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1994,33, 2584-2590
An extensive experimental program has been carried out in a pilot unit for the thermal cracking
of hydrocarbons. On the basis of the experimental information and the insight in the mechanisms
for coke formation in pyrolysis reactors, a mathematical model describing the coke formation
has been derived. This model has been incorporated in the existing simulation tools at the
Laboratorium voor Petrochemische Techniek, and the run length of a n industrial naphtha
cracking furnace has been accurately simulated. In this way the coking model has been validated.
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Ind. Eng. Chem. Res., Vol. 33,No. 11, 1994 2585
A,
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In this section the paraffin content in the reacting
mixture has decreased to a large extent.
For the same reasons, naphthenes can also be ne-
glected as direct precursors t o coke.
Unsaturates are a very important class of coke
precursors. They are reaction products of the pyrolysis
reactions so that their concentration in the high-
temperature zone of the reactor is high. Furthermore,
unsaturates are reactive and are good candidates for
radical addition. C4 components, which are present in
high concentration, are important coke precursors.
Longer chain unsaturated components decompose rap-
idly to smaller components.
Aromatics form a second class of important coke
precursors. The aromatic ring structure is close to the
structure of the coke matrix. Further, (branched)
A aromatics are reactive components, especially at the
high temperatures prevailing in thermal cracking coils.
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I I I I I 1 Figure 6. Evolution with time of ethylene yield in the various
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Figure 7. Evolution with time of the total energy input to the
furnace.
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Figure 8. Evolution with time of inlet pressures.
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Figure 10. Evolution with time of heat flux profile for coil 4. Figure 12. Evolution of profiles of thickness of coke layer in coil
4.
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Figure 11. Evolution with time of profiles of coking rate in coil
4. Figure 13. Profiles of external tube skin temperature, coil 4.
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reactor results from the requirement of achieving a 1.1oo ,
higher conversion, so as to keep the ethylene yield
constant, in spite of the increase in pressure. It
compensates for the decrease of the heat fluxes in the
second part of the reactor caused by the coke formation.
The coke layer reaches its maximum thickness in the
second part of the coil.
It should be stressed that these results can only be
obtained from a detailed furnace and reactor simulation.
Assuming a translation of the heat flux profile with
time, as is normally done when performing only reactor
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simulation, leads to an overestimate of the coking rates 0 1Lo
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and to predicted run lengths which are too short. Figure 14. Evolution with time of external tube skin tempera-
The evolution of the coking rates with time is shown ture.
in Figure 11 (reactor 4). The coke formation takes place The evolution with time of the coke layer is reflected
at the temperature of the gadcoke interface. The coking in the external wall temperatures. These are shown for
rates are high in the second part of the reactor. As a reactor 4 in Figure 13. The temperature rises with time
consequence, the coke layer grows fast there and creates to meet the heat flux requirements, in spite of the
an additional resistance to heat transfer. Further, the additional resistance to the heat transfer resulting from
coke layer also causes a decrease of the tube cross- the coke deposition. Initially, the temperatures are
sectional area and this leads to higher linear gas highest in the high-temperature section of the reactor,
velocities in this section, causing an improved convective where the coking rates are highest and the coke layer
heat transfer from the interface to the reacting gases. reaches its maximum thickness. The largest increase
These two effects lead to a decrease with time of the in the external wall temperatures is observed in this
interface temperatures in the single tube section of the section. The maximum value is reached at a reactor
reactor. Together with the interface temperatures, the length of 47 m. Initially the maximum value is ap-
coking rate also decreases with time. proximately 1000 "C.
In the split part of the reactor the coke layer is less Figure 14 shows the evolution with time of the
important. Increasing the heat fluxes with time in- maximum external wall temperature for the four simu-
creases the gadcoke interface temperatures and the lated reactors. This value should be watched carefully
coking rates. The coke layer tends to become more during operation, since there is a limitation imposed by
uniform along the tube with time. the metallurgy. In the present case the limiting value
The simulated thickness of the coke layer is given in is 1090 "Cand it is reached on reactor 4 after 1900h or
Figure 12 for reactor 4. The coke reaches its maximum about 80 days of operation, after which decoking is
thickness on the last pass, immediately after the last necessary. The simulated value is in excellent agree-
lower U-bend in the reactor. At the end of the run the ment with the observed plant value, which was 85 days.
coke thickness is 8.7 mm, corresponding to a reduction The temperature limit is reached on one reactor only.
in diameter of more than 15%. For the other reactors there still is a margin of some 10
2590 Ind. Eng. Chem. Res., Vol. 33, No. 11, 1994
"C,meaning that their run length could have been Literature Cited
extended for 5-7 days. In commercial operation, it
might be worthwhile to decrease the cracking severity Bianchini, E. C.; Lund, C. R. F. Kinetic Implications of Mecha-
on reactor 4,so as to prolong the production cycle. nisms Proposed for Catalytic Carbon Filament Growth. J . Catal.
