies in the carbon lattice, thereby
creating reactive carbon centers along the filament skin.
Hydrocarbon radicals and molecules from the gas phase
are incorporated at these reactive sites, whereby lateral
growth of the filaments occurs. In this way a porous
layer of interwoven filaments is formed. Carbon
migrating over the metal surface precipitates on the
metal surface surrounding the carbon stem. Surface
carbon may thus be formed, encapsulating the metal
and preventing further growth.
The properties of the metal are very important in
this mechanism. Encapsulation of the metal particles
reduces the rate of dehydrogenation of the chemisorbed
hydrocarbon atoms. At this stage the catalytic activity
of the metal particle diminishes and both carbon for
mation and CO production slow down (Albright and
McConnel, 1979; Trimm and Turner, 1981; Baker et
al., 1982; Albright and Marek, 1988a, 1988b, 1988c;
Francoise et al., 1995).
1.2.2 Radical coking mechanism At the gas/coke
interface layer, the polyaromatics are not completely
dehydrogenated. At this surface, hydrogen abstraction
reactions by free radicals from the gas phase can oc
cur. Hydrogen, methyl, and ethyl radicals are the most
active species. As a consequence, the concentration of
the active sites at the coke surface becomes a function
of the gas phase composition. This explains that the
feedstocks generating more active radicals also yield
more coke.
As shown in Fig. 2, at the free radical positions
on the coke surface, certain gas phase molecules or
radicals (coke precursors) react via an addition mecha
nism. All unsaturated molecules from the gas phase
are potential precursors. The long aliphatic side chain
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 +
~ Beta scission
I{~'.~
~ Coke
Coke
Hydrogen abstnl.ction
. H
. "'~
0~'
~
+ H,
Coke
??
~ ~
Dehydrogenation : i H
.. + , relatively unimportant at temperatures of700C or less.
h h
The exact temperatures depend to some extent on the
Coke
Fig. 2 Steps of growth of coke hy radical coking mecha
nism
of these molecules is subjected to decomposition. The
remaining part of the molecule reacts in a few steps to
a ring structure. in which the dehydrogenation reac
tions proceed very rapidly. In this way the aromatic
structure continues to grow further and the free radi
cal site 3t the coke surface is regenerated by further
hydrogen 3bstmction.
This mech3ni~Ill explains the formation of coke
layers containing carbon atoms in spc hybridization.
The hydrogen content of such a deposit is very low, in
agreement with industrial observ3tions. The cross-link
of aromatic layers explains \\ hy samples of coke
layers from industrial coils are extremely hard and can
hardly be drilled. This mechanism is the most impor
tant one in the coke formation (Ranzi et al., 1985;
Kopinke et al., 1988. 1993a, 1993b: Reyners et al.,
1994).
1.2.3 Polyaromatic condensation This third
mechanism implies the formation of polynucle3r aro
matics in the gas phase via free radical reactions As
shown in Fig. 3. aromatics are the most important in
termediates, some aromatics are produced by
trimerization and other reactions involving acetylene.
Starting with simple aromatics. condensation and de
hydrogenation reactions occurs to produce tar drop
lets or soot particles that can be liquid or even solid at
the conditions prevailing in a thermal cracking reac
tor. Part of the droplets impinges on the tube wall. Some
rebound into the gas phase, but it is more likely that
they adhere to the surface and are incorporated in the
coke layer. since the outer surface of the droplets is
not completely dehydrogenated. Hence, hydrogen ab
qraction reactions by gas phase radicals are possible
dnd the coke layer can grow further. This mechanism
YOL. 35 NO. 10 2002
Aromatic
Precursors
CO""
1 '"
b
_ICCO~
b
I
"'L
""PNAITAR ""Coke
) CondensatIOn j
/U,
Dehydrogenates
/ 1 to form coke
Fig. 3 Growth of coke by condensation mechanism
is considered important in the cracking of liquid
feedstocks, such as heavy naphtha, atmospheric or
vacuum gas oil. Condensation mechanism is generally
hydrocarbons being pyrolyzed (Lahaye et al., 1977;
Albright and Marek, 1988c).
1.3 Modeling of coke formation
As mentioned above the formation of eoke in the
cracking coils is thought to be caused by three reac
tion mechanisms, which have been explained in the
previous paragraphs. In the following the modeling of
the coking phenomena in thermal cracking reactors is
coneentrated by many authors on the main mechanism,
which is the radical coking mechanism. In all of pub
lished papers, it is stated that, the number of reactions
can be decreased by restricting the number of coke
precursors especially unsaturates and aromatics which
are reactive and good candidate for the radical addi
tion.
Kinney and Del Bel (1954) studied the pyrolysis
of unsubstituted aromatic hydrocarbons and suggested
that coke is formed from a step arise condensation of
the aromatic rings. Similarly, Virk et al. (1974) have
reported that coke is formed from aromatic substance,
especially from benzene condense together to form
diphenyl and two molecules of this component react
to give quadraphenyJ and so on until eventually coke
is formed.
Sundaram and Froment (1979) and Sundaram et
al. (1981) studied the coke deposition in the pyrolysis
of ethane and propane. He pointed out that the coke
precursor is propylene in propane pyrolysis, and is
mainly butadiene and aromatics in ethane pyrolysis.
Ranzi et ai. (1985) have reported that coke formation
during naphtha pyrolysis involves the continuous trans
formation of polymeric material into coke through de
hydrogenation and dealkylation reactions. In this
mechanism, olefins, diolefins, aromatics, polyaromatics
and acetylinic compounds have been postulated as the
coke precursors. However, no details of the model have
been revealed. Albright and Marek (1988a) developed
a general equation and found to correlate the coking
rates as a function of run time.
