Process
Optimization
Reduce coke formation and save operating costs with
optimization of DMDS into ethane cracking furnaces
Steam cracking furnaces produce ole-
fins, which are high-value feeds in the
petrochemical industry. Coke forma-
tion is an unavoidable part of a thermal
cracking furnace. The amount of coke
created depends on feed quality, operat-
ing conditions and the metal surface of
the coil. Coke can be generated through
different mechanisms, but the most im-
portant are catalytic and asymptotic, or
pyrolytic, mechanisms.1
In the catalytic mechanism, the metal
surface of the tube coils (containing Fe-
Ni) works as a catalyst and enhances
coke formation. After the metal surface
is deactivated by a layer of catalytic coke
deposition, then the pyrolytic coke can
be formed on top of this initial coke
layer. Coke precursors of this method
are mainly olefins (ethylene, propylene),
aromatics (benzene, toluene, xylene),
acetylenes and butadiene.2
The main consequences of coke for-
mation in the furnace coil are increasing
pressure drop, due to roughness and tube
cross-section reduction; and decreasing
heat transfer rate, which reduces yield
and service times and increases energy
consuption.3 Therefore, technologies
like tube coatings, pretreatment of tube
coils and injection of inhibitors have
been developed to reduce the rates of
coke formation in the tube coils to allow
longer service time runs without shut-
ting down for decoking.3 Most injected
inhibitors are carefully selected, and
their conditions have been optimized
to minimize coke formation rates while
keeping operating inhibitor costs down.
G. HAY, G. RASOULI and L. CARBOGNANI-
ARAMBARRI, Virtual Materials Group Inc.,
Calgary, Canada; and R. SUZUKI, K. URATA
and M. INOUE, JX Nippon, Tokyo, Japan
Simulation models created to optimize
the service time running conditions
should account for well-known mecha-
nisms of coke growth. They should also
account for those mechanisms that are
less well understood, or even detrimen-
tal to finding the best solutions on a
plant-to-plant basis.
Coke formation background. Sulfur-
based inhibitors are used to reduce the
formation of both coke and carbon mon-
oxide (CO). The latter is particularly
important during startup. Some authors
state that CO formation is tied to the
thermal oxidation of coke, but contra-
dicting theories suggest that no depen-
dency exists, and that the source of CO
formation is steam reforming.4
Inhibitor usage to reduce coke forma-
tion works on the basis that heteroatom
elements block the catalytic effects of
specific metallic elements in the fur-
nace tube coils, such as Fe and Ni.5 Most
cracking furnace tube coils also contain
higher levels of chromium to help de-
crease catalytic coke growth, but this is
not always enough to provide the long
service run times desired.
The largest rates of catalytic coke
growth will usually occur at the start of
service time runs, when the tube surface
is cleanest and already-deposited coke
does not limit diffusion of the process
gas.6 This makes inhibitor influence more
critical at the start of service time runs.
Negative effects of DMDS. Dimethyl
disulfide (DMDS) is a widely used coke
inhibitor in steam cracking furnaces
to reduce coke formation growth with
other sulfur-based inhibitors, including
dimethyl sulfide, thiophene, benzothio-
phene and carbon disulfide. Although
DMDS has positive effects as a coke in-
hibitor with heavy feeds like naphtha and
light feeds like ethane, it shows unexpect-
ed behavior with light feeds.7
The component partial pressures in
ethane feed vs. naphtha feed through-
out the furnace coils are different. The
temperatures reached create conditions
for unexpected increase in coke growth.
Decomposition of the sulfur-based in-
hibitors, such as DMDS into hydrosul-
fide (HS) radicals, is thought to influence
both catalytic and asymptotic coke for-
mation rates. Catalytic rates are thought
to increase due to increased active catalyt-
ic sites caused by the recombination reac-
tions of the HS radicals into the coke sur-
face. The interference of HS radicals with
heterogeneous noncatalytic radical reac-
tions is thought to be responsible for the
increased asymptotic coke formation.8
Simulation model creation and
results. A fully rigorous and reactive sim-
ulation model was built to represent the
convective, furnace and quench sections
of an ethane cracking plant in Kawasaki,
Japan. This model’s fundamental driving
mechanisms were embedded within the
simulation software. The model included
information related to the furnace to rep-
resent the plant’s process.9
To determine optimized inhibitor
feedrates, everything within this mod-
Hydrocarbon Processing | FEBRUARY 2017 49
 Process Optimization

