Beneficiation of Indian Coal

EFFECT OF ADDITIVES FOR BENEFICIATION OF
INDIAN COAL BY SOLVENT EXTRACTION
Thesis submitted in partial fulfillment of the requirements for award of the degree of
Master of Engineering in Chemical Engineering
Submitted by
SHASHWATA GHOSH
Class Roll No.: 001310302004
Examination Roll No.: M4CHE15-04
Registration No.: 124701 of 2013-14
Under the guidance of
Dr. ChanchalMondal
&
Dr. SudeshnaSaha
Department of Chemical Engineering

JADAVPUR UNIVERSITY
Kolkata- 700032
2015
Declaration of originality and compliance of academic ethics
I hereby declare that this thesis contains literature survey and original research work by
the undersigned candidate, as part of his Master of Chemical Engineering studies. All
information in this document have been obtained and presented in accordance with
academic rules and ethical conduct.
I also declare that, as required by these rules and conduct, I have fully cited and
referenced all material and results that are not original to research work.
Name: ShashwataGhosh
Examination Roll Number: M4CHE15-04
Thesis Title: Effect of additives for beneficiation of Indian coal by solvent extraction
Signature:
Date:
CERTIFICATION
To whom it may concern

This is to certify thatShashwataGhosh, final year Master of Chemical Engineering
(M.ChE) examination student of Department of Chemical Engineering, Jadavpur
University (Exam Roll No.M4CHE15-04; Reg. No. 124701 of 2013-14), has completed
the project work titledEffect of additives for beneficiation of Indian coal by solvent
extraction under the guidance of Dr. Chanchal Mondal and Dr. Sudeshna Saha in the
stipulated time during his post graduatecurriculum. This work has not been reported
earlier anywhere and can be approved for submission in partial fulfillment of the course
work.
___________________________
Dr. SudeshnaSaha
Assistant Professor
Chemical Engineering Department
Jadavpur University
_________________________
Prof. ChandanGuha
Head, Chemical Engineering Department
Jadavpur University
_________________________
Dr. SivajiBandyopadhyay
Dean, Faculty of Engineering & Technology
Jadavpur University
ACKNOWLEDGEMENTS
It is a great pleasure to express my gratitude and thanks to each and everyone who have
helped me to complete my research and compile this thesis in the stipulated time. I am
grateful to all faculty members of Chemical Engineering Department, Jadavpur
University for allotting this project to me. I would like to express my respect to Dr.
Chanchal Mondal for his valuable suggestions and guidance, which have helped me
throughout the entire tenure of the research work. I am certainly indebted to Dr. Sudeshna
Saha for her resourcefulness and guidance, which undoubtedly has helped me complete
this research in time. In fact, I owe her more than I can even mention.
I would like to express my heartfelt gratitude towards my parents and friends Mr.
Santanu Ghosh and Mr. Abhik Das, whose have always inspired me and helped me
develop a positive attitude. I am also indebted to Mr. Amritanshu Banerjee, a great friend,
whose noble company has always enriched me. Without his help, my thesis would have
remained incomplete.
I would also express my thanks to all my fellow classmates Mr. Victor Sarkar, Ms.
Sudeepta Bhattacharya and research scholars, Ms. Sujata Sardar, Ms. Epika Mandal.
Without their cooperation and inspiration, I could not complete my research in time. I am
also grateful Mr. Ashok Kumar Seal for his help and co-operation in providing me with
all necessary equipments I required for this work.
iv
ABSTRACT
High ash content of Indian coals not only reduces the efficiencies of boilers and furnaces,
but also affects the quality of metallurgical coke for use in blast furnaces. The present
study investigates the role of solvents and additives for extraction of coals and reduction
of ash content in the extracts obtained from an Indian coal. Toluene, a non-polar solvent
does not give significant yield of coal extract. Hence, a polar solvent like n-methyl
pyrrolidone (NMP) was chosen and the yields of extracts were observed for different
times of extraction and various additives. The additives used in the experiments were pnitro benzoic acid, quinoline, calcium fluoride and calcium chloride. It was observed that
the maximum yield of extract was 13.313% and was obtained by using Calcium chloride
as an additive with NMP. This yield was obtained with an additive concentration of 5%
(by weight of raw coal) of Calcium chloride under 1 hour of thermal extraction at a
temperature of 150C. However, the reduction in ash content of the coal extract in case of
Calcium chloride was 82.25%, which was lower than that obtained by the use of other
additives, or, NMP alone.
TABLE OF CONTENTS
Title
Page No.
1
Chapter 1 INTRODUCTION
1.1. Coal
1.2. Types of coal
1.3. Uses of coal
1.4. Chemical composition of coal
1.5 Proximate analysis of coal
1.6. Ultimate analysis of coal
1.7. Disadvantages of ash content of coal
1.8. Beneficiation of coal
10
1.9. Background of the project
10
1.10. Problem statement
11
1.11. Objectives
11
1.12. Originality of the work
12
Chapter 2 LITERATURE REVIEW
13
2.1. The chemical structure of coal
13
2.2. Solvent extraction of coals
14
2.3. Effect of rank of coal on solvent extraction
15
2.4. Effect of temperature and pressure on extraction of coal
16
2.5. Effect of nature of solvents on extraction of coal
18
2.6. Effect of hot filtration and room temperature filtration

on extraction
18
2.7. Effect of using mixtures of solvents for coal extraction
19
2.8. Effect of various additives on extraction of coals with

solvents
20
2.9. Kinetics of diffusion of solvent into the coal structure
21
2.10. FT-IR Analysis of raw, residue and extracted coals
22
vi
TABLE OF CONTENTS (Contd)

Title
Page No.
2.11. Coal beneficiation by agglomeration techniques
23
2.12. Beneficiation by the use of inorganic chemicals
23
2.13. Reduction of ash content of coal with solvents without

coal extraction
24
Chapter 3 EXPERIMENTAL MATERIALS & PROCEDURE
25
3.1. Materials
25
3.2. Experimental procedure
25
3.2.1. Proximate analysis of coal sample
25
3.2.2. Thermal extraction of coals
26
3.2.3. Extraction of coal by Ultrasonic irradiation
27
3.2.4. Recovery of extract
29
3.2.5. Analysis of the extract and residue
29
Chapter 4 RESULTS & DISCUSSIONS

