A TERM PAPER SUBMITTED ON

COAL BIO-DESULPHURIZATION: CURRENT

PRACTISES AND USE OF MICROORGANISMS
In partial fulfillment of the requirements for the award of the degree of

Master of Technology
(Biotechnology)
By

DeepikaBaranwal
Roll no. MTB/12/1016

Under the supervision of

Dr. SusmitaShukla
(Assistant Professor)

Amity Institute of Biotechnology

Amity University, Noida, Uttar Pradesh.
2013-2014
1

DECLARATION
I hereby declare that the term paper entitled Coal Bio-desulphyurization: Current practices
and use of microorganisms which is being submitted to the Amity Institute of Biotechnology,
Amity University, Noida in the partial fulfillment of the requirements for the award of the
Degree of Master of Technology in Biotechnologyis the result of intensive study of various
research papers by me during my two months summer break.The material contained in this term
paper has not been submitted to any University or Institution for the award ofany degree.

DeepikaBaranwal
M.Tech Biotechnology
ROLL NO. MTB/12/1016
Amity Institute of Biotechnology
Amity University
Noida.

ACKNOWLEDGEMENT
I would like to express sincere gratitude and appreciation to my term paper guide Dr.
SusmitaShukla,Assistant Professor, Amity Institute of Biotechnology for her kind support,
guidance, constructive criticism and timely advice during every stage of this term paper without
which it would not have completed.
I am also thankful to Dr. Prof. K.C. Upadhayay, Advisor &Dr.Prabir Kumar Paul, Head of
the Institution, Amity Institute of Biotechnology for providing the necessary opportunities for
the completion of my term paper.
I also acknowledge our college authorities for providing various magazines and journals for
references and internet facility.
I am sincerely thankful to God for giving me potential to complete this paper successfully, my
family and friends for being my source of strength and motivation who throughout my
academic career supported me with ample affection and constant belief in me.

LIST OF ABBREVIATIONS
SO2
HCl
HNO3
HF
O2
Cl2
H+
H2O
MgO
CB1
FGD
DBT
ASTM

Sulfur Dioxide
Hydrochloric Acid
Nitric Acid
Hydrogen Fluoride
Oxygen
Chlorine
Hydrogen Ion
Water
Magnesium Oxide
Coal bug-1
Fluel Gas Desulphurization
Dibenzothiophene
American Society of Testing Materials

CONTENT
1. ABSTRACT. 6
2. INTRODUCTION... 7
4

3. REVIEW OF LITERATURE...... 8
4. THEORY 10
4.1 COAL..10
4.2 METHODS OF IDENTIFYING SULFUR COMPOUNDS.12
4.3 DESULPHURIZATION METHODS.14-17
4.1.1 Pre combustion
4.1.2 During combustion
4.1.3 Post combustion
4.4 BIO-DESULPHURIZATION METHODS..18-22
Microorganisms
4.5 ACTUATION MECHANISM OF THE MICROORGANISMS.23
4.6 DISSOLUTION OF ORGANIC SULFUR..25
4.7 ADVANTAGES AND DISADVANTAGES...26
5. EXISTING SCENARIO.......................29
6. CONCLUSION..30
7. REFRENCES..31-33.

1.

ABSTRACT

Coal, a non-renewable and maximally exploited energy resource for the production of electricity.
Combustion of coal releases excess amount of sulfur causing various environmental problems. It
is believed that the best method to limit the amount of sulfur oxides emitted into the atmosphere
is to reduce the amountof sulfur in coal before, during or after combustion. The techniques used
include physical, chemical and biological processes. Biological processes offer many advantages
over the conventional physical and chemical processes. It is based on degradation of sulfur
compounds by microorganism. The processes are performed under mild conditions with no
harmful reaction products and the value of coal is not affected. Bio-desulphurization is
discussed from several points of view, with special attention being paid to the most
widely used microorganisms, the mechanism and reactions involved in sulfur
dissolution and, finally, the possibilities of the technique being widely used, taking into
consideration the present state of development of the process.

2.

INTRODUCTION

Coal reserves at present is one of the most exploited non-renewable source of energy. Coal
consumption is so high that the International Energy Agency has forecasted a substantial increase
in coal use over the next few years, rising from 3.5 10 12tons at present to over 5.3 10 12 tons
per year(IEA., 1998). This estimated rate of consumption clearly depicts the complete exhaustion
of our natural resources. Along with this, the nextadverse effect of coal consumption is the
increasing release of harmful gases in the atmosphere.
Various laws have been issued inorder to control the emission caused by the combustion of coal.
Legislationconcerningatmosphericpollutionisincreasinglystrictandemissionsarenowsubjectto
controlandmustbereduced.Forthisreasonitisnecessaryto look for alternative
andcleanerwaysofusingcoal (Beilke and Elshout, 1983).
Of the contaminants involved in coal combustion sulfur dioxide(SO 2) is the most important
together with nitrogen oxides, and this is principally responsible for acid rain. This problem of
S02 emission is complex because low sulfur content coal deposits have been gradually exhausted
and lower quality coal is now being used. Some new rules will lead to a reduction in S0 2
emissions in the medium to long term since it is recognized that a sharp reduction would be
difficult to attain both from an economic and technological point of view.
In this paper, a short survey is made of methods of coal desulphurization. Several aspects of
bio-desulphurization are discussed with special attention paid to the microorganisms used, their
actuation mechanism and possibilities of their commercial application.

