Coke Formation in The Thermal Crackin
Coke Formation in The Thermal Crackin
Coke Formation in The Thermal Crackin
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.
Introduction
One of the main problems in the thermal cracking of
hydrocarbons for olefin production is the formation of a
coke layer on the inner wall of the coils. This leads in
the first place to a decrease of the heat flux to the
reacting gas mixture and second also to an increase of
the pressure drop over the reactor. Periodically the
furnace operation has to be stopped and the coke has
to be burnt off by means of a mixture of steam and air.
In the previous papers in this series (Kopinke et al.,
1988, 1993a,b) relative rates of coke formation from
various types of carbon atoms (aliphatic, aromatic, ...I
were determined. The relative rates were determined
by adding a small but precisely defined amount of a I4Clabeled component to a naphtha feed.
The present paper provides a mechanistic interpretation of the experiments performed by Kopinke et al. and
of additional experimental information obtained in the
pilot plant for thermal cracking of the Laboratorium
voor Petrochemische Techniek.
Experimental information and mechanistic interpretation were combined to develop a model describing
quantitatively the coking process in thermal cracking
coils. The coking model was combined with a kinetic
model for the pyrolysis of liquid feedstocks, a reactor
model and a furnace model. The combination of these
models allows the accurate prediction of the run length
of a furnace for the thermal cracking of naphtha.
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2586 Ind. Eng. Chem. Res., Vol. 33, No. 11, 1994
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Figure 3. (a) Cross-linking with sp3
linking with sp2 carbon atom.
P+ C,H4-2C
+ P+ 2H,
Feedstock Characterization
specific gravity d(15/15)
0.7057
PNA analysis (wt %)
n-paraffins
33.0
isoparafhs
37.0
naphthenes
18.0
aromatics
12.0
boiling range ("C)
IBP
36.0
50%
94.5
FBP
161.0
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2590 Ind. Eng. Chem. Res., Vol. 33, No. 11, 1994
Conclusions
Literature data and experimental observations were
combined to obtain mechanistic insight into coke formation in thermal cracking. Three mechanisms contribute.
Initially a filament layer is formed by interaction of gas
phase species with metal particles from the reactor wall.
The main mechanism is the interaction between active
sites on the coke layer with gas phase species. The
active sites are free radicals and originate from hydrogen abstraction by small active gas phase radicals, such
as hydrogen and methyl radicals. At the free radical
sites unsaturated precursors from the gas phase react
via addition, followed by a set of dehydrogenation and
cyclization reactions finally yielding a graphitic coke
layer. A third mechanism involves the formation of
droplets in the gas phase which then impinge and
adhere t o the surface and are incorporated in the coke
layer. This last contribution is thought to be important
only in the cracking of very heavy liquid feedstocks.
The mechanistic considerations and the experimental
information were used to develop a kinetic model in
which a set of 12 coke precursors form coke via a set of
parallel reactions.
This coking model was combined with a kinetic model
for the cracking, a reactor model and a furnace model
to simulate the run length of a furnace for the thermal
cracking of naphtha. Detailed and accurate information
can be obtained from this simulation. The growth of a
coke layer is accurately simulated, and so is the evolution of the external tube skin temperatures. The
simulated and experimental run lengths agree within
5%.
Simulations of this kind can be used to optimize
furnace operation for various feedstocks and operating
conditions. They can be used as a guide for the
adaptation of the operating variables aiming at prolonging the run length of the furnace.
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