4.1. Characterization of raw coal sample
31
31
4.1. 1. Proximate analysis of raw coal
31
4.1.2. FT-IR Analysis
31
4.2. Effects of different solvents
32
4.3. Comparison of methods of extraction
32
4.4. Determination of optimum time of extraction
34
4.4.1. Comparison of percentages of extract recovered
34
4.4.2. Comparison of ash reduction in extracts
34
4.4.3. FT-IR spectra of coal extract and residue obtained

using fresh NMP
4.5. Comparison of results obtained using reused and fresh
(unused) NMP
4.5.1. Comparison of percentages of extract recovered
4.5.2. Comparison of ash reduction in extracts
vii
36
37
37
38
TABLE OF CONTENTS (Contd)

Title
Page No.
4.5.3. Comparison of FT-IR spectra of extracts obtained

using fresh and reused NMP
4.6. Effect of reusing the residue for thermal extraction
4.6.1. Percentages of extract recovered from fresh and
reused coal residue
4.6.2. Percentages of ash reduction in extract
4.7. Experimental results for use of additives along with
NMP
4.7.1. p-Nitro benzoic acid
39
40
40
41
41
42
4.7.1.1. Percentage of extract recovered
42
4.7.1.2. Ash content of extract
43
4.7.2. Quinoline
44
44
44
4.7.3. Calcium fluoride
46
46
47
4.7.4. Calcium chloride
48

4.8. Comparison of the experimental results for the different
additives
4.8.1. Comparison of the yields of extracts
48
49
51
51
4.8.2. Comparison of ash reduction in the extracts
52
4.8.3. Comparison of FT-IR results of the extracts for the

different additives
52
Chapter 5 CONCLUSIONS
54
5.1. Conclusions
54
5.2. Future prospects of the work
55
REFERENCES
57
viii
LIST OF TABLES
Table No.
Title
Page No.
3.1
Particulars of all experiments
28
4.1
Proximate analysis of raw coal
31
4.2
Comparison of percentages of extract recovered from Toluene

& NMP
32
Comparison of percentages of extract recovered by Thermal

extraction & Ultrasonic irradiation
33
Percentages of extract recovered and ash removed under

different times of extraction for fresh NMP
35
Percentages of extract recovered and ash removed under

different times of extraction for reused NMP
39
Percentages of extract recovered and ash removed from fresh

coal and reused residue
41
Percentages of extract recovered and ash removed for using pnitro benzoic acid as an additive with NMP
44
Percentages of extract recovered and ash removed for using

Quinoline as an additive with NMP
46

Calcium fluoride as an additive with NMP
48

Calcium chloride as an additive with NMP
50
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
ix
LIST OF FIGURES
Fig. No.
Title
Page No.
1.1
Sources of energy in India in 2013
1.2
Sources of electricity in the United States in 2011
1.3
Sources of electricity generation in India, 2011
1.4
Example of chemical structure of coal
2.1
Representative structure of coal
14
2.2
Effect of rank of coal on extraction yield
16
2.3
Variation of extraction yield with temperature
17
2.4
Variation of extraction yield with initial applied pressure
17
2.5
Flow diagram of the Hyper-coal process
19
2.6
The effect of solvent nature on the extraction efficiency at

ambient conditions.
21
3.1
Schematic representation of experimental procedure
27
3.2
Thermal extraction set up
29
3.3
Thermal distillation set up
30
3.4
Dried Extract in a petridish
30
4.1
Comparison of percentages of extract recovered by Thermal

extraction & Ultrasonic irradiation
33
Percentages of extract recovered under different times of

extraction for fresh NMP
34
Percentages of ash removal of extract under different times of

extraction for fresh NMP
35
4.2
4.3
4.4
FT-IR spectra of coal extracts obtained using fresh and reused

NMP
36
LIST OF FIGURES (Contd)

Fig. No.
Title
Page No.
4.5
FT-IR spectra of raw coal and residue obtained using NMP
37
4.6
Percentages of extract recovered under different times of

extraction for fresh & reused NMP
38
4.7
Percentages of ash removal of extract under different times of

extraction for fresh &reused NMP
4.8
39
Percentages of extract recovered from fresh &reused residue

40
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
Percentages of ash reduction in extract from fresh coal & reused

residue
41
Percentages of extract recovered for different concentrations of pnitro benzoic acid
42
Percentages of ash reduction in extract for different

concentrations of p-nitro benzoic acid
43
Percentages of extract recovered for different concentrations of

Quinoline
45

concentrations of Quinoline
45

Calcium fluoride
47

concentrations of Calcium fluoride
48

Calcium chloride
49

concentrations of Calcium chloride
50
xi
LIST OF FIGURES (Contd)

Fig. No.
4.48
4.19
4.20
Title
Page No.
Comparison of percentages of extract recovered for different

concentrations of the additives
Comparison of the percentages of ash reduction in extract for
different concentrations of the additives
51
Comparison of the FT-IR spectra of the extracts for the different

additives
53
xii
52
Chapter: 1
Introduction
_____________________________________________
1.1. Coal
Coal is an important fossil fuel & has immense reserves in various parts of the world. It is a
solid, brittle, combustible, carbonaceous rock formed by the decomposition and alteration
of vegetation by compaction, temperature, and pressure. The vegetation that form coals had
been buried millions of years ago and may be mosses and other low plants; although some
varieties of coal contain significant amounts of materials derived from woody precursors.
The plant precursors that eventually formed coal were compacted, hardened, chemically
altered, and metamorphosed by heat and pressure over time.
1.1.1. Types of coal

According to degree of metamorphism, several types of coal are available, which vary in
color from brown to black and are usually stratified. Peat is considered to be the precursor
of coal consisting of partly decomposed plant material that has accumulated in situ under
temperate marshy conditions. It is associated with large quantities of moisture. Near the
surface of deposit, peat is light brown & highly fibrous. As depth increases, the colour
darkens & finally becomes black. Peat represents the first stage of formation of coal. The
other major stages are lignite, bituminous coal &anthracite.
Lignite is the lowest rank of coal. It is often referred to as brown coal for its brownish black
colour and woody texture. Its moisture content is quite high, ranging from 30-50% and is
used almost exclusively as fuel for steam-electric power generation. The heat content of
lignite ranges from 9 to 17 million Btu/ton on a moist, mineral-matter-free basis [1].
Subbituminous coal occupies the next rank. The properties of this type of coal range from
those lignite to those of bituminous coal. It may be dull, dark brown to black, and soft and
1
crumbly at the lower end of the range, to bright, black, hard, and relatively strong at the
upper end with a moisture content of 20-30% by weight. It is primarily used as fuel for
steam-electric power generation. The heat content of this coal usually varies from 17 to 24
million Btu per ton on a moist, mineral-matter-free basis [1].
The next rank is occupied by Bituminous coal, which is black in colour with bands of
bright and dull materials and is harder than lignite. Its moisture content is usually below
20% by weight and is primarily used as a fuel for steam-electric power generation and for
manufacturing coke. The heat content of Bituminous coal ranges from 21 to 30 million Btu
per ton on a moist, mineral-matter-free basis [1].
Anthracite is the most mature & hardest form of solid fossil fuel, with a sub-metallic luster,
or, graphitic appearance. It is hard and brittle and is referred to as hard coal. It has a
moisture content below 15% by weight with low quantity of volatile matter and high fixed
carbon content and is mostly used for electricity generation and metallurgical applications.
The calorific value of this type of coal ranges from 22 to 28 million Btu per ton on a moist,
mineral-matter-free basis [1].
1.2. Uses of coal