3.REVIEW OF LITERATURE
In the present scenario coal is continuingly most exploited source of energy consumption in
medium as well as in future term (Schilling and Wiegand, 1987). Increasing use of coal caused
threat for environment, thus realizing the need for a control on the emission caused by the
burning of coal and a search for some alternative methods was found important (Beilke and
Elshout, 1983).
Inorder to work on desulphurization techniques studies were doneon the various forms of coal
(Rossi, 1990). Coal is found to contain sulfur in three distinct forms
a) Pyritic sulfur
b)Sulfate sulfur
c) Organic sulfur.
The exact formula was not predicted but basic groups and complex aromatic structures were
depicted (Rossi, 1990; Kargi, 1982).
Methods have been evolved for direct determination of sulfate, pyritic and organic sulfur
concentrations in coal (Laban and Atikin, 2000). Such methods are employed to evaluate the
amount of sulfur present in the coal.Various techniques have been involved for the reduction of
sulfur based on before meanwhile or after combustion. Pre-combustion treatment techniques
depend on the physical and chemical properties of the different sulfur compounds (Meyers,
1981).These methods of SO2 elimination also called FGD (Flue Gas Desulphurization) can be
further classified (Prior, 1977; Klingspor and Cope, 1990).
The biological technique for the elimination of sulfur from coal is done with with use of some
specific types of microorganisms (Karlsson et al., 1988).Zurubina et al. (1959) and Silverman el
al. (1963) carried out the first experiments on coal by extracting pyrite in an aqueous phase of
low pH, using bacteria of the Thiobacillusferrooxidans type.Microorganisms werefurther
classified based on their capacity to eliminate one type of sulfur (Kargi, 1986).
Species acidophilic bacteria which oxidize iron and/or sulfur (Eligwe, 1988; Ballester et al.,
1988; Torrna, 1977). Next was the use of mixed culture to lower down the sulfur content in
coal(Kargi, 1986; Beck et al., 1988; thermophilic species Sulfolobus (Kargi and Robinson, 1986;
Kargi, 1986); andPseudomona, the heterotrophs, whose most important characteristics as far as

desulphurization is concerned is their capacity to oxidize dibenzothiophene ( Krawlec, 1988)

along with its future studies were also conducted.
Silverman (Silverman et al., 1963) was one of the first researchers to establish the mechanism of
the biological oxidation of pyritic sulfur whereas the mechanism of organic sulfur dissolution is
practically un researched, although the researched is now started (Van Affenden et
al.,1991;Olsson et al., 1991).Mechanisms proposed to explain the dissolution of pyrite are based
on the form in which the bacteria act on the mineral by a direct or indirect mechanism ( Torm.,
1977).The biochemical mechanism of elimination, by the rupture of these C-S bonds and it tries
to characterize the enzymes involved using Brevibacterium as desulfuring agent (Kilbane,
1989;Van Affenden et al., 1991).Several flow sheets have been proposed for bio-desulphurization
in one or two stages (Sproull et al.,1986; Kargi, 1982) depicting the overall path for the
elimination of maximum amount of sulfur.

4.THEORY
Coal is the largest source of energy for the generation of electricity worldwide, as well as one of
the largest worldwide anthropogenic sources of carbon dioxide releases. In 1999 world
gross carbon dioxide emissions from coal usage were 8,666 million tons of carbon dioxide (IEA ,
2006). Coal-fired electric power generation emits around 2,000 pounds of carbon dioxide for
every megawatt-hour generated, which is almost double the approximately 1100 pounds of
carbon dioxide released by a natural gas-fired electric plant per megawatt-hour generated.

4.1COAL:
Coal is a black or brown sedimentary rock that can be ignited and burned to produce energy in
the form of heat. Coal's chemical makeup is a complex mix of elements that include sulfur,
carbon, oxygen, hydrogen and nitrogen, as well as small quantities of aluminum, zirconium and
many other minerals ( Blander, M., 2011) .
There are several different types and ranks of coal. Coal is classified by degrees of hardness,
moisture and heat content. Anthracite is hard coal, almost pure carbon, and containing the
highest Btu content. (British thermal unit - a measure of the energy required to raise the
temperature of one pound of water by one degree Fahrenheit.); Bituminous is soft coal, the most
common type in the United States, used to generate electricity and to make coke for the steel
industry; Lignite is the softest coal, has the highest moisture content and is used for generating
electricity in certain parts of the country and for conversion into synthetic gas; Subbituminous
has a heating value between bituminous and lignite, and has low-faced carbon and high
percentages of volatile matter and moisture.
Coal is basically composed of carbonaceous matter with several mineral inclusions. Sulfur is
present in the form of inorganic and organic compounds (Table l).

10

Main sulfur compounds in Coal

Inorganic
Pyritic
Pyrrhotite
Sulphate

(FeS2)
(FeS)
(FeSO4,Fe2(SO4)3,CaSO4,
BaSO4)
Organic sulfur

Sulphides
R1-S-R2
Disulphides
R1-S-S-R2
Thiols
R-SH
Thiophenes
Dibenzothiophenes
R groups = alkyl or aromatic groups
Table 1:

According to the nature of these compounds, the following Classification of sulfur can be
established:
A. Pyritic sulfur :
Principally composed of iron pyrite or marcasite, depending on the crystallographic structure,
although other crystalline species of iron sulphide have been found with a different
stoichiometry, such as pyrrhotite (FeS) (Rossi, 1990). It is found as finely scattered nodules or
inclusions. According to the morphology and distribution, it is referred to as crystalline, massive,
nodular, fusiform, granular or globular pyrite. Effectiveness of elimination of this type ofsulfur
depends on the morphology and above all on the degree of dispersion through the coal.
The quantity of pyritic sulfur varies (between 0.5 and 6%) depending on the type of coal.
Bituminous Coal usually has a higher percentage than subbituminous coal and lignites.

B. Sulphate sulfur :
Mainly in the form of iron sulphate (formed by chemical oxidation of pyrites in the air) or
calcium and barium sulphate. The content of this type of sulfur is usually very low in nonoxidized coals and is hardly worth mentioning since it is very easily solubilized by a simple
washing process. Some coals also have a small elemental sulfur content (<0.2%) (Greer, 1979).
11

C. Organic sulfur :
It is found as aromatic and aliphatic compounds forming part of the molecular
configuration of the coal. It is, therefore, very difficult to remove by mechanical separation
techniques. The exact formula of these organic sulfur compounds is not known although some of
the principal groups have been identified: sulphides (R1SR2), disulphides (R1S--SR2),
thiols (R--SH) and thiophene complex aromatic structures. Dibenzothiophene (DBT) is one of
the most abundant and refractory of the sulfur compounds and has been used as a model
compound in studies of bio-desulphurization.