el needed to be rigorously calculated. tures. As shown in FIG. 2, the mechanisms

It was determined that reducing the
These calculations allowed the relay of DMDS injection rates within the first
at play in each of the coke formation re-
proper dependencies between opera- two days could allow a rapid coke thick-
gions was analyzed further, and causes of
tional conditions and resulting coke for- ness to be produced. For this reason, the
coke formation were determined.
In the first and second
tube passes, the low tem-
peratures of the process gas
Some authors state that carbon monoxide (CO) formation and tube kept general coke
is tied to the thermal oxidation of coke, but contradicting growth rates low. In the third
and fourth passes, the in-
theories suggest that no dependency exists, and that the creased temperatures began
source of CO formation is steam reforming. to degrade the DMDS that
generated the HS radicals.
Combined with higher tem-
peratures, the coke growth
mation. Coke thickness tracking was also rates were left unchanged. When DMDS surpassed the more natural final passes,
introduced to this model as a function of was reduced in the model, the coke where high temperatures and ethylene
the service time, to include the influence thickness showed the expected high partial pressures contributed to the ma-
of the coke thickness to the mechanisms coke growth from the clean tubes. It was jority of the coke growth.
of coke growth being studied. decided that the first week of operations
For the coke growth rates, each com- would be kept unchanged. Plant study. With the potential im-
ponent within the model was considered In addition to this precaution, it was provement to operations determined
separately at the conditions of the coking decided at the beginning of the run to through the simulation study, an actual
surface on the tube coil. General reac- drop the DMDS rate in stages. This ac- study was completed at the ENEOS/
tion rates, and the associated activation tion would allow pressure drop increase JX ethylene production plant in Kawa-
energies of coke formation, were taken to be monitored, and increased inhibi- saki, Japan. This exercise was carried out
from sources and broken into contribu- tor rates to be returned, if the increase to find the optimization point for the
tion groups to create a generic estima- in pressure drop from the start of run DMDS injection rate for the full-scale
tion method for any component.10–14 A showed signs of becoming more severe. ethane-fed steam cracking furnace.
dependency of catalytic effects of the Although the decrease in pressure To determine if the plant’s opera-
tube alloy, based on coke thickness, was drop due to the reduced coke formation tional conditions supported the mecha-
also included in the model.6 was not extreme, it was considered to be nisms for the increased coke formation
FIG. 1 shows the increase in pressure a strong point for plant optimization. If predicted in the simulated furnace, the
drop due to coke formation being pre- correct, these trends would allow large sulfur components entering and leav-
dicted in the model, with different ad- savings for the purchase of the DMDS ing the furnace section were measured.
ditional rates of DMDS to the feed. The inhibitor, due to lower injection rates. At From the resulting analysis, it was found
first simulation run assumed that a high the same time, it would slightly increase that the DMDS was being completely de-
initial amount of DMDS would be main- the length of service runs attributed to composed into components, such as hy-
tained continuously throughout the ser- excessive pressured drop. drogen sulfide (H2S), as suspected. The
vice time run. The second simulation The majority of the coke formation in higher outlet temperatures of the ethane
run would reduce the DMDS feedrate the model predictions was expected to be cracker left the coils above 800°C, and
after the initial high-catalyst-driven re- near the middle of the tube coil instead of potentially up to set points of 840°C.
gion of the service, when coke thickness near the end, where coke usually is domi- In addition, a detailed analysis of the
rates are still relatively small. nant due to the highest process tempera- tube coil coke thickness was taken at
the plant site at the end of a service run.
This analysis confirmed the trends pre-
dicted in FIG. 2 at measured points be-
Pressure drop, kPa and DMDS injection, mg/h

