COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT Vol.

I - Desulfurization of Coal - Yasuo Ohtsuka

DESULFURIZATION OF COAL
Yasuo Ohtsuka
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
Japan
Keywords: Biological cleaning, Chemical cleaning, Coal, Desulfurization, Flue gas
desulfurization, In-bed desulfurization, Limestone, Organic sulfur, Physical cleaning,
Pyritic sulfur, Wet scrubbers.
Contents

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1. Introduction
2. Sulfur in Coal
2.1 Sulfur Content
2.2 Sulfur Form
3. Coal Cleaning for Sulfur Removal
3.1 Physical Cleaning
3.1.1 Separation Using Specific Gravity Difference
3.1.2 Separation Using Surface Properties
3.1.3 Magnetic and Electrostatic Separation
3.2 Chemical Cleaning
3.3 Biological Cleaning
4. In-bed Desulfurization
5. Flue Gas Desulfurization
5.1 Wet Scrubbers
5.2 Other Flue Gas Desulfurization Processes
6. Conclusion
Glossary
Bibliography
Biographical Sketch
Summary

Sulfur in coal exists in inorganic and organic forms, the former being mostly pyritic
sulfur. Total sulfur contents in major coalfields are in the range of roughly 0.510 wt%.
In coal combustion, to generate electric power and process heat, the sulfur is emitted as
SO2, which is seen as one of the main causes of acid rain. This effect has led to an
interest in the three main methods of removing coal sulfur: coal cleaning, in-bed
desulfurization, and flue gas desulfurization. Coal cleaning includes physical, chemical,
and biological processes. Since physical cleaning is generally based on the differences
in either specific gravity or surface properties between the organic matter in coal and the
associated minerals, it can remove the inorganic sulfur alone. This method is the
commercially proven technology. Chemical or biological cleaning can offer the
potential to remove organic sulfur, but these methods have not yet been used
commercially. Development work is currently directed towards establishing effective,
low-cost techniques. In-bed desulfurization involves the use of Ca-based sorbent, which
captures in situ the SO2 emitted during fluidized bed combustion. Although this high

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COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT Vol. I - Desulfurization of Coal - Yasuo Ohtsuka

temperature desulfurization process is well proven, the reduction of sorbent

consumption is required to minimize the costs for sorbent and residue management.
Flue gas desulfurization (FGD) removes the SO2 from the flue gas of coal-fired plants.
This post-combustion method is the most widely used technology for controlling SO2
emissions. Among commercial FGD processes, wet scrubbers account for more than
80% of the total capacity and achieve SO2 removal efficiencies of more than 90%. The
majority of them uses the limestone (or wet lime)/gypsum system. Spray dry scrubbers
and sorbent injection processes have been used for relatively small to medium capacity
boilers and for retrofitting on existing coal-fired plants.
1. Introduction

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Coal is one of the main sources of world energy. Economic growth and industrialization
in developing countries are leading to a rapid increase in the demand for energy; in
other words, an increased demand in the use of coal, which is inexpensive and readily
available, for electric power and process heat. When coal is burned, generally 90% or
more of the sulfur present in it is emitted into the atmosphere as sulfur oxides (mainly
SO2), if no desulfurization methods are used before, during, and after combustion. It is
well-known that SO2 emissions are considered one of the main causes of acid rain,
which leads to the acidification of soils, forests, and surface waters. The growth in coalfired capacity has therefore led to increasing concern about environmental issues, such
as increased emissions of SO2, nitrogen oxides (NOx), trace elements, and particulates,
although most effort has been directed towards the control of SO2 emissions. This
article focuses on the reduction of SO2 emissions in the use of coal, in particular from
coal combustion, and addresses the following options for this purpose:
The use of low-sulfur coal
Pretreatment of coal for sulfur removal.
In situ sulfur capture during combustion.
Post-combustion treatment of flue gas
2. Sulfur in Coal

2.1 Sulfur Content

The total sulfur content of coal can vary within a single deposit as well as between
deposits. As summarized in Table 1, the content for selected coalfields of major coal
producing countries ranges between below 0.5 wt% and roughly 10 wt%. Since coals on
the international market have stricter specifications regarding sulfur and ash content,
however, the former is generally in the range of 0.61 wt%. Global sources of such lowsulfur coals are diverse, with the largest deposits in China, South Africa, Australia,
USA, and Russia. With increasingly stringent environment legislation, coal sulfur
content has become one of the most important factors for fuel choice, and the supply of
low-sulfur coal on the international coal market has increased considerably in recent
years. Nevertheless, major users such as power stations have often been tied to local
supplies of high-sulfur coal because of quality, cost, or policy. In the USA and
Indonesia, for example, many low-sulfur coals are of low rank with decreased calorific
value and increased moisture content, compared with high-sulfur coals. With limited

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COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT Vol. I - Desulfurization of Coal - Yasuo Ohtsuka

supplies of high quality low-sulfur coal, blending with high-sulfur coals may help
utilities meet SO2 emission standards.
Coalfields and Region
Queensland basin
Western
Shanxi
Cerrejon
Ruhr
Raniganj and Jharia
Kalimantan
Upper Silesian basin
Kuznetsk basin
Witbank and Highveld
East Pennine
Illinois basin

Total sulfur content, wt%

0.2-1.3 (air dried)
0.2-1.2
0.4-6.0
0.4-0.9 (air dried)
0.7-0.8
0.5-0.8 (air dried)
0.1-0.9
0.8-1.8
0.3-0.8
0.3-2.4 (air dried)
0.8-4.0
0.2-7.7

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Country
Australia
Canada
China
Columbia
Germany
India
Indonesia
Poland
Russia
South Africa
UK
USA