4.2Methods of analyzing and identifying

sulfurCompounds:
Whilst there is a need for coal desulphurization, techniques to quantify and identify sulfur
compounds in coal are also required. The customary methods used are the standard methods of
the American Society of Testing Materials (ASTM): a coal sample is analyzed chemically to
determine total sulfur (ASTM, 1993) and sulfate sulfur; pyritic sulfur is calculated from pyritic
iron (ASTM, 1994); and organic sulfur is obtained indirectly by subtracting the sulfate and
pyritic sulfur contents from total sulfur content. The techniques are time-consuming and not
consistent. Many errors can be introduced in each stage of the analysis. Thus, it is difficult to
monitor accurately the efficiency of the different desulphurizationprocesses.
Recently, THE SEQUENTIAL DIGESTION method has been reported for the direct
determination of sulfate, pyritic and organic sulfur concentrations in coal (Laban and Atikin,
2000).
A three-stage extraction was developed, using acid digestion in a microwave oven.

In the first stage, 5M HClwas used to dissolve sulfate phases in coal. Pyrite was then extracted
using 2M HNO3. The final stage, for the determination of organic sulfur, involved the use of
concentrated HNO3, HCl, hydrofluoric acid (HF) and boric acid for thecomplete decomposition
of residue that remained following stage 2. The extract solutions from each stage were analyzed
for sulfur by inductively coupled plasma atomic emission spectrometry (ICP-AES).
12

The sums of the three forms of sulfur have shown consistent agreement with certified total sulfur
data for most of the coals studied. The good precision achieved by this technique suggests that
the process has an acceptable degree of reliability. However, the use of HF poses a potential
hazard which should be avoided.
All of the procedures described above are destructive methods. Non-destructive methods for
sulfur determination are preferable. The instrumental techniques which have been predominant
in sulfur determination in coal are based on ELECTRON MICROSCOPY, such as X-ray
photoelectron spectroscopy and X-ray absorption near edge spectroscopy (Davidson, 1994).
However, to date, uses of the non-invasive methods suffer from inadequate resolution. In
addition, the techniques are highly specialized. Further studies and development of the analytical
methods of sulfur in coal are required.

4.3DESULPHURIZATION METHODS:
The need to obtain coals low in sulfur from low quality coals (totalsulfur higher than 1.5%) has
led to the development of a large number of desulphurization methods. The choice of the most
suitable method being conditioned by the coal type of installation in operation and restrictions
referring to SO2 emissions. It is necessary, when discussing sulfur removal, to take into
consideration local economic and energy factors as well as environmental ones.
The different methods used can be classified into three broad groups depending on whether
they are applied before, during or after coal combustion (Table 2).
13

a) Physical

Main desulphurization methods

1. Desulphurization before combustion
Gravimetric

methods:

Magnetic
Electric
Flotation

b) Chemical

Oil agglomeration

methods
c) Microbiological
desulphurization
methods
2. Desulphurization during combustion
a) Injection of lime into boilers
b) Fluidized bed
3. Post-combustion desulphurization: Flue gas desulphurization
process (FGD)
a)
b)
c)
d)

Sorbent injection
Spray dry scrubbers
Wet scrubbers
Regenerable systems

4.3.1 Desulphurization before combustion :

Pre-combustion treatment techniques depend on the physical and Chemical properties of the
different sulfur compounds (Meyers, 1981), and can be divided into:
I.
II.
III.

Physical methods
Chemical methods
Microbiological methods (bio-desulphurization)
The first are based on the different physical properties of the inorganic compounds of sulfur in
relation to the coal; the second on selective chemical reactions which convert them into easily
soluble compounds; whilst bio-desulphurization is based on the capacity of certain
microorganisms to oxidize the sulfur compounds.
A brief account follows ofthe different variations used in the first two cases, since
microbiological desulphurization will be treated in more detail later.

14

PHYSICAL METHODS:
Gravimetric, magnetic, electric and flotation are the most common physical methods used.
Gravimetric techniques are based on the different densities of coal and pyrite (1:4). Coal is
ground to a size which liberates the pyrite and is then submitted to a process of selective
separation using shaking, boxes or tables, etc. This method is only suitable when the pyrite is
present in the form of large particles because if it is finely disseminated throughout the coal
matrix (with a size of less than 40-50 m), yields are very low.
Magnetic processes have the disadvantage of not being usable directly since neither coal nor
sulphides (except pyrrhotite) is magnetic. A previous treatment is necessary to transform pyrite
into a substance susceptible to magnetic concentration. It can, for example, be treated with
superheated steam and air to produce superficial transformations into magnetic, hematites and.
possibly, pyrrhotine. The Magnex process, on the other hand, uses iron pentacarbonyl to
incorporate superficial iron atoms into pyrite and convert it into pyrrhotine.