Pressure drop, kPa and DMDS injection, mg/h

DMDS normal injection DMDS normal injection tween the third pass and the coil’s outlet,
and opened the way for the start of the
Medium injection actual plant study. FIG. 3 shows the first
completed service time results from the
Small injection attempt to reduce the DMDS inhibitor.
The results followed many of the
Pressure drop increase suggested simulation model trends
Pressure drop increase
combined in FIGS. 1 and 2. However, it
showed an unexpected side effect in the
0 4 8 12 16 20 24 28 0 4 8 12 16 20 24 28
Service time, days Service time, days transfer line exchanger. Too much inhib-
itor would cause elevated coke growth
FIG. 1. Simulation predicted tube coil pressure drops with reduced DMDS injection rates.
rates in the front sections of the furnace
50 FEBRUARY 2017 | HydrocarbonProcessing.com
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 Process Optimization

7
Reyniers, M. F. and G.F. Froment, “Influence of
Pass 3 Pass 4 Pass 5 Pass 6 metal surface and sulfur addition on coke deposi-
Medium T Medium T Medium T High T tion in the thermal cracking of hydrocarbons,” Ind.
High DMDS Low DMDS No DMDS No DMDS Eng. Chem. Res., Vol. 34, Iss. 3, 1995.
High long olefins Low long olefins Low long olefins Low long olefins 8
Wang, J., M. F. Reyniers and G. B. Marin, “Influence
Low short olefins Low short olefins High short olefins High short olefins of dimethyl disulfide on coke formation during
steam cracking of hydrocarbons,” Ind. Eng. Chem.
Low aromatics Low aromatics High aromatics High aromatics Res., Vol. 46, Iss. 12, 2007.
High coke growth High coke growth Low coke growth High coke growth 9
Virtual Materials Group Inc., Company website,
online: http://virtualmaterials.com
10
Cai, H., A. Krzywicki and M. C. Oballa, “Coke for-
mation in steam crackers for ethylene production,”
Pass 1 and 2 Chemical Engineering and Processing, Vol. 41, 2002.
Low T
Coke thickness

11
Sundaramand, K. M. and G. F. Froment, “Kinetics
High DMDS of coke deposition in the thermal cracking of pro-
High long olefins pane,” Chemical Engineering Science, Vol. 34, 1979.
12
Towfighi, J., J. Modarres, M. Omidkhah and A.
Low short olefins Niaei, “Estimation of kinetic parameters of cok-
Low aromatics ing reaction rate in pyrolysis of naphtha,” IJE
Low coke growth Transactions B: Applications, Vol. 17, No. 4,
December 2004.
Tube coil length
13
Niaei, A., J. Towfighi and M. Sadrameli, “Prediction
of furnace run length for the pyrolysis of naphtha
FIG. 2. Theory of DMDS degradation rates vs. coke formation rate at a coil outlet temperature by a PC-based simulator,” Scientia Iranica, Vol. 10,
of 840°C. No. 3, 2010.
14
Kopinke, F. D., G. Zimmermann, G. C. Reyniers
and G. F. Froment, “Relative rates of coke forma-
tion from hydrocarbons in steam cracking of naph-
Pressure drop, kPa and DMDS injection, mg/h

Pressure drop, kPa and DMDS injection, mg/h

tha: Aromatic hydrocarbons,” Ind. Eng. Chem. Res.,

DMDS normal injection DMDS normal injection Vol. 32, 1993.
Medium injection
Medium injection
GLEN HAY is Vice President of Business Development
with Virtual Materials Group Inc. in Alberta, Calgary,
Small injection Canada. His experience is focused on reactors,
heat transfer units, and overall plant modeling
and optimization. He holds a BS degree in chemical
Pressure drop increase engineering from the University of Calgary and an
Pressure drop increase MS degree in advanced process control.

