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 products and reduces the decoking time of the furnace.
ethylene is based on thermal cracking of gaseous Primary reaction products are ethylene, propene,
and liquid hydrocarbons. Typical gaseous acetylene, hydrogen and methane. The hot gases leave the
feedstocks are ethane, propane and butane. convection zone and enter the radiant zone (750 – 875 °C).
Common liquid feedstocks are naphtha, gas oil and The hot cracked gases are cooled down immediately in
hydrocracker residue. In the presence of steam they are the transfer line exchangers (TLX, TLE) to avoid undesired
fed to the cracking furnace. This gas phase reaction is side reactions of the reactants. The transfer line
called pyrolysis or steam cracking. The production of exchanger is located very close to the cracking furnace
ethylene is a very complex process including cracking, outlet.
cooling, compression and separation steps.
The cracking furnace is the heart and starting point of Coke fouling
the ethylene production. The hydrocarbon stream is Coking is a side reaction from thermal cracking. It is a major
preheated in the convection zone (500 – 680 °C) of the operational problem in the radiant section of steam
furnace, where it is mixed with steam. Steam dilution cracking furnaces and transfer line exchangers. The coke
lowers the hydrocarbon partial pressure of the light formation is a very complex mechanism. In general, there
gaseous, cracked compounds to reduce their are four mechanisms, which describe the coke formation:
recombination and polymerisation reactions. It also nn Free radical mechanism.
lowers the partial pressure of high boiling and high nn Catalytic mechanism.
molecular mass aromatics, which reduces their tendency nn Condensation reactions of heavy polynuclear
to deposit and minimises coke deposition on the furnace compounds.
tubes. This favours the formation of primary reaction nn Mechanical entrainment of coke particles.

Hydrocarbon
Engineering Reprinted fro m July 2014
 Gaseous free radicals form pyrolytic coke, which reaction volume and finally leads to even more rapid coke
deposits on the radiant coil and transfer line exchanger. formation. Before the external tube skin temperature reaches
Catalytic coke formation is associated with the presence of its maximum material operating limit, the formed coke has to
active sites on the metal surface. Particles of nickel, iron and be removed frequently by controlled combustion with steam
chromium or alloys containing these metals catalyse the and air. This decoking process is a non-productive downtime
formation of filamentous carbon. The carbon deposits for the furnace, which negatively affects the mechanical
displace the metal particles and dissolve into the metal strength and tube life. The run length of a furnace is defined
under high temperature. Condensation reactions occur at the as the operation between decoking cycles. Depending on
metal surface or coke surface. High boiling hydrocarbons design and diameter of the coils, the run length may vary
condense at the interface, where they dehydrogenate to between 10 – 15 days for small diameter coils and
form coke. Coke particles, formed in the radiant section, can 30 – 90 days for larger diameter coils. Several methods to
be detached and entrained to the transfer line exchanger, mitigate coke formation are available, which extend the time
where they accumulate. Coke fouling in the transfer line between decoking cycles.
exchanger is a severe problem as the outlet temperature
rises and less heat is recovered for steam generation. Novel materials
The coke build up results in a negative impact on Steel manufacturers are developing new metallurgies to
product yield, reduction of heat transfer efficiency and minimise coke formation. Several novel tube designs have
increased energy consumption. The external tube skin been achieved in the last years. Two interesting examples are
temperature continuously rises while the pressure drop the spiral mixing element welded on the internal wall of the
increases. This influences the process selectivity, declines 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
Figure 1. Coke inhibitor injection into the steam. the steel surface.

Sulfiding
Table 1. Comparison of sulfiding agents agents
Dimethyl sulfide Dimethyl disulfide Di-tert-butyl polysulfide The continuous
Abbreviation DMS DMDS TBPS injection of a
Sulfur content 51% 68% 54%
sulfiding agent is the
historical method
Flash point, ˚C - 45 16 100
for coke reduction
Thermal decomposition, ˚C > 250 > 200 > 160 and controlling
Vapour pressure (20 ˚C), hPa 527 38 1 carbon monoxide