925
 Kumar and Kunzru (1985b), Sahu and Kunzru 35r---------------------------------~
(1988) studied the coke deposition in naphtha pyroly 30 ---CH4
--C2H4
sis and concluded that aromatics were coke precursors. 25
--C3H6
The rate of coke formation was found to be propor -C4H6
tional to the square of the concentration in the cracked -Aromatic

product. Lou el al. (1986) and Zou et al. (1987, 1991,

1993) found different results that both ethylene and

:l:::::a~~=:j
propylene are coke precursors, and ethylene is the more
intense precursor. Froment (1990) has reported the
o w a

U D ~ D ~
coking rate was correlated with respect to the concen Reactor length Iml
tration of a number of products such as C5+ olefins,
Fig, 4 Variation of product yields along the coil
diolefins. butadiene. butene. and aromatics, through a
first order rate equation. Significant information on
mechanisms and relative rates of coking was obtained
by Zimmerman and co-workers from studies using 14 C_ 0.014 ---800 hr
labeled components (Kopinke et al . 1988, 1993a, 0.012 ........... 1700 hr
\993b). Towfighi et at. (2002b) has reported the cok :! 0.01
ing rate was correlated with respect to the concentra
tion of olefins, diolefis and aromatics, through a power
j 0,008
~ 0.006
law rale equation.
~ 0.004
Olefin Research Group of Tarbiat Modares Uni V
0.002
versity achieved the calculation of the temperature and
product distribution in thc reactor with the help of an 0

0
6 12 18 24 30 36 42
accurate rigorous kinetic model for the decomposition Reactor length (m I
of the hydrocarbon feed (Towfighi el al., 2002a). Tak
Fig. 5 Variation of coke thickness along the coil at differ
ing into account the kinetics of coke formation
ent run length
(Towfighi ef at., 2002b). along with the simultaneous
simulation of the reactor and the firebox, provides a
detailed understanding of the behavior and an accu
rate prediction of the cracking furnace run length. The 1360 r------------------------------,
-O.Ohr
coupled furnace and reactor simulation can then be 1310 -800 br
optimized in order to obtain a favorable product dis 1260
tribution or to reduce unwanted side effects. such as ~
-;; 1110
fouling of the heat transfer surfaces by coke deposi S
tion. The test results of simulation in a sample indus i lIoO
trial naphtha cracking furnace as shown in Figs. 4-6, E
~ 1110
which is in good agreement with the industrial data.
The formation of coke in TLX is thought to be IMO~------__--------------------____J
o 10 20 30 40
occured by only two mechanisms. The first consists of Reactor length Iml
surface catalyzed reactions, and the second is the po Fig. 6 Variation of tube skin temperature along the coil at
lymerization of the pyrolysis products through unde different run length
sirable secondary reactions (Lahaye et al., 1977;
Sadrameli and Sharifnia, 1996). In contrast to the for
matitln of coke in cracking coils, only little is known
about the details of the formation of carbon rich prod catalyzed polymerization (Ranzi et al., 1985) or de
ucts which are deposited in the TLE tubes at tempera composition of unsaturated hydrocarbons at the inner
tures between about 350 and 600C. Events taken into surface of the TLE tubes followed by the thermal de
account are a mechanical transfer of coke like parti hydrogenation of the resultant polymers.
cles from the reactor coils into the TLE, a physical
condensation of the high boiling point cracked prod 2. Coke Reduction Techniques
ucts at the TLE walls (Kopinke ef al., 1993c; Batch et
al., 1995; Sadrameli el al .. 1999. 200l), a chemical In this review the effect of several techniques for
condensation of unsaturated cracked products from the reduction of cokc formation is investigated. For in
gas phase to droplets at temperatures above 350C, a stance, the effect of the most important new chemical
chemical interaction between the deposited products additives. alteration of the coil surfaces and the com
and reactive gas phase species, and even a metal position of feed on the coke formation in pyrolysis
furnaces is investigated.

926 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN


2.1 Coke reduction by addition of inhibitors
2.1.1 Thiochemical compounds In commercial
steam cracking of hydrocarbons, sulfur components are
added to the feed. Naphtha or heavier feed fractions
contain sulfur. This reduces the CO yield in the outlet
stream of the furnace. which is often interpreted as an
indication of a reduced coking rate. It is also reported
that in the absence of sulfur containing additive in the
feed. the pressure drop rapidly increase with time. A
number of bench scale and pilot plant experiments with
1100
sulfur containing additives have been reported. In some
reports, it is claimed that coking in the cracking coil
can be controlled by the addition of sulfur containing
additives (Bajus ef al., 1981, 1983; Depeyre et al.,
1985; Koltz, 1986). Godar and Corneli (1978) sug
gested a process of inhibiting fouling at elevated tem
perature by adding organo-sulfur compounds. In addi
tion, Callejas and Greenwood (1995) explained a
method of treating ethylene furnaces with hydrogen
sulfides under steam-containing environment to reduce
CO and/or coke formation. Herrebout and Grootjans
(2000) also disclosed process of inhibiting of coking
by adding thiohydrocarbons where the sulfur is part of
aromatic hetrocycles. preferably thiophene and/or
benzothiophene.
Bajus ct al. (1981) studied the effect of adding
thiophene to a reformer raffinate feed and reported that
the coke formation reduction was observed. Also the
effect of sulfur content in the feed was studied by add
ing thiophene to the naphtha. The rate of coke forma
tion decreased with an increase in the sulfur content of
the feed. Experimental results show that below 0.4 wt%
thiophene, the asymptotic coking rate was inversely
proportional to the thiophene content of naphtha
whereas at higher thiophene concentrations the inhibi
tion in the coking rate was less (Sahu and Kunzru,
1988).
The sulfur addition to the feed can reduce the rate
of coking in two ways. Firstly it reacts with the metal
surface to form metal sulfides, thus passivating the
reactor wall or it can take part in the homogeneous gas
phase free radical reactions. The effect of sulfur in
pas~ivaing the metal wall is well known through the
following reaction (Bajus et al., 1981; Towfighi and
Niaei, 2000).