Coal is an important source of energy and has a wide range of industrial as well as
domestic applications. According to World Coal Association (WCA) statistics, the total
global coal production in 2013 was 7823Mt, of which India produced 613Mt of coal and
occupied third rank among the worlds top 10 coal producers.
In 2013, India ranked 4th largest energy consuming nation in the world according to a
report released by U.S Energy Information & Administration. United States was the biggest
Energy Consumer followed by China and Russia. The major sources of energy in India in
2013 were coal, which supplied about 41% of the energy demand, followed by petroleum
and solid biomass and waste products (Fig. 1.1). Natural gas, nuclear power and renewable
sources also contributed to meet Indias energy demand.
Fig.1.1: Sources of energy in India in 2013

(Source: U.S. Energy Information Administration, International Energy Statistics, 2013)
The major industrial uses of coal are as follows:
(i) Use as a source of energy in thermal power plants: When coal is used for electricity
generation, it is usually pulverized and then combusted (burned) in a furnace with a boiler.
The furnace heat converts boiler water to steam, which is then used to spin turbines which
turn generators and create electricity. As per WCA statistics, in 2013 coal was used to
generate over 40% of the world's electricity and 70% of the electricity in India was
generated from coal.
According to U.S. Energy Information Administration (EIA) report, about 68% of the
countrys electricity in 2011 was generated by coal, natural gas, petroleum and oil (Fig.
1.2). The next was nuclear energy at about 20% and about 13% was contributed by
renewable sources, like solar, hydropower, wind, geothermal and biomass.
Fig.1.2: Sources of electricity in the United States in 2011

(Source: U.S. Energy Information Administration, 2011 data)
According to the EIA report, India had an installed electricity generating capacity of
211GW as of September, 2012. The various sources through which India produces its
electricity are given in Fig 1.3.
Fig. 1.3: Sources of electricity generation in India, 2011

(Source: U.S. Energy Information Administration, International Energy Statistics, 2013)
(ii) Use in blast furnace: Coke is a solid carbonaceous residue derived from low-ash, lowsulfur bituminous coal from which the volatile constituents are driven off by baking in an
oven without oxygen at temperatures as high as 1,000 C, so the fixed carbon and residual
ash are fused together. Metallurgical coke is used as a fuel and as a reducing agent in
smelting iron ore in a blast furnace. The result is pig iron and is too rich in dissolved carbon
as a result it must be treated further to make steel. According to WCA, approximately 15%
(over 1.2 billion tonnes) of total coal production in the world is currently used in the steel
industry and roughly 70% of total global steel production is dependent on coal.
(iii) Gasification to produce Synthesis Gas: Coal gasification can be used to
produce synthesis gas, a mixture of carbon monoxide (CO) and hydrogen (H2) gas.
Synthesis gas can be used to produce methanol & ammonia.
1.3. Chemical composition of coal

Coal consists of an organic mass with some quantities of inorganic substances, like, water
& mineral matter.
Moisture: Coal is always associated with moisture due to its nature, origin & occurrence.
Some amount of moisture is derived from the vegetable matter from which coal is formed.
Varying amounts of this water is present in different stages of coalification process. This is
evident from a comparison of the moisture contents of different ranks of coal, from lignite
to anthracite. Lignite has the maximum moisture content of 30-50%, which decreases to
less than 15% in anthracite. However, moisture content of coal is also due to washing of
coals as well as due to rain during transportation and storage of coal.
Complex organic mass: The exact organic structure of coal cannot be isolated & identified.
Coal composition is, therefore, studied by indirect methods. Fig. 1.4 shows an example of
the complex organic structure. The organic mass is a mixture of complex organic
compounds of carbon, hydrogen, oxygen, nitrogen & sulphur.
Mineral matter: Coal contains inorganic mineral substances, which are converted into ash
during the combustion of coal. Mineral matter may be of two types: inherent & extraneous.
5
The inorganic materials of the original vegetable substances are responsible for the inherent
mineral matter. The extraneous mineral matter is due to (i) the substances which get
associated with the decaying vegetable matter during the formation of coal and (ii) rocks &
dirt getting mixed during mining & transportation.
The former type of extraneous mineral matter is intimately associated with the organic
mass of coal & hence, difficult to remove by mechanical methods. This type of mineral
matter includes mainly clay, shale, sand and gypsum. The second type, comprising mainly
rocks and dirt is more amenable to coal cleaning methods. Inherent mineral matter cannot
be removed by any mechanical means. Indian coals suffer from the great disadvantage that
the mineral matter is high as well as is intimately associated with the coal structure due to
their drift origin [2].
Fig. 1.4: Example of chemical structure of coal
The bulk of the mineral matter is due to shale, or, clayey substances and consists of
aluminosilicates of different compositions. Most common clay minerals are kaolinite and
mixed-layer illitemontmorilloniteKaolinite-rich clay is commonly associated with coals in
most of the coal basins of the world. Other major constituents are calcite (calcium
6
carbonate) & pyrites. Among sulfide minerals that are present in coal, dimorphs pyrite
(FeS2) and marcasite (FeS2) are the dominant sulfide minerals in coal, pyrite being more
abundant. Sulphate minerals are present in coal, but their quantities in fresh, unoxidised
coal samples is insignificant. The sulfates, gypsum (CaSO4,2H2O) and barite (Ba2SO4) are
found in fresh coals, while a number of hydratedsulfates (FeSO4,xH2O) have been reported
in weathered coals. Carbonate minerals like Calcite (CaCO3) and ankerite (a mixed crystal
composed of Ca, Mg, and Fe carbonates) are abundant in some coals. Silica is also present
in coals while the most dominant form of silica being Quartz.[j] Among other minerals,
Authigenic apatite [calcium fluorochlorohydroxyphosphate, Ca5(PO4)3.F.Cl.OH] has been
found in coal produced at widely separated areas of the world [1].
During combustion of coal, the shale & other hydrated minerals lose water of hydration,
while sulphides, sulphates & carbonates decompose, or, get oxidized, leaving their basic
radicals to combine with excess silica (if any)[2]. As a result, there is a net loss in weight,
so that the ash of coal is less than the mineral matter content.
1.4. Proximate analysis of coal

