Mitigating
coke
formation
Berthold Otzisk and Christoph Eichman, Kurita Europe GmbH, Germany, discuss
methods for reducing coke formation in ethylene production.
T
he leading technology for the production of
ethylene is based on thermal cracking of gaseous
and liquid hydrocarbons. Typical gaseous
feedstocks are ethane, propane and butane.
Common liquid feedstocks are naphtha, gas oil and
hydrocracker residue. In the presence of steam they are
fed to the cracking furnace. This gas phase reaction is
called pyrolysis or steam cracking. The production of
ethylene is a very complex process including cracking,
cooling, compression and separation steps.
The cracking furnace is the heart and starting point of
the ethylene production. The hydrocarbon stream is
preheated in the convection zone (500 – 680 °C) of the
furnace, where it is mixed with steam. Steam dilution
lowers the hydrocarbon partial pressure of the light
gaseous, cracked compounds to reduce their
recombination and polymerisation reactions. It also
lowers the partial pressure of high boiling and high
molecular mass aromatics, which reduces their tendency
to deposit and minimises coke deposition on the furnace
tubes. This favours the formation of primary reaction
products and reduces the decoking time of the furnace.
Primary reaction products are ethylene, propene,
acetylene, hydrogen and methane. The hot gases leave the
convection zone and enter the radiant zone (750 – 875 °C).
The hot cracked gases are cooled down immediately in
the transfer line exchangers (TLX, TLE) to avoid undesired
side reactions of the reactants. The transfer line
exchanger is located very close to the cracking furnace
outlet.
Coke fouling
Coking is a side reaction from thermal cracking. It is a major
operational problem in the radiant section of steam
cracking furnaces and transfer line exchangers. The coke
formation is a very complex mechanism. In general, there
are four mechanisms, which describe the coke formation:
nn Free radical mechanism.
nn Catalytic mechanism.
nn Condensation reactions of heavy polynuclear
compounds.
nn Mechanical entrainment of coke particles.
Hydrocarbon
Engineering Reprinted fro m July 2014
 Gaseous free radicals form pyrolytic coke, which
deposits on the radiant coil and transfer line exchanger.
Catalytic coke formation is associated with the presence of
active sites on the metal surface. Particles of nickel, iron and
chromium or alloys containing these metals catalyse the
formation of filamentous carbon. The carbon deposits
displace the metal particles and dissolve into the metal
under high temperature. Condensation reactions occur at the
metal surface or coke surface. High boiling hydrocarbons
condense at the interface, where they dehydrogenate to
form coke. Coke particles, formed in the radiant section, can
be detached and entrained to the transfer line exchanger,
where they accumulate. Coke fouling in the transfer line
exchanger is a severe problem as the outlet temperature
rises and less heat is recovered for steam generation.
The coke build up results in a negative impact on
product yield, reduction of heat transfer efficiency and
increased energy consumption. The external tube skin
temperature continuously rises while the pressure drop
increases. This influences the process selectivity, declines the
Figure 1. Coke inhibitor injection into the steam.
Table 1. Comparison of sulfiding agents
Dimethyl sulfide Dimethyl disulfide
Abbreviation DMS DMDS
Sulfur content 51% 68%
Flash point, ˚C - 45 16
Thermal decomposition, ˚C > 250 > 200
Vapour pressure (20 ˚C), hPa 527 38
Reprinted from July 2014 Hydrocarbon
Engineering
reaction volume and finally leads to even more rapid coke
formation. Before the external tube skin temperature reaches
its maximum material operating limit, the formed coke has to
be removed frequently by controlled combustion with steam
and air. This decoking process is a non-productive downtime
for the furnace, which negatively affects the mechanical
strength and tube life. The run length of a furnace is defined
as the operation between decoking cycles. Depending on
design and diameter of the coils, the run length may vary
between 10 – 15 days for small diameter coils and
30 – 90 days for larger diameter coils. Several methods to
mitigate coke formation are available, which extend the time
between decoking cycles.