Electrical concentration methods are based on the differences in conductivity between sulfurbearing compounds and coal. However, this method cannot be used on steriles, it is very
sensitive to humidity, has little capacity and, lastly, is not effective on particles of less than 100
m due to interferences in the electric current and to air current.
Flotation depends on the different degrees of wettabilily of' coal and pyrite. This is one of the
most widely used methods and can be applied to very small particles. It is, in fact, used in many
washers to treat fractions of 0.5 mm or less. This use of the natural floating capacity of coal is
only viable with some coals since the youngest and most oxidized coals do not have this
capacity. What is more, finely ground crushed coal tends to oxidize rapidly so that its floatability
decreases. For this reason, the most recent techniques favors the flotation of pyrite, sinking the
coal (after a joint flotation to eliminate steriles).
To summarize, physical methods, which are the most widely used, have serious disadvantages
since they cannot eliminate organic sulfur, they have size limitations and much coal is lost when
the pyrite is finely distributed (losses of up to 40%), They are, therefore, not suitable for poor
coals with a high ash and sulfur content, especially lignites.
15

CHEMICAL METHODS :
A great variety of chemical desulphurization methods have been developed in the laboratory.
These are based on the solubilization of' the two types ofsulfur (Morrison, 2004) and can be
classified into two groups depending on the chemical procedures used:
a) Those which eliminate sulfur by oxidation using ions (Fe 3+), strong acids (HNO3, HC1,
HCiO4) and gases with a high oxidation potential (O2, Cl2, etc).
b) Those based on reactions which displace the sulfur by treatment withsodium hydroxide
solutions. The Battelle process and the General Electric (GE) microwave treatment belong to this
group.
Although these chemically based desulphurization processes eliminate large quantities of
pyritic sulfur and varying quantities of organic sulfur, they operate at high temperatures and
pressures and use corrosive leaching agents. They involve very high energy consumption and
very complex equipment. At present day prices of coal it is to justify the application of these
methods on an industrial scale.

4.3.2 Desulphurization during combustion :

Included in this category are those processes which carry out desulphurization inside the
combustion boilers themselves. These are based on the retention of SO2 ascalcium sulphate
after the addition of calcium carbonate (CaCO3) or dolomite (CaCO3~MgCO3),
There are two ways of retaining the sulfur (Podolski, 1984; Benz and Flament, 1985): by
injection of lime into the conventional burners or by combustion of a "fluidized" bed. The first
gives rise to problems with the burners and is not very efficient. The second reduces SO 2 emitted
by up to 90% by means of low cost absorbents added to the fluidized bed.
Although this is a modern and technologically well-developed procedure, it involves high
capital investment and is, therefore, not very widespread. At the moment it only seems viable in
new plants and in those of a high capacity.

4.3.3 Post combustion desulphurization :

16

This technique is applicable regardless of the form in which sulfur occurs in the coal and of the
type of coal since it is applied to the gases produced by combustion and where the sulfur is
combined with oxygen (principally as SO2).
These methods of SO2 elimination also called FGD can be classified into two general groups.
The first involves re-generable systems, which produce a final product with no-usable residues
and the second produces a commercially useful product, such as elemental sulfur or sulfuric acid.
Both methods use a wash tower, where gases from the burner come into contact with a sorbent
which extracts the SO2. It is the type of absorbent used which principally differentiates these
methods (CaO, CaO3, NaCO3, MgO, etc).
In general, these methods require complex installations, which have to be carefully
monitored and are, therefore, expensive to run in spite of the saleable product obtained.

4.4BIODESULPHURIZATION
Parallel to the physical and chemical methods described above, alternative biotechnological
techniques have been the subject of much investigation during the last decades. These include
desulphurization, liquefaction and gasification procedures, summarized in different reviews
(Kargi, 1986; Olson and Brinckman, 1986; Gouch, 1987; Bos and Kuenen, 1990). Table 4 shows
several examples of biotechnology applied to coal (Karlsson et al., 1988).
Table 3:
Examples of microbial action on coal on various stages of development (Karlsson el al., 1988)
Microbial

Potential

Status

action
Secreted

application
Coal slurry

Laboratory

proteins
Coal structure

Coal

Laboratory

degradation
Coal-N as

liquefaction
NO2 reduction

laboratory

nitrogen source
Surface

Pyrite flotation

Bench scale
17

properties
Pyrite

Desulphurizatio

Bench scale

oxidation
Oxidation of

n
Desulphurizatio

Pilot plant

organic sulfur

The most widely studied technique to date has been microbiological desulphurization.
Silverman et al. (1963) carried out the first experiments on coal by extracting pyrite in an
aqueous phase of low pH, using bacteria of the Thiobacillusferrooxidans type.

The principles of bio-desulphurization lies in the capacity of certain microorganisms to oxidize

the reduced compounds of sulfur found in coal and convert them into products soluble in an
aqueous medium.

Microorganisms :
In general, different types of bacteria are needed to eliminate pyrite and organic sulfur since the
principle of solubilization is different. Those which dissolve pyrite use sulfur as energy source,
while those which eliminate organic sulfur do so as a secondary metabolic function.
Microorganisms, then, can be classified according to their capacity to eliminate one type of
sulfur (Kargi, 1986) (Table 4) in three groups:
a) Obligate autotrophs, which oxidize only pyritic Sulfur.
b) Facultative autotrophs, which oxidize pyritic sulfur and somecompounds of organic sulfur.
c) Heterotrophs, which oxidize organic compounds only.
Table 4 :
Main microorganisms used in bio-desulphurization
1. Autotrophs

18

a) Obligate

Thiobacillus ferrooxidans
Thiobacillusthiooxidans
Leptospirillum ferrooxidans

b) Facultative

Sulfolobus acidocaldarius
Sulfolobusbrierleyi
Thiobacillus acidophilus
Thiobacillitermophilus (TH1)

2. Heterotrophs
Pseudomonas (Putida, aeruginosa, CBI, beijerinckia)
Beggiatoa

Within the first group (a) are included the microorganism responsible for the oxidation of
pyritic sulfur. There are acidophilic bacteria which oxidize iron and/or sulfur (Eligwe, 1988;
Ballester el al., 1988), the most commonly used of which has been an autotrophic species of
Thiobacillusferrooxidans, isolated in mine waters, mesophilic (optimum development
temperature of 28 to 35C) and capable of extracting large quantities of pyritic sulfur (more than
90% in some cases). It has been used pure and in mixed and natural cultures in which there are
other species in smaller proportions, such as T.thiooxidans, Leptospirillumferrooxidans and
Thiobacillusacidofilus, principally (Dugan and Apel, 1978; Andrews land Maczuga, 1984).
The advantage of using mixed cultures lies in the fuller exploitation ofthe characteristics of each
microorganism. Generally, a mixed culture of T.ferrooxidans and T.thiooxdans dissolves pyrite
to a substantially greater extentthan either of the bacteria separately. T.thiooxidans is thought to
favour the activity of T. ferrooxidans by oxidizing the elemental sulfur formed in intermediate
reactions. T.acidofilus is known as a satellite microorganism since in mixed cultures it feeds on
the degradation products of T. ferrooxidans and T.thiooxidans, preventing the saturation of the
reaction medium by these products.
Recent experiments have also indicated that T. ferrooxidans can eliminate some of the organic
sulfur (Chandra and Mishra, 1988). The most promising results have been obtained by using a
moderately thermophilic species, THI, with which they have managed to dissolve around 50% of
organic sulfur working at a temperature of 50C (Gckay and Yurteri, 1983).
19