S' + metal ~ metal sulfide
Bajus et al. (1983) found that. during n-heptane
pyrolysis, the addition of dibenzyl sulfide or dibenzyl
disulfide decreases the rate of coking. Also they ob
tained that the addition of butanthiol and carbon
disulfide decreases the coking rate during reformer
raffinate pyrolysis. In the same concentration of two
thiochemical, the carbon disulfide is more effective
than butanthiol on reduction of coke formation.
Dcpeyre et al. ( 1985) reported that addition of (C2Hs)2S
VOL. 35 NO. 102002
100
90
80 (
~ 70
60
"
~
SO
~
"
e 40
Q
i! 30
Q
20
10
0
300 500 700 900
Temperature I'q
Fig. 7 Percentage of decomposition of thiochemical com
pounds
and (CH')2S0 compounds to n-nonane steam cracking
catalyzed the rate of n-nonane decomposition and in
hibited secondary reactions leading to the formation
of C 4Ho and aromatic compounds.
The use of steam as a dilluent gives a rise to the
formation of CO. CO is not observed when nitrogen is
used as a dilluent (Pramanik and Kunzru, \985). Two
processes are important in describing this: the metal
catalyzed removal of carbonaceous intermediates and
coke by steam reforming processes and the slower
noncatalytic gasification of coke by steam.
Preoxidation of the surface increases the selectivity
toward CO formation and thiochemical compounds are
very effective on reduction of CO yield in industrial
cracker (Francoise cr al., 1995).
Figure 7 illustrates the relationship between tem
perature and decomposition of some common sulfur
compounds. A comparison of the physical properties
of various sulfur compounds is given in Table 1.
Dimethyldisulfide (DMDS) completely decomposes at
400-500C, even before entering the cracking coil,
since the temperature in the preheat section reaches
600C. Some other sulfur compounds are more stable
and require higher energy level to decompose.
Benzothiophene remains unchanged until 675C. Thi
ophene is a more stable molecule and decomposes
above 800C. For a given concentration of sulfur in
the feed the asymptotic coking rate decreases in the
following order:
Dimethyl disulfide> Ethylmercaptane > Dimethyl
sulfide> Carbon disulfide> Benzothiophene > Thi
ophene
For a given sulfur concentration in the feed, the
amount of sulfur fed per surface unit differs consider
ably for the various units. For ethane, propane and
butane cracking conditions typically used in industrial
practice, addition of 100-200 ppm-S as DMDS corre
sponds to 480-968 mg-S/m 2 while for the pilot unit
this value amounts to 47.85 mg-S/m2. When spiking
927
 Table 1 Physical properties of common presulfiding (thiochemical) compounds

Properties DMDS DMS NR\1 EM CS 2 DES MM H2S

Molecular weight 94.2 62.1 90.2 62.1 76 90 47 34
Boiling point 109.6 37 98 35 48 92 8 0
'7c Sulfur 68 52 36 52 54 36 67 94
J:'Xnsity 1.063 0.843 0.83 0.83
Sulfur content [gill 720 440 300 430 1058 301 58! 855
Vap. pressure 29.3 505 48 535 3&7 58 1530 18000
[mbar at 20"C1
Viscosity 0.62 0.28 0.5 0.23
(cpoise 20"C)
Tot'decomposition 400 450 425 400
[OCl
Tofdecomposition 520 650 650 565
(IOO'k)

DMDS: dimethyl disulfide: DMS: dimethyl sulfide: DES: diethyl disulfide: MM: methyl mercaptane:
EM: ethyl mercnptane; NBM: normal butyl mereaptane; CS2: carbon disulfide

naphtha feed, its sulfur content is used as a guide.
Reeently contradictorial results were reported on
the effect of sulfur containing additives on the coking
rate. Froment (1990) claimed that the CO yield is not
a reliable indicator for the coke formation. Velenyi et
al. (1991) reported an increase of the coking rate on
Inconel 600 in pyrolysis of ethane with hydrogen
sulfide in the feed. Francoise er al. (1995) observed
that addition of carbon disulfide results in an impor
tant reduction of the CO yield. both in the initial and
the asymptotic range. Sulfur compounds from the gas
phase are more readily chemisorbed on the metal par
ticles than water and hydrocarbon molecules. Cover
age of metal sites by sulfur then leads to a lower con
centration of active oxygen atoms at the surface and
hence to a lower catalytic CO production. When S, and
S, are empty sites on the surface of metal catalyst
(cracking coil surfaces contain with high weight per
cent ofNi and Fe) and the carrier respectively, the fol
lowing sequence can be formulated for the adsorption
of steam and formation of active oxygen atom (S,-O):
- + S,- = S,-H,O
H,O --
Where C"H", (hydrocarbon) is considered for steam
reforming (Rostrup-Nielsen, 1973; Wagner and
Froment, 1992). Sulfur compounds can alter the rate
of radical reactions through their interference with
hydrogen transfer and with termination reactions.
2.1.2 Phosphorous compounds Phosphorous
containing additives have been shown to be effective
in inhibiting coking rates. Naberezhnova et al. (1983)
reported that the organophosphorous compounds were
very effective in controlling the coke formation dur
ing pyrolysis of liquid hydrocarbons without affecting
the product yields. Boone (1983) of Nulco Company
reported the development of proprietary products con
taining phosphorous with or without sulfur which were
effective in reducing the coking rate during
hydrocarbon pyrolysis. The additive provided a film
to passivate the metal surface to prevent it from
catalyzing the coke formation. The increase in run
length varies from 50% to 223%. Moreover, the steam
air decoking time decreased by 5-10Ck and cleaning
of exchangers was easier because of softer coke
(Towfighi er al., 1999).
The effect of the addition of triethylphosphite
(TEP) on the rate of coke formation was investigated.
The reduction in the rate of coke formation was ini
tially higher and then gradually decreased such that, at
high concentrations of phosphous, the coking rate ap
proached a constant value (Ghosh and Kunzru, 1988).