Novel materials
Steel manufacturers are developing new metallurgies to
minimise coke formation. Several novel tube designs have
been achieved in the last years. Two interesting examples are
the spiral mixing element welded on the internal wall of the
cracking coil and the development of cast finned tubes.
Both designs improve the heat and mass transfer, which
saves fuel costs and increases the tube life as carburisation is
reduced. Cast finned tubes provide a very short residence
time, which improves the product selectivity.
Tube coating
There are a number of precoating technologies available,
which are applied on the radiant coil during manufacture. By
forming a very thin layer of diffusion barrier, catalytic coke is
reduced. Typical applications are glass ceramic coatings onto
the tube surface. In many cases this kind of precoating
technology improves the on stream time of a furnace to
some hundred days before decoking is required. Special
attention must therefore be paid to ensure that the heat
transfer does not deteriorate.
Another kind of pretreatment is the injection of an
additive after the decoking procedure, when the cracking
furnace is under steam flow. Aqueous metal salts or
proprietary phosphorus, tin and silicon based compounds are
typically used. They also work by forming a layer of diffusion
barrier. Control of the pretreatment effluents is
recommended as they can be trapped in the pyrolysis oil of
the primary fractionator or downstream processes.
A patented technology is the preliminary reduction of
the steel surface within a defined timeframe. The steel
surface is treated with steam and hydrogen or together with
inert gases such as nitrogen, helium, argon, etc., and steam.
The second step of the patented treatment procedure is the
injection of several coke inhibiting compounds to passivate
the steel surface.
Sulfiding
agents
Di-tert-butyl polysulfide The continuous
TBPS injection of a
54%
sulfiding agent is the
historical method
100
for coke reduction
> 160 and controlling
1 carbon monoxide
formation. Small amounts of sulfur are used to prevent coking
and undesired chemical reactions. These sulfiding agents are
believed to decompose to form sulfidic surfaces on the coil
surface. Others characterise the contribution of the sulfur
compounds with an improved product selectivity and
reaction speed, resulting in a decrease of the decoking
frequency.
As shown in Figure 1 the coke inhibition agent is injected
into the steam in front of the furnace. Special attention must
be paid to the fact that sulfiding agents should not be in
contact with condensed water to avoid unwanted fouling in
the steam line.
DMS and DMDS
Dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) are
well known, cost effective and proven sulfiding agents for
steam cracking operations. Typical dosing rates are between
20 – 100 ppm sulfiding agent during normal operating
conditions.
DMS is an organosulfur compound with the formula
(CH3)2S. It is a flammable liquid with a flash point of -45 °C.
DMS has a sulfur content of 51 wt% and is the most abundant
sulfur compound. It has a very unpleasant, cabbage like
odour. The olfactory threshold is around 3 ppb. DMS was one
of the first sulfur bearing additives for the presulfiding
process of catalysts. Meanwhile, it plays a minor role as a
coke inhibitor for steam cracking operations.
Dimethyl disulfide (DMDS) is a very common sulfiding
agent. It has the molecular formula C2H6S2 and is the simplest
disulfide with a very unpleasant, garlic like odour. DMDS is a
stable pale yellow liquid with a low flash point of 16 °C and a
sulfur content of 68 wt%. There are also special DMDS
formulations available for purchase, where small quantities of
a perfume are added. This improves the odour of DMDS so
that it is less unpleasant for the production personnel.
Due to the strong odours and low flash points of DMS
and DMDS, special handling, storage and transportation are
mandatory. Operators are required to wear special clothing.
Storage under nitrogen pressure in closed containers is
required to avoid fire hazards.
Under standard cracking conditions the complete
decomposition temperatures of DMS and DMDS are believed
to be above 550 °C. It has been reported, that these organic
sulfides do not readily undergo gas phase decomposition and
adsorb intact on the metal surface. It has also been reported,
that DMDS can affect the quench tower acidity, where the
DMDS sulfur is converted to SOx. This will result in additional
costs associated with the quench water pH control.