The proximate analysis of coal determines the percentages of moisture, ash, volatile matter
and fixed carbon of coal.
Moisture: The amount of moisture present varies according to the rank of coals. Moisture
is of two types: external & inherent. The external moisture depends upon the mode of
occurrence & handling of coal. Inherent moisture may be referred to as equilibrium, airdried, or, hygroscopic moisture & can only be removed by heating coal above 100. The
total moisture in coal is the determination of the moisture (in all forms except water of
crystallization of the mineral matter) that resides within the coal matrix. Air-dried moisture
is determined by observing the loss in weight of a coal sample on heating above 105C.
Air-dried moisture of coal decreases with increasing rank of coal and ranges from 30-50%
in lignite to less than 15% in anthracite.
Ash content: Ash refers to the residue left after combustion of coal under specified
conditions. The changes that occur during combustion of coal include loss of water from
hydrated silicate minerals, liberation of CO2 from carbonates, oxidation of iron pyrites to
7
iron oxide and reaction between sulfur oxides and bases like calcium and magnesium[j].
Generally, more than 90% of ash for Indian coals consists of silica, alumina, iron oxide &
lime. The remaining are oxides, sulphates & phosphates of sodium, potassium &
magnesium. Trace elements, like, Gallium, Germanium, Nickel, Beryllium & Boron may
also be present as trace amounts in Indian coals [2].
Volatile matter and fixed carbon: These denote the volatile and non-volatile products of
thermal decomposition of coals under specified conditions. Volatile matter does not include
moisture present in coal, but includes moisture formed by hydrogen and oxygen during
decomposition of coal [2]. When represented in air-dried and d.a.f. bases, it includes the
water of hydration of mineral matter, which vaporizes due to heat. However, on d.m.m.f.
basis, volatile matter includes only volatile products from organic matter of coal. With
increase in rank, or, maturity of coal, volatile matter decreases. The volatile matter of
Anthracite coal ranges from 3 to 10% d.m.m.f., while that in bituminous coals usually lies
between less than 20 to about 45% on d.m.m.f. basis [2]. Fixed carbon does not, however,
include ash content of coal. It is the non-volatile residue of the organic mass of coal. The
higher the volatile matter, the lower is the amount of fixed carbon of the coal.
1.5. Ultimate analysis of coal

The ultimate analysis determines the carbon, hydrogen, sulfur, nitrogen and oxygen in the
pure coal.
Carbon content is determined by Liebigs method by completely burning the coal in pure
oxygen and finding the amount of carbon dioxide formed. However, correction is made for
carbondioxide formed due to decomposition of carbonates.
Hydrogen content of coal is also determined using the same procedure of burning the coal
in pure oxygen. Amount of hydrogen is calculated after estimating the amount of water
formed. Corrections are used for moisture in the coal and water of hydration of minerals.
The hydrogen content of lignite to bituminous coals vary in the range of 4.5-6.5%, while
hydrogen content lies in between 1-2% in anthracite [2].
8
Nitrogen is estimated by Kjeldahls method. The sample is digested with oleum containing
a catalyst to convert nitrogen into ammonium sulfate. The ammonia is then estimated and
nitrogen content is determined. In most coals, the nitrogen content varies between 1-2%
[2].
Three forms of sulfur, namely pyritic, organic and sulphate are common in most coals. The
total sulphur can be estimated by Eschka, or, Bomb method. In the former method, the
entire sulfur content is converted into soluble sulfates by heating the coal with an oxidizing
mixture of magnesium oxide and sodium carbonate. Then sulfate is estimated. In the Bomb
method, total sulfur is converted into sulfate in a Bomb calorimeter. The pyritic and
sulfates are detrmined by methods of analytical chemistry, while organic sulur is obtained
by subtracting inorganic sulfur from total sulfur. The amount of sulfur in Indian coals is
usually low (0.7%, or, less), but some coals may have sulfur content around 4% [2].
Oxygen content is obtained by subtracting the percentages of carbon, hydrogen, nitrogen
and sulfur (on a d.m.m.f. basis) from 100.
Phosphorous content of Indian coals is usually less than 0.15% [2]. The estimation of
phosphorous content becomes important during production of metallurgical coke. But the
low phosphorous content of Indian coal shows no problems for iron and steel production
process.
1.6. Disadvantages of ash content of coal

Mineral matter does not contribute to the calorific value of coal, but creates difficulties in
the efficient utilization of coal. The thermal efficiency of coal is reduced due to high ash
content as the latter not only interferes with the combustion of coal but also reduces
temperature of the combustion zone. High ash content of coal leads to large heat losses and
carbon losses in boilers and furnaces. High ash content in coal also results in boiler
deposits & clinkering. Due to these reasons, burning of coal takes place very slowly
compared to low ash coal under identical conditions of feed rate and excess air supplied.
Consequently steam output of boiler decreases, thereby reducing efficiency of a boiler.
9
Efficiency of blast furnace is also reduced due to high ash in coking coals because rate of
combustion gets reducedas ash restricts passage of air in furnace grates. Transportation and
handling costs are also increased if the mineral content of the coal is high.
1.7. Beneficiation of coal

Depending on the composition of the coal seam, in which several types of inorganic
intrusions may be present due to sedimentation and volcanic activity, and depending on the
mining method employed, the run-of-mine coal will commonly contain rock, shale and
other undesirable contaminants[2].
Coal beneficiation is the process of removal of the contaminants and the lower grade coal
to achieve a product quality which is suitable to the application of the end user - either as
an energy source or as a chemical agent or feedstock. A common term for this process is
coal "washing" or "cleaning".
Chemical beneficiation of coal refers to the use of chemicals to remove the mineral matter
of coal. While physical beneficiation processes mainly remove mineral matter, which get
mixed during mining & handling operations, chemical beneficiation aims at removing the
mineral matter, which is intimately associated with the coal structure. Various inorganic as
well as organic chemicals can be employed for this purpose. Organic solvents mainly
dissolve organic constituents of coal, leaving behind mineral matter obtained as residue.
Amount of coal extracted by each solvent is not same for every solvent. The percentage of
coal, extracted by the solvent, therefore, depends both on coal structure as well as
properties of the solvent.
1.8. Background of the project