0 4 8 12 16 20 24 28 0 4 8 12 16 20 24 28 GHONCHEH RASOULI is a Process Simulator Software

Service time, days Service time, days Developer with Virtual Materials Group Inc. in
Alberta. Her experience is focused on reactors and
FIG. 3. Average tube coil pressure drop comparison run with reduced DMDS injection rates. coke formation. She holds a BA degree in chemical
engineering from the University of Tehran, an MS
degree from AmirKabir University of Technology in
modeling catalytic reactors and a PhD from McGill
coils, while too little would allow too feeds cracked at lower temperatures will University in pressure-induced phase separation of
much coke growth in the downstream not experience a strong negative influ- compressible polymer solutions.
sections. As a result of this finding, the ence, if any, from excessive DMDS injec-
LANTE CARBOGNANI is part of the technical
DMDS rates in FIG. 3 were raised to me- tion rates. support staff for Virtual Materials Group Inc. in
dium injection over the initial rates by Alberta. He has experience in process modeling,
LITERATURE CITED
the end of the service run. engineering design, and research and development
1
Albright, L. F. and J. C. Marekt, “Mechanistic model in upgrading and refining processes. He holds a BS
for formation of coke in pyrolysis units producing degree in chemical engineering from Simon Bolivar
Observations. The negative effects of ethylene,” Ind. Eng. Chem. Res., Vol. 27, Iss. 5, 1988. University in Venezuela and an MS degree in chemical
the DMDS inhibitor, when added in ex- 2
Cai, H., A. Krzywicki and M. C. Oballa, “Coke for- engineering from the University of Calgary in Canada.
cess, can be observed in the initial results mation in steam crackers for ethylene production,”
Chem. Eng. and Proc., Vol. 41, Iss. 3, 2002. RYOTA SUZUKI is a refining and chemical process
shown in FIG. 3 and continued results 3
Grace Chan, K. Y., F. Inal and S. Senkan, engineer at JX Nippon Oil and Energy Corp. He holds
gathered at the ENEOS/JX ethylene “Suppression of coke formation in the steam crack- a BS degree in chemistry from Keio University, as well
production plant. These trends matched ing of alkanes: Ethane and propane,” Ind. Eng. as an MS degree and a PhD in molecular chemistry
Chem. Res., Vol. 37, Iss. 3, 1998. from Keio University.
with a growing collection of public liter- 4
Froment, G. F., “Production of synthesis gas by
ature suggesting that DMDS will exhibit steam- and CO2-reforming of natural gas,” J. Mol. KOHEI URATA is part of the senior staff of JX Nippon
this negative behavior with ethane feed Catal. A-Chem., Vol. 163, Iss. 1–2, 2000. Oil and Energy Corp. in Kawasaki, Japan. He holds a
at higher coil temperatures.
5
Snoeck, J.-W., G. F. Froment and M. Fowles, BS degree in chemical science from Tokyo Institute
“Filamentous carbon formation and gasification: of Technology and an MS degree in chemistry and
Since this study did not include heavi- Thermodynamics, driving force, nucleation, and materials science.
er feeds or significantly lower coil outlet steady-state growth,” J. Catal., Vol. 169, Iss. 1, 1997.
temperature ranges, the extrapolation 6
Bach, G., G. Zimmermann, F.-D. Kopinke, MASAFUMI INOUE is part of the senior staff of
S. Barendregt, P. Oosterkamp and H. Woerde, JX Nippon Oil and Energy Corp. in Kawasaki, Japan.
cannot be made with any certainty con- “Transfer-line heat exchanger fouling during pyrol- He holds a BS degree in chemical science from
sidering the data gathered. At the same ysis of hydrocarbons: Deposits from dry cracked Tokyo Institute of Technology and an MS degree
time, the literature suggests that heavier gases,” Ind. Eng. Chem. Res., Vol. 34, Iss. 4, 1995. in chemistry science.

52 FEBRUARY 2017 | HydrocarbonProcessing.com