PETROLEUM COKE DESULFURIZATION

1. Introduction

Petroleum coke is a refinery product. It is produced in ‘coking process’ as a by-

product. Since, the main aim of petroleum refiners is to produce more and more
gasoline and middle distillates from crude oils, they pay very little attention to the
quality of petroleum coke. Moreover, due to scarcity and soaring prices of low
sulfur crudes, a large number of refineries have been processing higher sulfur
crudes, with the resultant increase in sulfur in petroleum coke. Based on statistics,
the percentage of sulfur in petroleum coke in year 2007 has increased by about 20%
from that in the year 1997 (Figure-1). In future, it is expected that this trend will
continue. Although, market exists for high sulfur coke in cement industry and
power plants, but demand for low sulfur, high quality petroleum coke is
continuously increasing in many industries like aluminum industry and steel
industry, which uses petroleum coke in the form of carbon and graphite electrodes.

2. Types of Sulfur in Petroleum Coke

Sulphur in petroleum coke is a function of sulfur in coking feed stocks. Generally,

vacuum residue is used as a coking feed stock for making regular grade petroleum
coke. For making speciality needle coke, aromatic rich feed stocks such as FCC
clarified oils, ethylene tars and lube oil extracts are used. Generally, the sulfur
present in petroleum coke is roughly double than the sulfur in feed stock. The sulfur
compounds present in the coke may be of organic or inorganic nature viz. thiols,
sulfides, thiophenes, benzothiophenes, dibenzothiophenes, pyritic, sulfates etc.
Pyritic and sulphate sulfur in coke is attached by physical attraction (adsorption)
and can be removed by simple washing and dissolving in water. However, the
removal of organic sulfur needs a drastic treatment to break strong carbon-sulfur
bonds. Thiophenes are the most prevalent forms of organic sulfur in the crude oils
and hence in the petroleum coke. Since, the sulfur in the petroleum coke is present
in the form of thiophene. benzothiophenes and dibenzothiophenes - the part of very
 Petroleum Coke Desulfurization

stable complex molecules called asphaltenes and embedded deeply in coke - its
removal is not so easy. The removal of organic sulfur requires high temperature
thermal treatment or chemical treatment methods or combination of both. Several
alternate methods have been proposed and are at different stages of development
but none of these methods is known to be commercially successful as yet.

3. Why Petroleum Coke Desulphurization?

The most important drivers for the surge in attempts at petroleum coke
desulfurization have been the growing demand of low sulfur coke by many
industries and its use as a vital feed component in some key processes. For example :

• Largest consumer of petroleum coke i.e. aluminum industry requires far low
sulphur petroleum coke (<2.5wt%) for production of high purity aluminum

• Graphite electrodes industry needs very low sulfur petroleum coke because high
sulfur petroleum coke (>0.5wt%) causes “puffing or volume expansion” which
may cause fracturing of graphite electrodes during manufacturing process.
Graphite electrodes are used in steel industry for melting scrape

• High sulfur petroleum coke (>2.5wt%) is used in cement industry and power
plants but it produces SO2 which poses serious environment pollution problems
and is a grave health hazard

• Low sulfur petroleum coke is a clean feed for gasification process to produce
syngas
4. Literature Information on Petroleum Coke Desulfurization

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 Petroleum Coke Desulfurization

The information available in literature shows that traditionally petroleum coke is

desulfurized by chemical methods i.e. hydrodesulphurization, oxidative
desulphurization, alkali salt desulphurization etc. The important methods for
petroleum coke desulphurization are briefly desired hereafter :

– Solvent Extraction

Some researches have used solvent extraction to desulfurize petroleum coke. For
this purpose, a variety of solvents like phenols, pyridine, aromatic aldehydes
naphthalenes, BTX CCl4, CS2 etc were employed. It was found that organic
solvents like furfural and phenol are most effective in most cases but level of
sulfur removal is limited to 14-20%. This was due to poor penetration of solvent
to deeply embedded sulfur molecules in coke. A higher extraction temperature
shows only a marginal advantage in desulfurization. A combination of oxidation,
hydrogenation, application of ultrasound along with solvent extraction may
enhance the extent of desulfurization.

– Oxidative Desulfurization

Many researchers utilized oxidative desulfurization approach for petroleum coke

desulfurization. In this approach, desulfurization of petroleum coke is facilitated
with the help of liquid or gaseous oxidizing agents, such as hydrogen peroxide,
nitric acid, air, steam, butagas etc. The use of sulfur bearing gas such as SO2 has
also been found to be quite effective for removal of sulfur from coke. The level of
sulfur removal in oxidative desulfurization process generally is restricted to 30%.

– Hydro-desulfurization (HDS)

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 Petroleum Coke Desulfurization

Hydrodesulphurization (HDS) is most common method applied in petroleum

refineries to reduce sulfur from feed as well as products (liquid distillates). In
hydrodesulphurization (HDS) process, coke is made to react with hydrogen gas
at high temperature ~800-1300°C and at high pressure to achieve desulfurization
upto 92%. Around 50% sulfur is easily removed off through HDS at 725°C. The
removal of sulfur present in the polynuclear structure needs still higher
temperature i.e.1200-1500°C. Increase in hydrogen flow rate and pressure have
positive effects on sulfur removal.

– Thermal Dsulfurization of Petroleum Coke

In this process, petroleum coke obtained from delayed coker is thermally treated
at temperature in the range of 1300-1600 C for a period of 6 to 24 hrs, in an
atmosphere of hydrogen or oxygen containing gas. The extent of desulfurization
depends upon desulphurization temperature, heating rate, thermal soaking time,
reaction atmosphere etc. Thermal desulfurization is able to desulfurize the
petroleum coke upto 96%.

Some times, the high desulfurization temperatures also decrease real density of
coke due to development of porosity, caused by “puffing”.

– Alkali Metal Compound Treatment

Petroleum coke treatment with alkali metal salts is another good option for
removal of sulfur from coke. Among all the petroleum coke desulfurization
processes, this method is most effective and capable of removing sulfur upto
98%. However, a major but main drawback associated with this process is
consumption of huge amount of alkalie metals and difficulty in its complete
recovery/removal from coke after desulfurization.

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 Petroleum Coke Desulfurization

Sometimes, alkalie metals (NaCO3) are also added to coke feedstocks prior to
coking. This approach lowers the sulfur in petroleum coke upto75% on feed
basis.

A brief summary of various petroleum coke desulfurization methods is given in

Table -1

Table -1

Process Solvent/Temperature/ Pressure Max.%

Solvent Extraction
Oxidative Desulphurization
Hydro-desulphurization
Thermal Desulphurization
Alkali Metal Treatment
Desulphurization
Solvent : Chloro-phenol, Pyridine etc 20 %
Oxidant ; Air, Steam; Temp : 1100 ˚C 31 %
H2; Temp : 800 ˚C; High Pressure 87 %
Temp : ~ 1600 ˚C 96 %
Reactant NaOH; Temp: 800 ˚C 98 %

Besides these, biological methods have also been applied widely for coal
desulfurization but not for petroleum coke.

Figure 1 : Year Wise Trend of Sulfur in