Coal is an important source of energy and is used in many industries like coal-fired thermal
power plants. Coal is also converted into coke, which is used as a fuel as well as a reducing
10
agent in smelting iron ore in a blast furnace. But presence of high percentage of ashforming minerals in coal is disadvantageous. Though extraneous mineral matter can be
removed by physical coal cleaning methods, inherent mineral matter cannot be removed by
easy physical methods. Mainly chemical treatment is required to remove those minerals.
Indian coals consist of high percentage of ash-forming minerals, which are converted into
ash during combustion of coal. Mineral matter mainly consists of aluminosilicates apart
from pyrites and few other compounds. Presence of high ash not only interferes with
effective utilization of coals due to heat losses, but disposal of large amounts of ash is also
an important problem. Many studies have been conducted to reduce the ash content of coal
by use of various solvents and chemicals. This project also deals with the removal of ash
using solvents and additives.
1.9. Problem statement

The ash content of Indian coals is very high, seldom exceeding 50%. This makes them
unsuitable for use in boilers and blast furnaces, as high ash results in large heat losses,
thereby reducing efficiencies of boilers. Also, ash content of coal interferes with the
combustion of coal in blast furnaces. Moreover, disposal of large quantities of ash is also a
problem. All these disadvantages of ash content of coal have been discussed in details in
section 1.6. This project deals with extraction of Indian coal by the using different solvents
and additives, which brings down ash content of extracted coal. This extracted coal can be
used in boilers and furnaces and also for making metallurgical grade coke for blast
furnaces. However, the quantity of extracted coal remains quite little and studies are being
undertaken to increase the percentage of coal extracted by solvent. This project focuses on
the effectiveness of various additives in increasing extraction yield of coal.
1.10. Objectives
The main objective of this project is to determine the effect of additives during extraction
of an Indian coal with solvents on extraction yield. However, the extent of this project also
includes studying the effect of additives to decrease in ash content of the extract from that
of the original coal sample. For this, measurement of ash content of the raw coal, residue
11
and extract will be done. Additionally, to study organic functional groups, extracted by the
solvent-addtive mixture, FT-IR analysis will also be conducted.
1.11. Originality of the work

There are previous studies of coal extraction with the solvents used in this present research
work. But the originality lies in choosing the additives used in this work. For the present
work, additives have been selected after studying the chemistry of coal extraction process
and experimental work of coal extraction using these additives are not available in
literature as per knowledge.
12
Chapter: 2
Literature review
Many studies have been conducted to reduce the ash content of coal by the use of various
chemicals. Most of the studies include extraction of coal using organic solvents which in
turn reduce ash content of the extracted coal to a large extent. The effects of various
parameters like temperature, pressure, effects of additives, etc. have been studied. The
main aim of this review is to determine the various factors which decrease the ash content
of coal as well as increase extraction of coal. The effects of the various chemicals used in
these studies provide important information as to how ash content of coal can be reduced
to a significantly low percentage.
2.1. The chemical structure of coal

A number of workers have attempted to give a representative structure of coal that is
consistent with the observed chemistry of coal. In Fig. 2.1, a representative structure of
coal has been presented. According to this structure, coal consists of highly substituted
aromatic rings with a number of functional groups. The figure shows coal as a highly
cross-linked amorphous polymer, consisting of a number of stable aggregates connected
by relatively weak cross-links. These cross-links have marked by arrows in the figure.
This highly cross-linked structure fragments into radicals at high temperatures in
presence of hydrogen-donor solvents. In absence of hydrogen donor solvents, these
radicals may recombine to form char, or, coke. So, coal becomes highly reactive in
presence of hydrogen donors and liquefies easily [3].
It has also been observed that aromaticity varies with the rank of coal and can be low for
sub-bituminous coals, which contain significant amounts of polycyclic aliphatic rings.
13
High aromaticity of coal products is due to the processes used to convert coal and does
not imply high aromaticity of the starting product. Presence of hydrogen donor solvents
can increase solubility of coal fragments in solvent, but hydrogen is not necessary for
coal solubility. Temperatures above 750F are required for rapid conversion [3].
Fig. 2.1: Representative structure of coal [3]
2.2. Solvent extraction of coals

Solvent extraction of coals is accomplished by contacting the coal with a solvent under
specified conditions of temperature and pressure. After extraction, the residual coal
material is separated from the solvent containing the extracts. The extraction solvent is
well mixed with the coal to allow soluble constituents of coal to transfer to the solvent
phase. The residual coal and solvent are then separated by physical methods, such as
gravity decanting, filtering, or centrifuging. Distillation may be done to recover the
solvent from the extracts.
14
The solvents used to extract coal can be classified as follows [4]:

Non-specific solvents: Non-specific solvents can extract a small amount of coal (up to
about 10%) for temperatures up to 100. They are low boiling liquids, like methanol,
ethanol, acetone, ether, etc. The extract is believed to be occluded in the coal matrixdue
to waxes & resins. These resins and waxes donot form a significant portion of the coal.
Specific solvents: They extract up to 40% coal at temperatures below 200. They are
non-selective in nature & the nature of the extract is similar to that of the parent coal.
These are, generally, nucleophilic in nature due to the presence of a lone pair of electrons
on the nitrogen atom. e.g. NMP, Pyridine, Dimethylformamide, Dimethylacetamide, etc.
Degrading solvents: They can extract up to 90% of coal at temperatures of about 400.
They degrade coal thermally into smaller fragments. After extraction, the solvent can be
recovered without change in its chemical form. E.g. phenanthrene, diphenyl, etc.
Reactive solvents: These solvents react with the coal chemically. They are generally
hydrogen donors. The smaller fragments formed by thermal disintegration of coal are
stabilized by hydrogen which is donated by the solvent. Both the solvent & coal undergo
appreciable changes during extraction. e.g. tetralin.
2.3. Effect of rank of coal on solvent extraction

Rank of coal has a considerable influence on the chemical nature and quantity of extracts
obtained by the solvent extraction of coal. The soluble products of the extraction, referred
to as extracts vary according to the means by which they are obtained.
For higher rank Bituminous coals, it has been observed that the extraction yields increase
with an increase in temperature and there is a peak temperature at which a maximum
extraction yield is obtained. Beyond this peak temperature, the extraction rate again
drops. This is related to the thermal relaxation of molecules. At the peak temperature,
relatively small molecules may be released from the cross-linking coal structure to the
solvent, resulting in dissolution of coal in the solvent [5].
For lower rank coals, like sub-bituminous and lignite coals, extraction yield has been
observed to increase with increase in temperature. A suitable solvent and high
temperature of about 673K gives an extraction yield of over 70% and very low, or,
negligible ash content, as shown in figure 2.2. In figure 2.2, BD, BL and POP are lignite
15
coals, while CV and GEN are sub-bituminous coals. A higher proportion of vitrinite and
lower value of MMVR (mean maximum vitrinite reflectance) has been reported to give
higher extraction yield as lower MMVR values signify higher reactivity of coal.[6]
Fig. 2.2: Effect of rank of coal on extraction yield