Such a trend of coking rate with run time is well estab
lished in references (Kumar and Kunzru, 1985b;
Francoise et al., 1995). As can be seen from these re
sults, coking rates were significantly reduced in the
presence of triethylphosphite. This reduction in the
coking rate is comparable to the limited data reported
by Boone (1983). The results discussed above show
that the phosphorous neither takes part in the homoge-

928 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 neous reactions nor catalyses the coke-steam reaction.
This seems to be correct phosphorus-containing addi
tives passivate the metal surface.
Vaish and Kunzru (1989) reported the effect of
triphenylphosphite (TPP) addition on the rate of coke
formation. Coking rates were significantly reduced in
the presence of triphenylphosphite. Comparison of
the results of the effect ofTEP and TPP on the coking
rate for the same naphtha and for the same phospho
rous concentration in the feed shows that,
triphenylphosphite is a more effective coke inhibitor
than triethyl phosphite. The possible reason can be
postulated that. the metal-phosphorous complex is
more stable with triphenylphosphite or a larger metal
surface is occupied with each molecule of
triphenylphosphite.
Also they reported that the phosphorous com
pound affects the rate of decomposition of coke. From
experimental data. it can be seen that. there was no
significant decomposition of coke below 700 K. For
the coke obtained from phosphorus-containing naph
tha. coke removal started at a temperature of 700 K,
and decomposition of coke was completed in 12 min.
On the other hand for the coke obtained from phos
phorus-free naphtha. coke removal started at 738 K,
and decomposition of coke was eompleted in 16 min.
This indicates that the coke obtained from phospho
rus-containing naphtha is more reactive. A possible
reason for this could be that phosphorus compounds
catalyze the carbon oxidation reactions.
Oas et al. (1992) investigated that the presence of
benzyl diethyl phosphite (BOP) and triphenyl phos
phine sulfide (TPPS) in the naphtha feed, significantly
reduce the rate of coke formation. For instance, with
naphtha containing 200 ppm of phosphorous (as BOP).
the asymptotic coking rate. is reduced by 87.7%. Ad
dition of either BOP or TPPS had no significant effect
on the hydrocarbon gaseous product yields. Since the
product distribution is not affected, the additive only
influences the heterogeneous coke forming reactions.
~1(Jst probably, BOP and TPPS passivate the metal sur
fac"e by decomposing into the free radicals which com
bine \\ ith the surface. At high temperatures, BOP can
be decomposed in three ways of reactions as follows:
(ChH,CK)PO(OC,H),
--; C,H,CH; + (C,H,O),P'O (I)
(C~H5CK)P0(OC,H,).
--; (C!)f,CH"P'O(OC}l,) + 'OC,H, (2)
(C(,HSCH,)PO(OC,H,).
--; (C 6H,CH,)POO'(OC,H,) + C 2H,' (3)
The phosphorous-containing free radicals can be
combined with the metal surface to form a passivating
film. A possible reason for BOP's being more effective
YOL. 35 NO. 10 2002
0.1 r--------------
--TEP
---TPP
---BDP
-+--TPPS
o zoo 400 600 800 1000
Phosphorous Content or F..,d (ppml
Fig. 8 Effect of phosphorous content of feed on coking
rate
coke inhibitor than TPP could be that the metal-phos
phorous complex is more stable with BOP or larger
metal surface area is occupied by each molecule of the
complex. In addition in the decomposition of each
molecule of TPPS, two radicals, Le. C 6 H s S' and
(C6H,)JP' which can passivate the metal walls are
form'ed, whereas in the case of BOP only one
passivating radical is formed per molecule dissociated.
At the same phosphorous concentration, TPPS was
found to be more effective than BOP in reducing the
rate of coke formation. Also EOAX analysis of the coke
surface showed that the addition of organophosphorous
compounds significantly reduced the concentration of
metals, such as iron, nickel, and chromium, incorpo
rated in the coke. It is concluded from these results
that the organophosphorous compounds inhibit the
coking rate by passivating the surface (Chowdhury and
Kunzru, 1993; Kumar, 1999). As shown in Fig. 8, in
the same concentration of various phosphorous com
pounds, TPPS is a more effective coke inhibitor than
others and the asymptotic coking rate decreases in the
order of:
TPPS > BOP> TPP > TEP
Reed (1995) of Phillips Petroleum Company has
reported that a new coke inhibitor named Phillips
antifoulant (phosphorous based compound) is effective
for reduction of the coking rate. Experimental data
clearly show that the antifoulant run reached the time
limit with no increase in pressure drop because the
coking rate was very low in both the coil and TLE and
stable cracking temperature had been reached. Also
Tong (1995), Tong et al. (1998) and Tong and
Poindexter (1998) of Nalco/Exxon Company reported
that a phosphorous-based coke inhibition treatment
method named as "COKELESS" has been developed
in the laboratory. The application of the COKELESS
program on both liquid and gas industrial crackers, has
shown very promising results. Lower tube metal
temperature, higher throughputs and higher severity at
929
the same coil outlet temperature has been observed.
Likewise, the following patents disclose phospho
rous compounds for inhibiting the formation of coke
in the pyrolysis furnaces. Weinland (1978) suggested
that phosphate and phosphite mono and di-esters in
small amounts, act as antifoulant additives in ethylene
furnaces. Certain phosphite esters, phosphate esters and
thiophosphate esters are disclosed by Kaplan and
Lindley (1985), Kaplan and Kisalus ( 1989) as being
effective for reducing fouling in ethylene furnaces.
Porter and Reed (1985) have reported a method of in
hibiting coke formation in ethylene furnaces by treat
ing the furnaces with a combination of tin- and phos
phorous-containing compounds, or antimony- and
phosphorous-containing compounds, or tin-antimony
and phosphorous-containing compounds. Kisalus
(1989) has presented a method of reducing fouling in
ethylene furnaces by using triphenylphosphine.
Phosphorothioates, phosphorictriamides, phosphonate,
thiophosphonate (Tong and Poindexter, 1994a, 1994b,
1998) and dithiophosohoric acid ester (Taylor et al.,
1995) are suggested as coke inhibitors in ethylene fur
naces. An improved method for the inhibition of coke
formation in pyrolysis furnaces is investigated by Tong
and Poindexter (1999), using a combination of sulfur
and phosphorous-containing compounds having an
atomic ratio of sulfur to phosphorous of at least 5.