1989,177, 455-466.
Clymans, P. J.; Froment G. F. Computer Generation of Reaction
Conclusions Paths and Rate Equations in the Thermal Cracking of Normal
and Branched Paraffins. Comput. Chem. Eng. 1984,8(2), 137-
Literature data and experimental observations were 142.
combined to obtain mechanistic insight into coke forma- Figueiredo, J. L.; Orfao, J. J. M. Carbon Deposits on Metal
tion in thermal cracking. Three mechanisms contribute. Catalysts-Mechanisms of Formation and Gasification. Catal.
Initially a filament layer is formed by interaction of gas Today 1989,5,385-393
phase species with metal particles from the reactor wall. Hillewaert, L. P.; Dierickx, J. L.; Froment, G. F. Computer
The main mechanism is the interaction between active Generation of Reaction Schemes and Rate Equations for
sites on the coke layer with gas phase species. The Thermal Cracking. AIChE J . 1988,34(11, 17-24.
active sites are free radicals and originate from hydro- Kopinke, F. D.; Zimmermann, G.; Nowak, S. On the Mechanism
gen abstraction by small active gas phase radicals, such of Coke Formation in Steam Cracking-Conclusions from Re-
sults obtained by Tracer Experiments. Carbon 1988,26 (21,
as hydrogen and methyl radicals. At the free radical 117-124.
sites unsaturated precursors from the gas phase react Kopinke, F. D.; Zimmermann, G.; Reyniers, G.; Froment, G. F.
via addition, followed by a set of dehydrogenation and Relative Rates of Coke Formation from Hydrocarbons in Steam
cyclization reactions finally yielding a graphitic coke Cracking of Naphtha. 2. Paraffins, Naphthenes, Mono-, Di-, and
layer. A third mechanism involves the formation of Cycloolefins, and Acetylenes. Ind. Eng. Chem. Res. 1993a,32
droplets in the gas phase which then impinge and (11,56-60.
adhere t o the surface and are incorporated in the coke Kopinke, F.-D.; Zimmermann, G.; Reyniers, G.; Froment, G. F.
layer. This last contribution is thought to be important Relative Rates of Coke Formation from Hydrocarbons in Steam
only in the cracking of very heavy liquid feedstocks. Cracking of Naphtha. 3. Aromatic Hydrocarbons. Ind. Eng.
Chem. Res. 1993b,32(ll), 2620-2625.
The mechanistic considerations and the experimental Plehiers, P. M.; Froment, G. F. Firebox Simulation of Olefin Units.
information were used to develop a kinetic model in Presented at the AIChE Spring National Meeting, March 6-10,
which a set of 12 coke precursors form coke via a set of 1988.
parallel reactions. Plehiers, P. M.; Reyniers, G. C.; Froment, G . F. Simulation of the
This coking model was combined with a kinetic model Run Length of an Ethane Cracking Furnace. Ind. Eng. Chem.
for the cracking, a reactor model and a furnace model Res. 1990,29 (41, 636-641.
to simulate the run length of a furnace for the thermal Rao, M. V.; Plehiers, P. M.; Froment, G. F. The Coupled Simulation
cracking of naphtha. Detailed and accurate information of Heat Transfer and Reaction in a Pyrolysis Furnace. Chem.
can be obtained from this simulation. The growth of a Eng. Sci. 1988,43(6), 1223-1229.
coke layer is accurately simulated, and so is the evolu- Van Damme, P. S.; Froment, G. F. Thermal Cracking Computer
tion of the external tube skin temperatures. The Control in Pilot Plants. Chem. Eng. Prog. 1982,78 (91, 77-82.
simulated and experimental run lengths agree within
5%. Received for review December 9, 1993
Simulations of this kind can be used to optimize Revised manuscript received March 9, 1994
furnace operation for various feedstocks and operating Accepted July 6 , 1994@
conditions. They can be used as a guide for the
adaptation of the operating variables aiming at prolong- @ Abstract published in Advance A C S Abstracts, September
ing the run length of the furnace. 15, 1994.