Microbial leaching with microorganisms which oxidize sulfur and iron can be used to
eliminate pyritic sulfur, although one of the problems in using cultures of Thiobacillusand
Sulfolobus in the microbial leaching of sulfur minerals and coal is the formation of insoluble
precipitates (jarosites), However, this can be avoided by operating at a low pH.
Leptospyrillum can dissolve pyrite at pH values at which T.ferrooxidans does not work. This
bacterium oxidizes iron, when used as a pure culture or when mixed with other sulfur-oxidizing
bacteria. Microbial leaching with Leptospyrllum eliminated 85% of pyritic sulfur in 40 days,
30% of which was oxidised to elemental sulfur and the rest transformed into soluble sulphate.
With a mixed culture 83% of the pyritic sulfur was eliminated. These results suggest that
elimination of pyritic sulfur by both types ofculture is very similar and that T. ferrooxidans is not
essential for the oxidation of pyrite (in a mixed culture).

However, the accumulation of elemental sulfur due to the oxidation of pyrite by

Leptospyrillum indicates an indirect leaching mechanism. As mentioned above, this
accumulation can be avoided by using Leptospyrillummixed withT.ferrooxidans. After 14 days
elemental sulfur remains constant and less than 10%.
Among the second group (b), new species capable of solubilizing organic sulfur and pyritic
sulfur have been identified, for example the thermophilic species Sulfolobus (Kargi and
Robinson, 1986; Kargi, 1986) which develops at temperatures between 60 and 80C, in acidic
medium (pH 1.541). The exact mechanism by which these microorganisms solubilize organic
sulfur is not known. According to Kargi the species Sulfolobusacidocaldarius is capable of
oxidizing to sulphate 65% of the sulfur content in dibenzothiophene.
However, these results have not been repeated in other coals and most research has failed to
demonstrate the biochemical metabolism of organic sulfur (Kilbane, 1989).
Thisuncertainty concerning the results is largely due to the difficulties involved in determining
the exact organic sulfur content of coal and to the possibility that some organic sulfurs dissolves
naturally at high temperatures.
As regards the elimination of inorganic sulfur,S.acidocaldarious oxidizes it twice rapidly as
T.ferrooxidans,reducing by50% the residence time.Sulfolobusprovides two reasons a)the
possibility of eliminating compounds of organic sulfur, which are the most difficult to dissolve,
20

and b)the improvement in the chemical oxidation kinetic at temperatures which favour the
development of these microorganisms.
The third groups of microorganisms (C) are the heterotrophs which need organic substrates to
develop and which also contribute to the degradation of inorganic matter by liberating chelating
and complexing agents. The most studied species of this group are Pseudomonas, whose most
important characteristics as far as desulphurization is concerned is their capacity to
oxidizedibenzothiophene ( Krawiec, 1988).
The experiments involving P. pudita and P.aeruginosa should be mentioned as they dissolve
up to 75% of pyritic sulfur and 37% of the organic sulfur (Ray and Reyners,1988).
In some species of Pseudomonas, the DBT oxidation capacity is codifiedin a plasmid and it is
therefore, possible to improve them by generic engineering. Indeed, the mutated microorganism
Coal bug-1 (CB1) has been developed from Pseudomonas.

This organism operating in non-sterile environment can separate sulfurfrom the thiophenic rings
present in DBT and coal. The sulfur is converted into sulphate and, in the case of DBT, the coal
atoms, initially bound to the sulfur, are converted into phenolic centers. This is the optimum form
of desulphurization since it is not accompanied by a significant rupture of the coal structure.
The efficiency with which CBI eliminates thiophenic sulfur from coal slurry depends on the
type of coal, on the coal microorganism ratio and on the coal particle size. The process can act
continuously and is already operating in a pilot scheme.
CBI oxidizes thiophene at temperatures between 25 and 40 o C, atan approximately neutral pH
and can eliminate upto 40% of organic sulfur from some types of coal. However, it has not been
shown efficiently in the dissolution of pyritic sulfur and so this has to be eliminated by other
means. Since CBI does not survive at low pH media is necessary for T. ferroxidans and S.
acidocaldarius, it cannot be used in cultures mixed with bacteria which eliminate pyrite
(Kawatra et al.,1987).
The Atlantic Research Corporation, which developed CBI, is now working on CB2, a
microorganism capable of attacking diphenilsulphate directly. It has been tried on coal and it can
eliminate upto 30% of organic sulfur.

21

Naturally, the results are specific to certain types of coal and depend on the nature of the
organic compounds in each type.
Apart from the above mentioned microorganisms,there are other bacteria, not so well known or
developed, which have produced hopeful results.
Little, for example, is known of the capacity of the species Beggiatoa to eliminate sulfur from
coal. This is a flat filamentousbacterium which oxidizes sulphides to elemental sulfur and then to
sulphates. Recent studies have been made with Beggiatoaalba ATCC 33555 and desulphurization
experiments have been carried out on coal. This organism operates atpH7.5 (Lee et al., 1991).
Other studies concentrates on the development of microorganisms such as Escherichia coli,
Thermothrix, Thiosphaera, Alcaligenes and Brevibacteriumspecies, among others.