Table 1. Total sulfur contents for selected coalfields of major coal producing countries

2.2 Sulfur Form

Figure 1. Ratio of pyritic sulfur/organic sulfur as a function of total sulfur content

Sulfur present in coal exists as both inorganic and organic forms. The inorganic form is
mostly pyritic sulfur (FeS2), which occurs in two crystalline habits, pyrite (cubic) and

Encyclopedia of Life Support Systems (EOLSS)

COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT Vol. I - Desulfurization of Coal - Yasuo Ohtsuka

marcasite (orthorhombic), the former being more common. Although sulfate and
elemental sulfur are also observed, their contents are low. The sulfatic form is mainly
gypsum and iron sulfate, the latter usually resulting from oxidation of pyritic sulfur
during storage.
Pyritic and organic sulfur together account for the large majority of sulfur in coal. The
ratio of the two forms as a function of total sulfur content is shown in Figure 1, where
35 coal samples from major coal producing countries are used. Although there is no
distinct relationship, the ratio is less than two in most samples. Since pyritic sulfur can
be removed by physical cleaning, as mentioned below (see 2.1), it is usually easy to
reduce the total sulfur in the coal with a high ratio of pyritic sulfur/organic sulfur.

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The ASTM standard test method (D 2492) applies to the determination of pyritic and
sulfatic sulfur. In this method, briefly, coal particles are first extracted with hot dilute
HCl to remove sulfatic sulfur, and the residue is then extracted with dilute HNO3 to
measure the iron content, which makes it possible to calculate the content of pyritic
sulfur from the 1:2 stoichiometry of FeS2. Organic sulfur is determined by difference;
that is, by subtracting the sum of pyritic and sulfatic forms from total sulfur content, and
is thus subject to the accumulated errors in these measurements. To remove such
uncertainty, some analytical techniques for the direct determination of organic sulfur,
such as chemical and instrumental methods, have recently been proposed.
The forms of organic sulfur are less well established. Organic sulfur compounds have
been identified in extracts and soluble reaction products from coal, and thiophenic
sulfur forms in coal have been evidenced substantially. Chemical methods, such as flash
pyrolysis, temperature-programmed reduction and oxidation, have been used to quantify
organic sulfur forms.
Furthermore, new instrumental quantification techniques, which involve X-ray
photoelectron spectroscopy and X-ray absorption near edge structure spectroscopy, have
recently been developed. Since all of these quantitative analyses rely on models to deconvolute the data, however, there are difficulties in data interpretation. In summary, the
majority of the organic sulfur in high rank coal is in thiophenic forms, and the
proportion of non-thiophenic groups including sulfide forms is higher in low rank coal,
but the presence of thiol forms in coal is unclear. A better understanding of organic
sulfur forms and quantities is essentially needed for chemical and biological coal
cleaning (see 3.2 and 3.3).
3. Coal Cleaning for Sulfur Removal

The coal cleaning process has traditionally focused on reducing ash-reforming minerals
and not necessarily aimed at removing sulfur in coal until recently. However,
increasingly stringent regulations for SOx emissions during coal combustion have
encouraged technical development of coal cleaning for sulfur removal. Physical
cleaning techniques to remove inorganic sulfur forms, mainly pyritic sulfur, are well
established and widely used. On the other hand, chemical and biological cleaning can
offer the potential to remove organic sulfur, but these methods have not yet been
applied commercially.

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COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT Vol. I - Desulfurization of Coal - Yasuo Ohtsuka

3.1 Physical Cleaning

Physical cleaning of coal is essentially based on the differences in either specific gravity
or surface properties between the organic matter and the associated minerals, although a
few separations that are conducted on the basis of their magnetic and electrostatic
properties have been proposed. All of these methods are generally carried out within
three distinct size ranges, that is, coarse (10150 mm), intermediate (0.510 mm), and
fine (< 500 m). Coarse and intermediate sizes are separated by gravity-based methods,
which become increasingly inefficient for smaller particles. Methods based on surface
property differences are then used. Since conventional techniques are not readily
applicable to ultra-fine particles (generally below 100 m), advanced technologies focus
mainly on cleaning ultra-fines.

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Bibliography

Couch G. R. (1991). Advanced coal cleaning technology, IEACR/44, 95 pp. London: IEA Coal Research.
[This highlights physical, chemical and biological cleaning processes.]
Takeshita M. and Soud H. (1993). FGD Performance and Experience on Coal-Fired Plants, IEACR/58,
138 pp. London: IEA Coal Research. [This reviews the performance and experience of flue gas
desulfurization technology.]
Vernon J. L. and Jones T. (1993). Sulphur and Coal, IEACR/57, 62 pp. London: IEA Coal Research. [This
summarizes legislation on SO2 control and reduction of SO2 emissions.]
Biographical Sketch

Yasuo Ohtsuka is an associate professor at the Research Center for Sustainable Materials Engineering,
the Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, and he
is leading the Laboratory of Catalytic Conversion Chemistry. His research interest includes fossil fuels
conversion, heterogeneous catalysis, environmental protection, and porous materials. After receiving a
Ph.D. in applied chemistry at Tohoku University, he joined the Chemical Research Institute of NonAqueous Solutions (the former name of IMRAM). He was a visiting fellow at CSIRO Division of Coal
and Energy Technology, Sydney, in 1988, and at Energy Research Laboratories, CANMET, Ottawa, in
1993. The Fuel Society of Japan (currently the Japan Institute of Energy) awarded him the prize for
advancements in fuel science in 1989. His groups paper presented in the Division of Fuel Science
Symposium at the ACS National Meeting held in 2000 was also awarded the Richard A. Glenn Award.
He is one of the authors in a Japanese textbook entitled Organic Resources Chemistry to be published
in 2002.

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