(Rahman et al., 2013)[6]
2.4. Effect of temperature and pressure on extraction of coal

For higher rank coals, like Bituminous coals, it has been observed that the extraction
yield increases with an increase in temperature and there is a peak temperature at which a
maximum extraction yield is obtained, as shown in figure 2. Beyond this peak
temperature, the extraction rate again drops. The peak temperature at which the extraction
yield becomes maximum has been related to the softening temperature of coal. When the
coal softening point is closer and closer to the extraction temperature, the coal extraction
becomes higher and higher [5]. At the softening point, the structure becomes relaxed and
beyond the softening point, the coal is restructured by cross-linking, which results in a
decrease in extraction yield [7]. This is possibly due to the enhanced coalsolvent
interaction at this temperature and consequently, higher solvent induced thermal
relaxation of coal molecules is occurring and releasing mainly small molecules and free
radicals from the cross-linking coal structure to the solvent .[5] In figure 2.3, Kideko and
Roto south are sub-bituinous coals, while Sunhwa is a Bituminous coal.
16
Fig. 2.3: Variation of extraction yield with temperature

(Kim et al., 2007)[7]
For lower rank coals, such as lignite and sub-bituminous coals, there is no softening
temperature at which the coal structure becomes relaxed and so a polar solvent is required
to breakdown the structure. The ash content of coal extracts from both Bituminous as
well as sub-bituminous coal decreases as the extraction temperature increases. The initial
applied pressure has no significant effect on the extraction yield and ash reduction;
extraction yield and ash reduction can be enhanced more by increasing extraction
temperature rather than the initial pressure, as shown in Fig.2.3 [7].
Fig. 2.4: Variation of extraction yield with initial

applied pressure (Kim et al., 2007)[7]
17
2.5. Effect of nature of solvents on extraction of coal

For higher rank coals, like Bituminous coal, it has been reported that non-polar aprotic
solvents like 1-methylnaphthalene can give satisfactory yields of about 70% by weight
(d.a.f.) and ash content reduced to several hundreds of ppm at 340-360. However, it has
also been observed that if a hydrogen donating solvent like tetralin is used, the extraction
rate becomes more than that obtained when an aprotic solvent is used at the same
extraction temperature. This has been attributed to intermolecular hydrogen transfer from
the solvent to coal to stabilize small molecules derived by thermal decompositionof coal
which brings about due to coal softening phenomenon [5]. Polar solvents, like NMP have
been reported to give extraction yield above 60% for Bituminous coals at temperatures
above 350 [7].
However, in case of lower rank coals, such as lignite and sub-bituminous coals, there is
no softening temperature at which the coal structure becomes relaxed and so a polar
solvent is required to breakdown the structure. In case of sub-bituminous coals, it has
been observed that a polar solvent like NMP can give an extraction yield of over 80% at a
temperature of about 400 [7]. Hydrotreated aromatic hydrocarbons have given higher
extraction yields for low rank coals than 1-methyl naphthalene because latter contains
polar components [6]. NMP has been reported a better solvent than non-polar ones for the
low rank coals which have higher amount of polar sites [8].
Yoshida et al. [9] have reported that nitrogen containing solvents are effective for giving
higher yields of extracts during solvent extraction of coals. Thus, nitrogen containing
solvents, like amines may be used for enhancing extraction yield.
2.6. Effect of hot filtration and room temperature filtration on extraction

Coals of various ranks have been extracted with a variety of organic solvents, viz tetralin,
1- methyl naphthalene, dimethyl naphthalene and light cycle oil (LCO -a by-product of
cracking of vacuum gas oil to gasoline). It has been observed that high extraction yield
can be obtained if a suitably high extraction temperature is maintained; but, if the
separation of residue and solution is conducted at room temperature, the extraction yields
will not achieve the required specification of Hyper-coal [10].
18
The term Hyper-coal refers to ash-free coal [5]. This has been attributed to the separation
conducted at room temperature as the extract components soluble at high temperature
might have deposited while quenching and decreased the percentage of coal extract. [10]
Hence, filtration after extraction should be performed at a high temperature in order to
maintain a satisfactory extraction yield.
Fig. 2.5: Flow diagram of the Hyper-coal process

(Okuyama et al., 2004)[5]
2.7. Effect of using mixtures of solvents for coal extraction
Beneficiation of coal by mixtures of solvent, like CS2 & NMP (in the ratio 1:1) has been
reported to give a higher extraction yield than that obtained when NMP is used alone.
NMP is a polar solvent, but when CS2 is added, a synergistic effect is obtained. It has
been reported that with CS2 addition, the viscosity of the solvent mixture decreases and
the ability of the mixed solvent to penetrate the cross-linked coal structure increases. As a
result mixed solvent can interact with solvent-soluble molecules which in turn increase
the extraction yield [11].
Large synergistic effects have been observed for coals used with NMP/HHA (1,4,5,8,9,10
Hexahydroanthracene) mixed solvents. Also dissolution yield increases while using
19
mixed solvents. This is due to the fact that the extent of synergistic effect is highly
dependent on the kind of coal used. It has been reported that hydrogen donation from
HHA to the coal radicals is the key reaction [8].
2.8. Effect of various additives on extraction of coals with solvents

It has been observed that addition of strong bases, like NaOH, or, sodium tertiary
butoxide can increase the degree of dissolution of coal in solvents like NMP, DMF, etc.
Depending on the extraction conditions, carbon extraction efficiencies of up to 90% have
been obtained, as shown in Fig. 2.6. Sodium, or, potassium hydroxide is added as a
solution with water. However, addition of water has been observed to be detrimental for
DMF due to base catalyzed hydrolysis of DMF to dimethyl amine and formic acid in
presence of water. Addition of sodium sulfide has been observed to further reduce the ash
content of the extracted coal. It has also been reported that as the NaOH/Na2S molar ratio
became high, coal extraction yield also increases. [12]
The addition of a small amount of polar compound such as methanol to nitrogencontaining polar solvent has been observed to have greatly increased the thermal
extraction yield for subbituminous coals at 360 [13].
Addition of salts like lithium and tetrabutylammonium salts with various anions to polar
aprotic solvents, or, solvent mixtures have also been observed to increase the extraction
yield for several coals. The yields increase in the order F->Cl->Br->I-, implying that
smaller ions with large electronegativity are responsible for increase in yields. Hard bases
like F- & Cl- attract proton and since, the solvent is polar and aprotic, these anions will
not be solvated and can interact with some hard acidic sites in coal. However, soft bases,
like Br- & I- get solvated in the soft acid like CS2-NMP mixture and cannot interact with
the coal. It has also been reported that hard bases, like acetate ion can increase extraction
yield. It has also been reported that the addition of alkali metal salts, like LiCl can
increase the polarity of the solvents-salt solutions which in turn increase the extraction of
coal [14].
It has been observed that if polar components of an industrial solvent like CMNO (crude
methyl naphthalene oil) can be separated, the extraction yields obtained with the
extracted polar materials are 20-30% higher than that with CMNO (Kashimura et al.,
20
2006). It has been reported that the major polar component of CMNO was quinoline and
the minor constituents were isoquinoline, indole and methylquinoline. Indole has greater
ability to extract coal constituents compared to quinoline. But if both are used with a nonpolar solvent, then a higher extraction yield compared to quinoline-nonpolar solvent
mixture is obtained [13].
Fig. 2.6: The effect of solvent nature on the extraction efficiency at ambient
conditions. Solvent:coal:KOH=100:10:1.56 on a mass basis. (Makgato et al., 2008)[12]
2.9. Kinetics of diffusion of solvent into the coal structure