4.5ACTUATION MECHANISM OF THE

MICROORGANISMS
The mechanism of the chemical reactions involved in bio-desulphurization is not understood in
detail. Silverman was one of the first researchers to establish the mechanism of the biological
oxidation of pyritic sulfur. The most advanced theories are the resultof studies on the studies on
the bioleaching of mineral ores and for this reason the mechanisms established refer only to
pyritic sulfur. The mechanism of organic sulfur dissolution is practically un researched, although
the researched is now started (Van Affenden et al.,1991;Olsson et al., 1991).
Mechanisms proposed to explain the dissolution of pyrite are based on the form in which the
bacteria act on the mineral. For this reason one speaks ofa direct or indirect
mechanism.According to the direct mechanism, the action of the bacteria is by physical contact
between the bacteria and pyrite by means of intercellular enzymes. This catalyzes the following
global reaction:
MS+2O2 MSO4
Thismechanism is based on microscopic observation of the mineral surface. The adhesion of the
bacteria to the pyrite surface provokes pitting and hollows where there is contact (Bennet and
Tributsch, 1978).

22

As important as or even more important than the direct mechanism may be the indirect action of
bacteria which catalyzes the oxidation of ferrous to ferric oxide.
Oxidation of pyrite in an aqueous and oxidation medium gives rise to the formation of ferric
sulphate through a series of reactions which can be resumed thus:
FeS2+ 3.5 O2 + H2OFeO4 + H2SO4
The fero-oxidising bacteria act on the ferrous ion it to ferric, thus obtaining the energy necessary
to synthesize the cellular material from carbon dioxide:
2FeSO4 + 0.5O2 +H2SO4 Fe2(SO4)3 +H2O
The velocity of this reaction in the presence of bacteria is approximately 10 6 times greater than in
their absence.
In its turn, the ferric ion is a strong oxidant in acid solutions and acts as a leaching agent on the
pyrite, according to the following reaction:
FsS2 + 2 Fe3+ 3 Fe2+ +2 S0
The elemental sulfur which results from the oxidation of pyrite [4] can be oxidized by ferric ion:

S0 + 6FE3+ + 4H20 6FE2+ +SO42- + 8H+

Or by oxygen, in which case the bacteria, which oxidise the sulfur, catalyse the reaction :
2S0 + 3O2 +2H2O 2SO4 2- + 4 H+
In this way, the oxidizing and acidic medium suitable for the oxidation of metallic sulphides is
regenerated in a cyclic manner by the action of the bacteria:
14Fe3+ + FeS2 + 8H2O 15 Fe2+ + 2S0
Bacteria (T.ferrooxidans) and oxygen
2SO4 + 16 H+
The effect of iron ions in bacterial desulphurization may be counterproductive, due to their
inhibitory effect on the bacterial oxidation caused by high concentrations of these ions in the
solution. Furthermore, the ferric ion may be hydrolyzed to form insoluble hydroxides Fe(OH) 3
and basic sulphates [(HFe3(SO4)2(OH)6)] if the pH is above 2.0. The precipitation of jarosite or
hydroxides has an unfavorable effect on bacterial activity and inhibits the transfer of the oxygen
and, therefore, the oxidation.
Both the direct and indirect mechanisms of pyrite oxidation act simultaneously and together. The
essential condition for the oxidation reactions to occur is that the pyrite surface should be

23

accessible and, for this reason, the porosity of the coal in question plays an important role (Hone
et al., 1987).
Both mechanisms can act ifthe pores are sufficiently large for the microorganisms to penetrate
and pyrite particles. If the pores are very small (micropores), the diffusion of ferric ions asa far as
the pyrite is possible but the bacteria cannot penetrate, in which case only indirect oxidation is
possible.

4.6DISSOLUTION OF ORGANIC SULFUR :

The mechanism of organicsulfur elimination is much more complex and less understood than
that of pyritic sulfur. As has been said before, organic sulfur forms part of the structure of
coalwith chemical bonds (S-C) dispersed throughout the hydrocarbon compounds and for it to be
eliminated, these bonds have been broken. For this to happen, the organic compounds of sulfur
must come in contact with the leaching agent and so as the coal has to be finally crushed. Since
there are many different organic compounds ofsulfur, there is probably no one microorganism
capable of degrading all of them and so a specific enzyme must be found for each bond.
The first studies on the dissolution of organic sulfur have beenconcentrated on the degradation
of heterocyclic compounds, using dibenzothiophene as model compound (Kargi and Robinson.
All these studies provided information on the kinetic of elimination but not on the biochemical
mechanism involved. More recent research (Kilbane, 1989;Van Affenden et al., 1991)
concentrates on this biochemical mechanism of elimination, on the rupture of these C-Sbonds
and tries to characterize the enzymes involved using Brevibacterium as desulfuring agent. Olsson
et al (1991) proposes a direct mechanism for the elimination of organic sulfur by a species of
Sulfolobus and has identified the resulting compounds of dissolution and their influence on
microbiological activity.
24

4.7ADVANTAGES

AND

DISADVANTAGES

OF

BIODESULPHURIZATION :
There are three potentially attractive advantages of microbiological desulphurization:
a) The low costs involved because of the simplicity of the equipment and the low consumption of
reagents during process since these micro-organisms regenerate the leaching agent.
b) Low energy consumption as the process works at near ambient temperatures and atmospheric
c)

pressure.
The possibility of eliminating the finely dispersed pyritic sulfur and part of the organic sulfur

with no loss of coal.

To the above must be added other advantages as regards the economic viability of the process:
d) The possibility of reducing the ash content.
e) The compatibility of the process with the hydraulic transport of coal and with the coal-water
mixture technique.
However it must be said that the process is slow, and in general long periods of treatment are
necessary (1 or 2 weeks). Further research should concentrate on reducing this time to make the
process economically competitive.