2.1.3 Alkali metals and other inorganic compounds
It is now well established that the oxidation
fication) of coke can be catalyzed by certain metals
and inorganic compounds. Bennett and Price (l982)
reported that contamination of the coked surface with
Na, K. Li, Rb, Cs carbonates or oxides. Ba and Sr ox
ides enhance gasification of coke. Experimental data
shows that alkali metal salts affect the gasification of
deposited coke in order of:
K > Na > Rb > Cs > Li
Their experimental data showed that above ele
ments catalyze the oxidation rate markedly, by factors
up to l35. All the alkali metal ox ides or carbonates
were aCjive. The alkaline earth oxides also enhanced
oxidation, although to a smaller extent than the alkali
metal carbonates or oxides. Again the effectiveness of
these contaminants decreases with burning off. but even
after 50% gasification it enhances the oxidation rate
by a factor between 2 and 4.
It was found that coke formation was significantly
reduced in pyrolysis of n-hexane (Bahadur et al., 1987),
naphtha (Mandal and Kunzru, 1986) in the presence
of K,COj The most active materials are K 2C0 3 ,
Na 2C0 3, K,O, Na,O and Na,S04' Sodium and
potassium carbonate can enhance decoking rates by
factorsof8and 16 respectively. Narayanaetal. (1999)
found that by using a mixture of 75 ppm ofpottassium
and 50 ppm of antimony, coke yield is reduced by 96%
930
in the pyrolysis of ethane. In addition Babash and
Mukhina (1999) have reported that the use of water
soluble combinations of chemicals, magnesium or
calcium acetate, potassium carbonate and phosphorous!
sulfates as an inhibitor, was introduced at the Russian
ethylene plant and has been applied successfully for
two years. These are effective catalysts in the following
basic coke-steam conversion reactions:
CO 2 + C ~ 2CO
The inhibitor solution is introduced into the
feedstock flow in the transition zone from the convec
tion to the radiant section of the furnace '::011. where
feedstock temperature is 600-650C.
The following benefits have been re.;orded:
Increase in furnace operational runl1mg lime.
Decrease in the carbonization of COllis and increase
in the life span.
Reduction in time span of decoking l~perations.
Elimination of the risk of tube's burnout from
steam air decoking by its replacement \\ Hn endothermic
steam purging in the presence of coke gasification
catalysts.
Decrease of coil damage derived fr,-~:n 10\\ er wall
temperatures and reduction of cyclic theml.3l loads as
sociated with lower frequency of decokmg operations.
Reduction in utility costs of .2.-+ per.:ent.
In other research work Chan el at. 199& I reported
the effect of H 2PtCl o additives in v. ater. on coke for
mation in the steam cracking of ethane and propane.
This was accomplished by comparing the amounts and
rates of coke production on quartz and Incoloy sur
faces in both the absence and presence of the additives.
What is important, however is the significant and con
sistent reduction in coke formation in the presence of
the additive in the feed stream. For example, at 830C,
the coke formation rate decreases from a high value of
0.34 mg/cm 2min in the absence of the additive to a
low value of 0.089 mg!cm~min, representing a factor
of 3.8 decrease in coke formation in the presence of
the additive.
2.2 Alteration of the reactor surface chemistry
Different pretreating methods are investigated to
suppress coke formation. Holman et al. (1982) studied
the effect of the surface pretreatment and showed the
preoxidation resulted in much higher coke formation
compared with the prereduction of the surface. It can
be seen that all of methods form a passive layers on
the metal oxides have the function of inhibiting coke
formation. In this way, the catalytic action of the metal
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
surface decreases or even disappears completely
(Marek and Albright, 1982b). Experimental data from
different pretreated methods show that the catalyzing
intensity to coke deposition can be concluded in the
order of (Zou et al.. 1987): Oxidized Ni > Ni > oxi
dized SS > SS > SS treated with hydrogen> SS treated
with diluted hydrochloric acid >SS treated with hy
drogen sulfide> SS trealed with diluted sulfuric acid
> quartz.
Different pretreating methods result in different
duration time of passivating function in coking/decok
ing operations. The more durable protective layer, the
more lasting passivating function and rice versa. It was
found that the different reactor surface activities, not
only influences the surface reaction and coke
deposition but also has remarkable effects on the gas
phase product distribution. The experimental data
(Marek and Albright 1982b) indicates that the greater
the activity of the reactor surface, the lower the yields
of ethylene and propylene and the higher the hydro
gen yield accordingly. It indicates that the active reac
tor surface enhances ethylene and propylene to form
more coke by dehydrogenation and condensation re
actions.
Another research work also shows that, surface
morphology changes significantly after chemical pre
treatment (Holmen et al., 1982). Pictures taken with
the scanning electron microscope (SEM) before and
after the treatments of Incoloy800 with hydrogen
sulfide. helium. 6mlt steam in hel ium, or oxygen show
that the various portions of a metal surface were
changed to different extents. The relative effect of these
treatments on morphology was in the following order:
Changes in the morphology during helium treat
ment are believed to be caused by high temperature.
SEM pictures show an Incoloy 800 surface after helium
treatment slightly rougher than the untreated 1ncoloy
800 surface. He! ium treatment of pol ished Incoloy 800
resulted in grains of metal outlined by a network of
ch~mnel.
Following approaches have been taken or are be
ing considered by industry:
Pre-sulfiding is done by some operators when
starting up a new coil and in some cases after each
decoking operation, A typical procedure uses 175-200
ppm DMDS, DMS or hydrogen sulfide on steam-only
for 4 to 6 hrs at 680C prior to feed in. The sulfur com
pound is then reduced to 75-100 ppm on feed after
feed in and continued at this level during the full run
length. The effectiveness is measured by monitoring
CO content before the methenator.