Coal has a cross-linked structure. Due to this structure, swelling of coal is the first stage
in processes like solvent extraction. As the solvent penetrates the coal matrix, coal-coal
interactions are replaced by coal-solvent interactions. This is why, coal swells due to
contact with a solvent during extraction. Pande et al.[15] studied the kinetics of swelling
of a bituminous, non-coking coal in two solvents namely NMP and Ethylenediamine
(EDA) and their mixture (1:1)(vol/vol) at temperatures ranging from 15C to 60C. For
the swelling experiments, solvent, or, solvent mixture at the desired temperature was
added to centrifuged samples of coal and that temperature was maintained in a thermostat
for the desired time. Swelling ratios were calculated for the different solvents/solvent
mixture for the particular time and temperature. It was observed that the swelling ratio in
21
the mixed solvent was highest and that in NMP was lowest. It was reported that the
activation energy for swelling of coal in the mixed solvent system was found to be more
than that in either of the solvents. Mixed solvent has greater ability to disrupt more
number of stronger non-covalent interactions. A comparison of the extraction yields of
the coal at room temperatures showed that the mixed solvent not only has greater
swelling power, but also has ability to break other types of coal-coal interactions, such as
stronger hydrogen bonds and - aromatic interactions. The bonds cannot be broken by
either of the solvents alone. Again, the rate of swelling in EDA was faster than that in
NMP. As a result, when the mixed solvent was used, faster swelling solvent EDA opened
the coal structure for penetration by NMP. It was also reported that the swelling kinetics
was characterized by a Fickian diffusion process.
2.10. FTIR Analysis of raw, residue and extracted coals

Rahman et al. [6] have reported FTIR spectra of raw, residue and ash-free coals (extracts)
obtained after solvent extraction. The FTIR spectra is shown in Fig. 6. The peaks indicate
presence of C-H stretching in phenyl groups, C=C double bonds in the aromatic rings,
C=O stretching in the samples and also C-H stretching in aromatic rings and/or from
branched aliphatic chains. However a pair of sharp peaks in the range of 1000-1100 cm-1
and 3600-3700 cm-1, observed in case of the raw and residue coal samples were missing
in the spectra of ash-free coal. These two peaks have been reported to designate presence
of mineral matters in the raw coal and residue, thereby showing that ash-free coal
contains no or, significantly low quantities of mineral matter.
Similar observations have been reported by Yoshida et al [10]. They have also observed
peaks in extracts, which are due to extraction solvents remaining in the former.
According to their study, for coals extracted at 350C and 370C, the other peaks were
similar to those of raw coal and residue; but for the extract obtained at 380C, the ratio of
intensity of aliphatic C-H stretching to that of aromatic C-H stretching was higher than
that at 350C, indicating that chemical reactions like gas evolution became significant at
380C.
22
2.11. Coal beneficiation by agglomeration techniques

Beneficiation of bituminous and lignite coals can be done by agglomeration using
binding oils containing either p-xylene, or deodorized rectisol naphtha and the reduction
in ash content has been studied with respect to particle size, mixing speed, mixing time,
oil to coal ratio and oil characteristics. It has been observed that the ash reduction of 320
mesh bituminous coal was more than that of 200 mesh coal showing reductions of 17%
and 14%, respectively. Thus, the ash reduction of smaller sized particles is greater than
that of the larger ones. Higher mixing speeds and longer mixing times has been reported
to have removed greater percentage of ash, but smaller flocs are formed, which are
difficult to handle. Hot water dried lignite shows greater removal of ash compared to as
received lignite. [16] However, this method does not remove ash to a much larger extent
as done by other chemicals.
2.12. Beneficiation by the use of inorganic chemicals