25

5. EXISTING SCENARIO
Two different routes could be currently used for reducing the sulfur content of coal:
a) Microbial oxidation of the sulfur as the only treatment
b) Modification of the surface properties of pyrite by microorganisms to improve their separation
by conventional physical processes.
Several flowsheets have been proposed for bio-desulphurization in one or two stages (Sproull et
al.,1986) and Figure 1 shows a typical process scheme. A physical method of desulphurization
can first be applied to the coal (floatation, for example) and in this casethe fraction with
ahighsulfur contentwould be fed into the bioreactors. The same or different microorganisms can
be used in the two reactors: for example T.ferrooxidans in the first to eliminate pyritic sulfur at
35o C and Sulfolobus in the second to eliminate organic sulfur at 70 oC. The solutions are
continuously recycled and since they contain the products of sulfur oxidation, the suitable
composition is maintained by precipitating sulphates by the addition of lime.
70
60
50
40
30

Microbiology

Coal Chemistry

Process Design

Economic/ Engineering

20
10
0
1

The greatest complication with this flow sheet is the reactor design, since long residence times
are necessary, even with systems which are agitated, and because of the corrosion acid solutions.
Three different configurations are proposed for large scale operation ( vaseen, 1985): agitated
reactors in series, horizontal reactors or pipes for the transport of coal slurries.

26

It is relativelyeasy to control the process in the agitated reactors,whether they are moved
mechanically or pneumatically. The latter, similar to Pachuca tanks used in Hydrometallurgy,
seem more suitable because this type of movement favors coal-microorganism contact and the
cells are not destroyed by mechanical impact.
Horizontal rotate reactors are large cylindrical reactors which turn at a velocity (1-20rpm) which
maintains the coal and bacteria in suspension and which have an air supply throughout their
length. The reactors are usually quite large with a diameter ratio of 20/1 in case of T.
ferrooxidansdesulphurization.
Costs are reduced by the use of appropriate transport pipe, although in this case it is much more
difficult to control the process as regards pH, aeration, precipitation products of oxidation on the
walls, etc. However this is a very interesting alternative especially if advances can be made in
coal-water mixtures so that a liquid fuel might be used directly with no need for drying step
(Armson, 1986).
The possibility of bio-desulphurization in heaps is also under consideration as this procedure has
been shownto be economically interesting in the bioleaching of minerals. Both investment costs
and energy requirements are less than with agitated systems.
The other method of In situ desulphurization which basically consists of percolating an acid
solution with bacteria (mine waters) through heaps of coal. Among the parameters which affect
the efficiency of this process and which are yet to be determined are the appropriate particle size
of the coal and pyrite, sulfur distribution, coal porosity and jarosite precipitation.
The best results obtained by this method (Beier, 1987) indicate that it may be possible to
eliminate 90% of the pyritic sulfur from coal ata cost of $3 per ton. However, recent studies
suggest that the elimination of pyrite is 10-15% less with agitated systems in periods of time
longer than 100 days.
Indeed, the principal advantage of using microbiological desulphurization as the sole
treatment is its slow kinetics. The time needed to eliminate large quantities of sulfur is such that
it adversely affects the size of the installations necessary and the cost. If this time could be
reduced, the process would obviously be more appealing.
Probably the best way of reducing these costs would be to use the second alternative mentioned
above, a combination of bio-desulphurization and conventional physical methods, principally
those which depend on the surface properties of the pyrite or coal ( floatation and oil
agglomeration) ( Kempton et al., 1980; Attia and Elzeky, 1985).
27

Presently, work is being done to convert pyrite, initially with bacteria over short times or even
the floatation cell itself and in this way favour pyrite-coal separation.

28

6. CONCLUSION
After going about all the advantages and disadvantages, the selection of the best option is a
complex subject and all the factors which intervene in the running of a thermal power station
must be kept in mind. For example, if the coal is of high quality, a physical bio-desulphurization
or cleaning method may be sufficient and costly alternative can be avoided.
On the other hand a large power station using low quality coal may find the installation of a
fluidized bed economically acceptable, since the large quantities of coal treated wouldoffset the
capital investment.
Without doubt the best method is that which entails the least cost but which cleans the coal
rapidly andreliable . Bio-desulphurization, because of

Its flexibility in treating all types of coal

Its attack times can be reduced to reasonable levels
It involves natural resource exploitation
It maintains a cleaner and safer environment
It is cheap investment with better results
Higher desired output is achieved.

At present time there is a tendency to research and development on an industrial scale,

concentrating on the following points:
1. Increasing the reaction speeds by the use of thermophilic microorganisms or mixtures which,
either through working at high temperatures or by symbiotic phenomena, can increase the
2.
3.
4.
5.

oxidation reactions.
Developing genetically new more specific microorganisms capable of solubilizing organic sulfur.
Developing reactors which permit a better kinetic.
Improvement of the floatation method and research into coal-water mixtures.
Construction of pilot plants which reveal energy requirements and actual costs.

7.REFERENCES
Andrews, G.F. and Maczuga ,J (1984)Bacterial Removal of pyrite from Coal,Fuel, 63,297-302.

29

Armson,R.(1986). Water makes coal a brighter fuel, new scientist, August 28, 44-47. Atkins, A.S (1978)
Studies on the oxidation of sulphide minerals (pyrite) in in the presence of bacteria
ASTM. 1993. Standard test method for total sulfur in the analysis sample of coal and coke. ASTM
D3177.
ASTM. 1994. Standard test method for forms of sulfur in coal. ASTM D2492.
AttiaY.A.,yElzeky, M.A. (1985). Biosurface modification in the seperation of pyrite from coal by
froth flotation in coal science and technology 9,(Y.A. Attia, ed.). processing and utilization of
high sulfur coals pp. 673-682. Elsevier, Amsterdam.
Ballester,

A.,

Gonazalez

F.

and

Blazquez,

M.L.

(1988)

.Biolixiviacion

de

menasnaturales.Posibilidadesactuales de utilizacion. Rev, Metal, Madrid.