TBPS
Kurita has many years of experience with the injection of
polysulfides at steam crackers and promotes the use of
Di-tert-butyl polysulfide (TBPS). This additive has the
molecular formula (main constituent) C8H18S4 with a sulfur
content of 54 wt%.
TBPS has a number of significant advantages in
comparison to DMS and DMDS. First among the operating
personnel notices a low TBPS odour, which is similar to gas
oil. This polysulfide has a far higher flash point of 100 °C,
which reduces the risk of potential flash fires. It is classified as
non-hazardous and requires no special handling and storage.
TBPS has a very low vapour pressure at ambient temperature.
Having a viscosity of 14 mPas at 20 °C it can be finely
dispersed or atomised into the steam to the cracking furnace.
The injection system for TBPS is simple to realise as it can
be stored in a storage or smaller day tank. Storage under
nitrogen is not required. The injection into the dilution steam
can be done with a small dosing pump or by using nitrogen
pressure. The injection flow into the dilution steam can be
controlled with a coreolis meter or other suitable
measurement technology. The thermal decomposition
temperature of TBPS starts above 160 °C as shown in Table 1.
Naphtha feed from the crude distillation unit already
contains sulfur and requires no further coke inhibition agent
after pretreatment of the furnace tubes. Ethane, LPG and
unconverted oil from hydrocrackers (UCO) require a
continuous dosing of TBPS after decoking. Typical TBPS
dosing rates are 20 - 100 ppm during normal operation. As a
pretreatment procedure TBPS is injected into the dilution
steam for 2 - 4 hrs after decoking operation.
The continuous injection of TBPS significantly reduces the
coke formation with an increased run length of the cracking
furnace. Ethylene producers report that the negative impact
on quench tower acidity that is usually observed with other
sulfiding agents and attributable to SOx formation is not
observed under TBPS treatment. Typical control settings as an
indication for the successful TBPS treatment are the CO and
CO2 concentrations. Some ethylene plants keep the CO
concentration after caustic scrubber below 0.05 mol%, as CO
can poison the hydrogenation catalyst. The CO2
concentration before caustic scrubber should be below
400 vppm and after caustic scrubber below 1 vppm
(otherwise ethylene would be off spec).
Conclusion
The decoking process negatively affects the mechanical
strength and tube life. The tube service life time is
economically important as the furnace capital costs are
around 20% of the total ethylene costs. Novel tube materials
and coatings are successful technologies for an extended run
length of the furnace with less decoking procedures.
Sulfiding agents like DMS and DMDS are the historical coke
inhibition agents, which reduce the CO and coke formation
with an increased run length of the cracking furnace. Kurita
promotes the use of the polysulfide TBPS, which is a modern
sulfiding agent. TBPS provides a very good performance
combined with an increased operational safety, less odour,
good storage stability and easier handling.
References
1. DIP TAN, C., TERRY, R., and BAKER, K., Department of Chemistry,
Northeastern University, Boston, Massachusetts 02115, ‘The
impact of selected sulfides on coke formation on various metal and
alloy surfaces’.
2. European Patent EP1631699, Nova Chemicals (International) S.A.
1700 Fribourg (CH), ‘Passivation of steel surface to reduce coke
formation’, Representative: WATSON, R.J. et al, Mewburn Ellis
LLP, 33 Gutter Lane, London, EC2V 8AS (GB).
3. SRINIVAS, R.S. and HUMBLOT, F., Arkema Inc, Patent application
number: 20090283451.
4. HELLER, F.E. and ROBERTS, C.D., The Lubrizol Corporation,
'Atomized Polysulfide used in Ethylene steam cracker', Patent
7154016, Application No. 10475457 filed on 03/06/2002.
Hydrocarbon
Engineering Reprinted fro m July 2014