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coke
formation
Berthold Otzisk and Christoph Eichman, Kurita Europe GmbH, Germany, discuss
methods for reducing coke formation in ethylene production.
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
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
Dimethyl disulfide
Di-tert-butyl polysulfide
Abbreviation
DMS
DMDS
TBPS
Sulfur content
51%
68%
54%
Flash point, C
- 45
16
100
Thermal decomposition, C
> 250
> 200
> 160
527
38
Hydrocarbon
Engineering
Sulfiding
agents
The continuous
injection of a
sulfiding agent is the
historical method
for coke reduction
and controlling
carbon monoxide
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
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