Beilke, S. and Elshout, A.J. (eds) (1983) Proc. ECE Workshop Acid Deposition. D.
Reidelpublishing comp. 1983.
Beier , E.(1987). Pyrite decomposition and structural alterations of hard coal due to microbeassistd pyrite removal, Proc.biologicaltretament of coal workshop, pp. 389-424. Vienna, Va.
Bennett, J.C and Tributsch, H., (1978). Bacterial Leaching patterns on pyrite crystal Surface, J
Bacteriol., 134, 310-317.
Blander, M. Calculations of the influence of additives on coal combustion deposits. Aragonne
National Laboratory. Retrieved 17 December 2011).
Chandra. D. and Mishra, A.K (1988). Desulphurization of coal by bacterial means resources.
Conservation and Recycling. 1. 293-308.
Dugan, P.R. and Apel, W.A. (1978), Microbial Desulphurization of Coal, In Metallurgical
Application of Bacterial Leaching and Related Microbiological Phenomena,(L.A, Murr,
A.E.Torma and J.A.Brierly, eds), pp.223-250. Academic Press,New York.
Eligwe, C.A (1988). Microbial Deulphurization of coal.
Greer, G.T. (1979). Organic and Inorganic Sulfur in Coal.Scanning electron microscopy.
Gockay, C.F. and Yurteri, R.N. (1983) Microbial Desulphurization of Lignites by a Thermophilus
Bacterium.
IEA. 1998. International Energy Agency WorldEnergy Outlook, 1998 edition.
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International Energy Annual 2006.Energy information Administration, 2008.Archived from

original on 23 may 2011.
Kargi, F. (1986).Microbial Methods for desulphurization of coal.Trends Biotechnol.
Kargi .F. and Robinson, J.M. (1986).Removal of organic sulfur from Bituminious coal.Use of
ThermophilicSulfolobusacidocaldarious.
Kawatra, J.D., Wyza, R.E., Lippold, j., De Souza, A. and Anspach, G. Bioprocessing of coal.
Basic Life Sci. (Environ. Biotechnology).
Kempton .A.G., Moneib, N., McCready, R.G.L. and Capes, C.E. (1980).Removal of pyrite from
coal by conditioning with THIOBACILLUS FerrooxidansFollwed by Oil agglomeration.
Hydrometallurgy, 5, 117-125.
Kilbane, J.J. (1989). Desulphurization of coal: The microbial solution. Tibtech.
Krawiec.S. (1988).Detection and Initial characterization of bacteria with the ability to desulfurize
Dibenzothiophene to Biphenol. Proc. Annu. Int. Pittsburgh coal conf.
Laban, K.L. and Atikin, B.P. 2000. The direct determination of the forms of sulphur in coal using
microwave digestion and i.c.p-a.e.s analysis. Fuel, 79.
Lee, K.L., Blazquez, M.L. and Yen, T.F. (1991). New Filamentous Bacteria for coal
desulphurization. (D.L. Wise. Ed.). Bioprocessing and Biotreatment of coal. Marcel dekkerinc.
Metallurgical Applications of Bacterial Leaching and related phenomenia,(L.A Murr,A.ETorma
and J.A Brierley,des). Pp. 403-424, Academic press, new york.
Morrison, G.F. (2004). Chemical Desulphurization of coal. IEA Coal research London.
Rossi, G. (1990). Biohydrometallurgy,McGraw-Hill Publ. Co. New York.
Podolski, W.F. (1984). Fluidized bed combustion.Thescience and technology of coal and coal
utilization.

Ray, C. and Reynerrs, P. (1988).Microbial desulphurization of coals by Oranism of the Genus

Pseudomonas, Biotec.Process.
31

Silverman, M.P., Rogoff. M.H. and Wender, I. (1963).removal of pyritic sulfur from coal by
bacterial action.
Van Afferden , M., Beyer, M., Schacht, S. and Klein, J, (1991). Potential Biochemical
Mechanism for the removal of organic sulfur from coal. Aint.Symp.Environmental
Biotechonology. Pp. 123-126. Oostened.
Vaseen, V.A. (1985), Commercial Microbial Desulphurization of coal. Processing and Utilization
of High-Sulfur Coals, Coal Science And Technology #9, pp. 699-715. Elsevier.

32

AMITY UNIVERSITY

AMITY INSTITUTE OF BIOTECHNOLOGY

RESEARCH PAPER ON:

COAL BIO-DESULPHURIZATION:
CURRENT PRACTISES AND USE OF
MICROORGANISMS

Guided by :- Submitted by :Dr. SusmitaShuklaDeepikaBaranwal

Lecturer,AIBM.Tech[BIOTECH],Sem-3rd

Amity Noida.

Sec-A,

33

CONTENT
5
INTRODUCTION.
6
REVIEW OF LITERATURE
7
MATERIAL AND METHODS
7.3
COAL
7.4
METHODS OF IDENTIFYING SULFUR COMPOUNDS
7.5
DESULPHURIZATION METHODS
8 Pre combustion
9 During combustion
10 Post combustion
10.3 BIO-DESULPHURIZATION METHODS
Microorganisms
10.4 ACTUATION MECHANISM OF THE MICROORGANISMS
10.5 DISSOLUTION OF ODRANIC SULFUR
10.6 ADVANTAGES AND DISADVANTAGES
11 EXISTING SCENARIO...
12 FUTURE PROSPECTIVES.
13 REFRENCES.

34

LIST OF ABBREVIATIONS
SO2Sulfur Dioxide
HCl Hydrochloric Acid
HNO3
Nitric Acid
HF
Hydrogen Fluoride
O2
Oxygen
Cl2
Chlorine
H+
Hydrogen Ion
H2O
Water
MgO
Magnesium Oxide
CB1
Coal bug-1
FGD
Fluel Gas Desulphurization
DBT
Dibenzothiophene
ASTM American Society of Testing Materials

35