Pre-oxidation is useful in preparing a new coil for
\)peration. It involves heating the radiant coil to 760
~88;:lC while on steams only and holding for about 10
VOL 35 NO. 102002
hrs. The temperature is then increased to about 930
960C and held, on steam only, for another 10 hrs.
These steps form a stable and adherent Cr20 3 surfaces
film.
2.3 Tube materials of the reactors
2.3.1 Effect of tube material The effect of con
struction material on the coking rate was investigated
for many of metal alloys and quartz tubes. As men
tioned in Section 1.2, catalytic coking occurs on clean
tubing surfaces with high weight percentage ofNi and
Fe that catalyze dehydrogenation of hydrocarbons at
elevated temperature. It has been experimentally
observed that the rates of coke deposition were initially
high and gradually decreased to a constant asymptotic
value with progress of the reaction. The high initial
rates are due to the catalytic effect of the metal surface
on the coke forming reactions and as the eoke layer
builds up, the catalytic activity is progressively
reduced. Similar trends for the coking rate has been
reported on the all of metal alloys in pyrolysis of
hydrocarbons (Trimm and Turner, 1981; Kumar and
Kunzru, 1985b; Francoise et al.. 1995). Surface
reactions are in general much less important in quartz
reactors. It has been experimentally observed that metal
particles migrate from the reactor walls to the top of
the growing carbon chain, which would explain the
effect of material of construction on the asymptotic
coking rate (Brown and Albright, 1976).
Using an SEM equipped with EDAX to analyze
for metals shows that coke formed on alloy surfaces
often contains highly dispersed metal particles of
nickel, chromium, and especially iron. These metal
particles had apparently been extracted from the alloy
surfaces. This mechanism explains the simultaneous
formation of metal-catalyzed filamentous coke and
corrosion, perhaps along with erosion, of the metal
surface (Albright and Yu, 1979; Albright and McGill,
1987; Graff and Albright, 1982; Marek and Albright,
1982a).
As steam-cracking processes first became com
mercial in the early 1950s, they were small capacity
units, using 304 stainless steel (SS) tubing. As operat
ing units became larger and coil outlet temperature
reached 720-820C, 310 SS and Incoloy 800 were in
troduced. To get high heat fl ux in short-residence-time
heaters and minimize tube metal temperature, smaller
diameter cracking tubes were adopted. Now stronger,
cast materials with high Si HK-40 alloy, the modified
HP-45 alloys and several specialty, modified higher
Ni alloys are used. Figure 9 shows the basic groups of
thermal cracking coils alloys. Key considerations in
selecting appropriate metallurgy for pyrolysis furnaces
are:
Oxidation
Carburization
Creep strength
High temperature ductility
Cost.
931
 1950-1955
1955-1960
1960-1965
1965-1975
1975-1990
1990-Today
Fig. 9 Basic groups of thermal cracking furnace alloys
Unfortunately, there is no simple assessment of
properties that ensures max imum cost effectiveness for
the lifetime of a cracking coil. The properties of the
reactor surface affect the rate of coke formation. This
is because the physical and chemical properties of the
reactor surface will influence the radical and surface
reactions in pyrolysis of hydrocarbons. The formation
of a stable, compact, protective oxide film is needed
to minimize oxidation and carburization of coils. To
proviJle adequate oxidation resistance, a minimum of
2S% Cr is desirable. Higher Cr imparts a more stable
oxide film, but introduces instability in the alloy struc
ture. Cr. Ni and Si are effective barriers to carburiza
tion. High weight percentage are beneficial and provide
a protective and regenerative oxide film. Oxides of
silicon, chromium, aluminum, manganese, and others
formed stable, compact and protective film and reduce
catalytic coke by reducing the carbon diffusion rate or
solubility (Parks and Schillmoller. 1996; Wysiekierski
et al., 1999). The order of the stability of these oxides
are as below:
Alp, > TiO > TiO~ > Si(\ > Crp3 > SiO > Mnp1 >
Mn 3 0 4 > FeO > FecO) > NiO > Cr01
932
These oxides thermally stable in high temperature,
i.e. Crp3' SiO" and Alp) up IOS0, 1100, 11S0C re
spectively. Today the best industrial operating results
and maximum effectiveness were fouild by use of Al
loy 28/48 Wand Alloy 3S/4S. The presence of W im
proves carburization resistance; W plus Nb is better
than W alone. Synergistic additions of W, Nb, Ti and
Zr greatly improve carburization resistance (Parks and
Schillmoller, 1996).
2.3.2 Effect of polishing By polishing alloy sur
face, there is a change in emmitance of the surface in
heat transfer by radiation. The emittance, which influ
ence radiation and therefore the temperature of the re
actor surface, may vary from below 0.1 for a polished
surface up to 0.9 for a plain or a carbonized surface.
Highly polished surface, with low emittances, oper
ates as much as SO-100C below that of unpolished
surface (Albright and McGill, 1986). Accordingly, re
duction of metal surface temperature significantly re
duces the carbon formation for no other reason than
the slower chemical reaction rate and phase changes
in solution equilibria that occur at these lower tem
peratures. Also the rate of carburization of alloys de
crease by a factor of O.S for every 40C tube metal
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

temperature decrease (Albright et ai., 1979; Baker et
al., 1982).
Temperature alone is not sufficient to explain the
difference observed. Mechanically polishing a surface
will result in a reduction of the general roughness or
number of disorders that have resulted from manufac
turing (Marek and Albright, 1982b: Brown and Hill,
1982). This was demonstrated in laboratory scale study
by a marked reduction in the surface roughness from
71 rms for the unpolished surface to 6 rms for the
polished. Furthermore, if acti ve metal particles already
exist on the surface, they will be removed or reduced
in size and number by polishing. Indeed experimental
data showed that significant reduction in coke
deposited during pyrolysis of various feedstocks. The
ratio of coke formed on the unpolished surface to that
formed on the polished varied from 5.6 for isobutane
up to 28.1 for ethane (Crynes and Crynes, 1987).