Reprinted from July 2014 Hydrocarbon

Engineering
formation. Small amounts of sulfur are used to prevent coking non-hazardous and requires no special handling and storage.
and undesired chemical reactions. These sulfiding agents are TBPS has a very low vapour pressure at ambient temperature.
believed to decompose to form sulfidic surfaces on the coil Having a viscosity of 14 mPas at 20 °C it can be finely
surface. Others characterise the contribution of the sulfur dispersed or atomised into the steam to the cracking furnace.
compounds with an improved product selectivity and The injection system for TBPS is simple to realise as it can
reaction speed, resulting in a decrease of the decoking be stored in a storage or smaller day tank. Storage under
frequency. nitrogen is not required. The injection into the dilution steam
As shown in Figure 1 the coke inhibition agent is injected can be done with a small dosing pump or by using nitrogen
into the steam in front of the furnace. Special attention must pressure. The injection flow into the dilution steam can be
be paid to the fact that sulfiding agents should not be in controlled with a coreolis meter or other suitable
contact with condensed water to avoid unwanted fouling in measurement technology. The thermal decomposition
the steam line. temperature of TBPS starts above 160 °C as shown in Table 1.
Naphtha feed from the crude distillation unit already
DMS and DMDS contains sulfur and requires no further coke inhibition agent
Dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) are after pretreatment of the furnace tubes. Ethane, LPG and
well known, cost effective and proven sulfiding agents for unconverted oil from hydrocrackers (UCO) require a
steam cracking operations. Typical dosing rates are between continuous dosing of TBPS after decoking. Typical TBPS
20 – 100 ppm sulfiding agent during normal operating dosing rates are 20 - 100 ppm during normal operation. As a
conditions. pretreatment procedure TBPS is injected into the dilution
DMS is an organosulfur compound with the formula steam for 2 - 4 hrs after decoking operation.
(CH3)2S. It is a flammable liquid with a flash point of -45 °C. The continuous injection of TBPS significantly reduces the
DMS has a sulfur content of 51 wt% and is the most abundant coke formation with an increased run length of the cracking
sulfur compound. It has a very unpleasant, cabbage like furnace. Ethylene producers report that the negative impact
odour. The olfactory threshold is around 3 ppb. DMS was one on quench tower acidity that is usually observed with other
of the first sulfur bearing additives for the presulfiding sulfiding agents and attributable to SOx formation is not
process of catalysts. Meanwhile, it plays a minor role as a observed under TBPS treatment. Typical control settings as an
coke inhibitor for steam cracking operations. indication for the successful TBPS treatment are the CO and
Dimethyl disulfide (DMDS) is a very common sulfiding CO2 concentrations. Some ethylene plants keep the CO
agent. It has the molecular formula C2H6S2 and is the simplest concentration after caustic scrubber below 0.05 mol%, as CO
disulfide with a very unpleasant, garlic like odour. DMDS is a can poison the hydrogenation catalyst. The CO2
stable pale yellow liquid with a low flash point of 16 °C and a concentration before caustic scrubber should be below
sulfur content of 68 wt%. There are also special DMDS 400 vppm and after caustic scrubber below 1 vppm
formulations available for purchase, where small quantities of (otherwise ethylene would be off spec).
a perfume are added. This improves the odour of DMDS so
that it is less unpleasant for the production personnel. Conclusion
Due to the strong odours and low flash points of DMS The decoking process negatively affects the mechanical
and DMDS, special handling, storage and transportation are strength and tube life. The tube service life time is
mandatory. Operators are required to wear special clothing. economically important as the furnace capital costs are
Storage under nitrogen pressure in closed containers is around 20% of the total ethylene costs. Novel tube materials
required to avoid fire hazards. and coatings are successful technologies for an extended run
Under standard cracking conditions the complete length of the furnace with less decoking procedures.
decomposition temperatures of DMS and DMDS are believed Sulfiding agents like DMS and DMDS are the historical coke
to be above 550 °C. It has been reported, that these organic inhibition agents, which reduce the CO and coke formation
sulfides do not readily undergo gas phase decomposition and with an increased run length of the cracking furnace. Kurita
adsorb intact on the metal surface. It has also been reported, promotes the use of the polysulfide TBPS, which is a modern
that DMDS can affect the quench tower acidity, where the sulfiding agent. TBPS provides a very good performance
DMDS sulfur is converted to SOx. This will result in additional combined with an increased operational safety, less odour,
costs associated with the quench water pH control. good storage stability and easier handling.

TBPS References
Kurita has many years of experience with the injection of
1. DIP TAN, C., TERRY, R., and BAKER, K., Department of Chemistry,
polysulfides at steam crackers and promotes the use of Northeastern University, Boston, Massachusetts 02115, ‘The
Di-tert-butyl polysulfide (TBPS). This additive has the impact of selected sulfides on coke formation on various metal and
molecular formula (main constituent) C8H18S4 with a sulfur alloy surfaces’.
2. European Patent EP1631699, Nova Chemicals (International) S.A.
content of 54 wt%. 1700 Fribourg (CH), ‘Passivation of steel surface to reduce coke
TBPS has a number of significant advantages in formation’, Representative: WATSON, R.J. et al, Mewburn Ellis
LLP, 33 Gutter Lane, London, EC2V 8AS (GB).
comparison to DMS and DMDS. First among the operating 3. SRINIVAS, R.S. and HUMBLOT, F., Arkema Inc, Patent application
personnel notices a low TBPS odour, which is similar to gas number: 20090283451.
4. HELLER, F.E. and ROBERTS, C.D., The Lubrizol Corporation,
oil. This polysulfide has a far higher flash point of 100 °C, 'Atomized Polysulfide used in Ethylene steam cracker', Patent
which reduces the risk of potential flash fires. It is classified as 7154016, Application No. 10475457 filed on 03/06/2002.

Hydrocarbon
Engineering Reprinted fro m July 2014