One other consideration, polishing, is a change in
chemistry of the surface, which is exposed, to the re
acting gas. Not only the reaction chemistry but also
the phase behavior relating to carbon solution at the
surface will change hy polishing. In reviewing other
studies, polishing metah of different chemical com
positions usually results in rates of carbon formation
similar to that of quart!, v. hich is generally considered
most inert. With lower ~urface temperature (radiation
effects), less mechanical surface defects, and possibly
a change in che111i~try, Ie~, carbon and an inactive car
bon is created under the new conditions, and this pre
venh or greatly reduce, filamentous carbon formation.
Therefore, with reduced filamentous carhon, the ac
tive metal particles canl10t continue to be generated
and/or be exposed to further catalyze carhon forma
tion.
2.3.3 Effect of alonization of surface Albright
and Yu (1979) investigated the effect of alonization on
coke formation phenomena. They ohtained valuable in
formation by com pari ng the morphologies of coke
formed on stainless steels by using a scanning elec
tron microscope (SEM) equipped with EDAX, from
different coke precursors in a pilot scale system. Par
tiCularly noteworthy is the finding that for aluminized
(alonized) Incoloy 800 surfaces filamentous coke was
not ohserved and iron, nickeL and chromium were not
detected in the coke (Albright et ai., 1979; Albright
and Yu, 1979: Graff and Alhright, 1982; Marek and
Albright. 1982a; Albright and McGill, 1987).
Results from industrial installations of alonized
furnace coil composed of Incoloy 802 tubing and non
alonized Incoloy 802 in a Gulf Canada Ltd. ethylene
furnace, indicated that the al uminum rich layer remains
on allonized surface after 3 112 years and following
results were observed (Albright and McGilL 1987):
The alonized tube had not any loss of metal from
the surface during the 3 112 years.
The roughness of the inner surface of the alonized
VOL. 3S NO. 102002
12
N
~
..
e
...
10
~" 8
'sc.. 6
~
.
.:<
0 4
...U
0
2
"e=
0
..: 0
Ni HP HK Alonized HP
Fig. 10 Amount of coke deposition on various substrates
tube did not change.
Based on ED AX analyses, the aluminum content
was in the range of 42 to 87 wt%.
The presence of high percentages of Cr, AI, Nb
and Si in the alonized surface.
The alonized tube has not shown any carburiza
tion and intergranular increase of carbon.
The non alonized coil by contrast had lost approxi
mately 20% of its wall thickness especially on the in
ner surface, because of carburization and subsequent
metal dusting.
The non-alonized tube is heavily carburized on
the surface.
The increase of carbon along grain boundaries
beneath the surface of non-alonized tube.
In other industrial experience, has investigated the
effect of surface alonization on HP coils and similar
result is obtained for alonized HP surface. Results of
laboratory work in the pyrolysis system of ethane
(Albright and McGill, 1987) on HP substrate are shown
in Fig. 10, and ethylene pyrolysis (Marek and Albright,
1982a) on Incolloy 800 substrate, have indicated the
reduction in weight of coke by a factor of 6-7. The
fact that alonized coils operate at lower temperatures
than non-alonized coil is likely caused by at least two
factors. First, less coke is formed on the alonized
surfaces. Second, the thermal conductivity of the coke
on the alonized surfaces is greater.
2.3.4 Effect of silica coating Brown et ai. (1982)
found that silica coating process reduced the rate of
coke formation in pyrolysis coils. Silica coating is pro
duced on alloy steel substrates by the decomposition
of an alkoxysilane in a carrier gas. Briefly, an
alkoxysilane (e.g. tetra etheyl orthosilicate) is injected
(I % by weight) into a preheated stearn flow, which
passes into the coating vessel where steel substrates
are radiantly heated to 600-850C. Silica films, largely
amorphous in character, have been deposited with a
wide range of thickness, as thin as 1 micron or less.
Metallurgical examination of silica coated alloys
showed no deleterious action on the bulk alloy. Indeed
silica coating has been found to protect the alloy sur
face from oxidative attack in high temperature steam
933
 jng and cracking operations. Thi, Jh\) reouces degra
dation of the alloy by pre\ enllng carburization
(Wysiekierski et at., 1999).
Coke deposition measuremenh were made on both
uncoated and coateo tuhe,. \In HK40, Incoloy 800.
niekel foil, quartz v. ilh I;' pkJI industrial feedstocks in
a laboratory scale i Bnl\\ n ef al., 1982). Hence the
results showeo the coking rate on HK40 was four tt,
six times higher than that on silica coated HK-tli .;I:
830C and the similar results was obtained frtm, ,tte:
alloys. From these tests it became C]e,H thJ: unJe,
certain conditions of temperature, stcc;f1) [.(Ill .;InJ n,)\\
rate, coke formation catalyzeo b~ the I!'d,ll su~strJ:e
and silica coating would conslderJh;.\ redu.:e :he rdte
of coking. Also at 850C, up t\) J t ,l":I,lr ttt In redu.:ti\ln
in coking rate was obtained b~ sillc'dl.'(latin,: \'n Incl)loy
800, above 900C the c'ilJting \\ as less dfi,lent. The
effect of the decoking operallon on c"ke tc1rmation in
subsequent cracking runs \\ as als" studied It i<; shown
that, after many times of steam/air dec'llkIng cycle, no
deleterious action upon the silica c('.(ling.
2.4 Effect of feed composition
It is v.ell known that the nature of the feedstock
affects the coke formation. After 60-80 days of opera
tion, a naphtha cracker v. ill often need to be sh ut down,
due to excessive tube metal temperatures. Ethane fur
naces on the other hand exhibit much longer run lengths
and usually are shut oown for high-pressure drop or
other operational reasons. Pyrotec Company has inves
tigated the nature of the coke deposits in the radiant
coils and found significant differences between the
coke, is deposited by naphtha and that is deposited by
the ethane and lighter LPG. The comparison of crack
ing rate of straight run naphtha and ethane feed stock
in a conventional vertical tube furnace ~howed that the
external tube wall temperature profile of naphtha fur
naces rises much sharper than ethane furnaces (Ranzi
et al., 1985).
Thermal conductivity of the coke oeposited by
naphtha and gas oils is in the range of 3-5 kcallmhrC,
This coke is amorphous and is often soft to the touch.
Coke deposited by ethane or LPG has thermal
conductivity values 2-3 times higher, giving values in
the range 10f 10-12 kcal/mhroC. This coke has a
regular structure and is therefore much harder than
naphtha coke. This difference in thermal eonductivity
is reflected in the tube metal temperature profiles. The
tube metal temperatures of naphtha furnaces rise much
faster due to the increased resistance from the coke
layer. Ethane coke offering less resistance leads to a
smaller increase in tube metal temperature, for the same
coke thickness.
The rate of coke formation depends on the char
acteristics of feedstock defined by its structure, mo
lecular weight, PIONA analysis and sulfur content.
Coke formation in diolefin pyrolysis is more intensive
than its formation in olefins processing which in turn
934
Table 2 Tile re~alive rates of coking as feed composition
Feed Relative coking rate Relative coking rate
in cracking coils inTLE
PaITJ.~:n' 0.2-0.8 0.14-0.5
Olel~::" 0.73-1.03 0.35-0.8
Bu:;:zruene 1.68 1.35
A,:~,~ ;ene >5 3.0
:\a.ph:elle, 1.2 1.45
Aromatics 1.5 0.33
Put} aromatics 12-30
is more inlensi ve than its formation in paraffin hydro
carbon decomposition. In 1,3-butadiene pyrolysis coke
is formed five to six times faster than that of ethylene.
The rate of coke formation is increasing in going from
paraffin to naphthalene and from naphthalene to aro
matic hydrocarbons. Aromaties include the important
class of eoke precursors. The aromatic ring structure
is close to the structure of the coke matrix. Further
(branched) aromatics are reactive components, espe
cially at the high temperature prevailing in the ther
mal cracking coils. Table 2 shows the relative rates of
coking as feed composition in cracking coils and TLE
(Ranzi et al., 1985; Kopinke et at., 1993a, 1993b;
Babash and Mukhina, 1999).
Based on the experimental data on pyrolysis of
hydrocarbons, tendency of various compounds to form
coke in pyrolysis furnaces increases in the following
series:
Methane < ethane < ethylene < propylene < benzene
< ethylbenzene, xylene < styrene < alkenes C4 <
cyclopentadiene < methyl naphthalene < antheracene
< methyl antheracene < acetylene.
When feedstock molecular weight increases, the
rate of coke formation also increases. In atmospheric
gas oil pyrolysis the coking rate is two to four times
higher than the coking rate in the naphtha cracking
under the same conditions.
Conclusion
The formation of coke in cracking coils mainly is
thought to be caused by catalytic coking and heteroge
neous noneatalyitic mechanisms or radical coking.
Catalytic coking can be controlled by alloy selection,
such as high Cr-high Si alloys or by surface treatments
with AI, Cr, Si or coatings. Radical coking can be con
trolled by adding crackable sulfur to feed, by increas
ing the steam/hydroearbon ratio and adding other an
tifouling additives. Literature survey shows that addi
tive passivate the both catalytic and asymptotic cok
ing mechanisms in three ways. The additive may be
preferentially adsorbed on the surface and retard the
adsorption of coke preeursors, tar droplets, or soot
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
particle. In addition, the additive may chemically in
terfere with the surface reaction processes, thus pre
venting the buildup of coke. Third the additi ve may
promote the surface gasification of coke and/or pre
cursors.
Many approaches have been taken or are being
considered by industry. They are based on reduced coke
production in the coils and on increased rates of coke
removal, or removal of coke precursors, during pyroly
sis. They include:
Adding crackable sulfur or DMDS, DMS, H 2S to
the feed stock.
Using anti-fouling liquids based on
organophosphoro compounds,
Catalytic gasification of coke to form CO and
hydrogen,
Vapor diffused aluminum enrichment (alonization)
to protect of alloy surface,
Metallurgy, upgrading from HP-Mod to the 35Cr/
45Ni alloys,
Coating and surface enrichment using Si, AI, Cr,
Selected pretreatment of the inner surface of the
coils.
Literature Cited
Albright, L. F. and J. C. Marek: "Coke Formation during Pyrolysis:
Role of Residence Time, Reactor Geometery, and Time of Op
eration," Ind. tllg. Chem. Res., 27,743-751 (1988a)
Albright. L. F. and J. C Marek: "Analysis of Coke Produced in
Ethylene Furnaces: In,ight of Proces, Improvement." Ind. Eng.
Chem. Res., 27.751755 (1988b)
Albright, L. F. and J. C. Marek: "Me.:hanistic Model for Formation
of Coke in Pyrolysis Units Producing Ethylene:' Ind. Eng.
Chelll. Res .. 27.755-759 (l988cl
Albright. L. F. and C. F. M.:Connel: "Deposition and Gasification
of Coke During Ethane Pyrolysis," ACS Symp. Ser., 183, 205
224 (1979)
Albright. L. F. and W. A. McGill: "Metallurgical Control of Coke
Formation in Olefins Fuma.:e,; through Alonizing," Presented
at the Spring National Meeting of AIChE, New Orleans, USA
(1986)
Albright. L. F. and W. A. I\kGill; "Aluminized Ethylene Furnace
Tube Extended Operating Life," Oil & Gas.1., 8. 46-50 (1987)
Albright, L. F. and Y. C. Yu: "Production of Coke and Other Py~
rolysis Productioll From Acetylene, Butadiene, and Benzene in
Various Tubular Reactor." At" Chem. Ser.. 183, 193-203 (1979)
Albright, L. F.. C. F. l\1eConnd and K. Welther: "Types of Coke
Formed during the Pyrolysis of Light Hydrocarbons," ACS
Symp. Ser., 183. 175191 (1979)
Babash, S. E. and T. ~. Mukhina: "Effective Coke Inhibition in
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