Beneficiation of Bituminous coals has also been done with aqueous HF followed by
HNO3 at temperatures of about 65. It has been observed that HF, if used alone reduces
the ash content to about 2.6% by weight, while further treatment with HNO3 reduced the
ash content to about 0.6% by weight. It was reported that prior to treatment with HNO3,
compounds such as AlF3, NaAlF4, CaF2, MgF2 formed during leaching and pyrites (FeS2)
does not react with HF. If HNO3 is used, then the fluoride ions react with the H+ ion of
HNO3 to form HF. However, HNO3 only reacts with pyrites above a particular HNO3
concentration, which suggests that it reacts with the organic coal structure to a certain
extent. Some amount of sulphur in the coal has also been observed to have decreased.[17]
Chowdhury, et al. [18] treated high ash Indian Western Coal Fields-Nagpur coal,
containing over 50% ash with 25% (w/w) aqueous ammonia solution under ambient
conditions. Then the treated coal was washed and made to react with concentrated
sulfuric acid and small quantities of calcium fluoride at 350 over four hours. Calcium
fluoride was added to promote in situ production of hydrofluoric acid in the reaction
mixture. The coal was dried and further boiled with dilute hydrochloric acid. The ash
content of the treated coal was reduced to 9.6% from 32.9% of the untreated coal. The
first treatment was aimed at disrupting the bonding forces in the coal structure (where
23
majority of the mineral matter was located) to aid in enhanced demineralization during
the second treatment. After the first treatment, the ash content reduced from 32.9% to
28.5%. After the second treatment with concentrated sulphuric acid, the ash content
increased due to the formation of calcium sulphate. However, subsequent treatment with
dilute hydrochloric acid was done to dissolve the calcium sulphate and reduction of ash
content to 9.6%.
2.13. Reduction of ash content of coal with solvents without coal extraction
It has been reported that ash content of the extract reduces after treatment of coal with
solvents. Saha, et al. [19] treated samples of coal with different solvents such as NMethyl-2-Pyrrolidone (NMP), Furfural, Aniline, Acetic Acid and Toluene by varying the
amounts of solvents. Coal was treated with the above mentioned solvents for a particular
amount of time and then the solvent was removed from the coal by thermal distillation,
followed by drying. Comparative study of different solvents show NMP is the best
solvent with respect to the removal of ash content from coal. The maximum reduction of
ash content of coal is 72 % at 1:10 coal to solvent ratio, 120 and 1 atmospheric
pressure in presence of NMP as an extractant which has high chemical and thermal
stability. The same experiment, when performed using with Crotonaldehyde, Acetonitrile
and Benzene showed that the highest percentage of ash removal was 53.84% when the
coal to solvent ratio was 1:70 [20].
It can be concluded from these literature review that ash content of coals can be reduced
with both inorganic chemicals as well as organic solvents. Solvent extraction of coals is
an effective method of reducing the ash content of coals, but the extraction yields remain
low. Most experiments aim at increasing the extraction yield of coals. Since polarity of
the solvents greatly influence the extraction yield of coals, various additives can be mixed
with the solvents to enhance their polarities and extraction yield as well.
24
Chapter: 3
Experimental Materials &
Procedure
____________________________________________
3.1. Materials
A coal sample of Indian origin was used in all experiments carried out during this study.
The coal was pulverized to 60 mesh (<210m) for extraction and proximate analysis.
Toluene and 1-Methyl-2-pyrrolidone (NMP), procured from Merck were used as it is as
solvents. The additives used in these experiments were p-Nitro Benzoic acid (obtained
from Sisco Research Laboratories Pvt. Ltd.), Quinoline (procured from Loba Chemie Pvt.
Ltd.), Calcium Fluoride (purchased from Loba Chemie Pvt. Ltd.) and fused Calcium
chloride (procured from Merck).
3.2. Experimental procedure

3.2.1. Proximate analysis of coal sample
Proximate analysis of the coal sample was carried out to determine the percentages of
moisture, volatile matter, ash and fixed carbon of the raw material.
3.2.1.1. Determination of moisture content: The moisture content was determined
by heating about 5 g of coal in an uncovered petridish at 110C for about an hour
in a hot air oven. The sample was taken out of the oven with the cover on it,
consequently cooled in a desiccator and weighed. This procedure is repeated till
the weight of the sample reached a constant value. The percentage of moisture in
the coal was calculated from the loss in weight of the sample.
25
3.2.1.2. Determination of volatile matter: The volatile matter of the coal sample
was determined by taking 1 g of the sample in a silica crucible and was covered
with a lid. Thereafter, the sample was heated in a muffle furnace at 925C for
exactly 7 minutes. The warm crucible was cooled on a cold iron plate and then
transferred to a desiccator. The percentage of volatile matter in the coal was
calculated from loss in weight of the sample.
3.2.1.3. Determination of ash content: About 1 gram of the coal was taken in a
silica crucible and placed in a muffle furnace at 400C without lid. The sample
was heated from 400C to 450C in about 30 minutes and this temperature was
maintained for another 30 minutes. Subsequently, the incineration was completed
by heating the coal sample for 1 hour at about 775C. The crucible was taken out
of the muffle furnace, covered with the lid and cooled in a desiccator. The
percentage of ash of the coal was determined from the loss in weight of the
sample.
3.2.1.4. Determination of fixed carbon: Percentage of fixed carbon in the coal was
calculated by subtracting the percentages of moisture, volatile matter and ash
from 100.
3.2.2. Thermal extraction of coals
Fig. 3.1 shows a schematic diagram of the experimental procedure. Approximately 20 g
of the pulverized coal was taken in a beaker and 200 g solvent and additives with
different weight percentages were added to it. Then thermal extraction of the coal was
carried out by heating coal-solvent slurry with constant stirring. After reaching the
prerequisite temperature, it was maintained for desired period of time. The temperature of
extraction was selected such that it was lesser than the boiling point of the solvent. The
beaker was covered with a piece of aluminium foil during thermal extraction to prevent
loss of solvent by evaporation. The ratio of coal to solvent was 1:10 (by weight) in all
the experiments. The speed of rotation of the stirrer was also kept constant throughout all
the experiments carried out during this research work. The percentages of additives, time
and temperature of extraction for all the experiments are represented in Table 3.1.
26
After thermal extraction, filtration was carried out to separate the liquid phase and the
undissolved solid coal residue using filtration. The residue was washed several times with
fresh solvent to remove extract that remained with the residue. Solvent containing extract
was kept aside for recovery of the extract which is explained in details later in this thesis
at section 3.4. The residue was dried in a hot air oven to remove excess solvent. The
thermal extraction set up is shown in Fig. 3.2.
3.2.3. Extraction of coal by Ultrasonic irradiation
Approximately 20 g of pulverized coal was extracted with 200 g of NMP without any
additive under ultrasonic irradiation (333 kHz) for 30 minutes at room temperature.
After extraction, filtration was carried out to separate the extract and the residue by using
the same procedure as described in section 3.2.2. The residue was dried in a hot air oven
and the solvent containing the dissolved extract was keep aside for recovery of the
extract.
Solvent
Pulverized coal
Additive
Thermal extraction of
coal with solvent and
additive with constant
stirring
Removal of
unextracted part
of coal (residue)
by Filtration
Separation of extracted
coal from solvent by
Thermal distillation
Drying of
residue in
Hot air oven
Recovered solvent
Removal of remaining
solvent from extract in
Hot air oven
Coal Extract
Fig. 3.1. Schematic representation of experimental procedure
27
Coal
Residue
Table 3.1: Particulars of all experiments

Sl.
No.
Solvent
Additive
1
2
Toluene
NMP
Concentration
of additive
(in weight %
of raw coal)
-
3
4
5
NMP
NMP
NMP
150
Thermal
150
Thermal
150
Thermal
NMP
(recycled)
NMP
(recycled)
NMP
(recycled)
NMP
0.1
150
Thermal
10
NMP
0.5
150
Thermal
11
NMP
1.0
150
Thermal
12
NMP
2.5
150
Thermal
13
NMP
5.0
150
Thermal
14
15
16
17
18
19
20
NMP
NMP
NMP
NMP
NMP
NMP
NMP
p-nitro benzoic
acid
p-nitro benzoic
acid
p-nitro benzoic
acid
p-nitro benzoic
acid
p-nitro benzoic
acid
Quinoline
Quinoline
Quinoline
Quinoline
Quinoline
Calcium fluoride
Calcium fluoride
0.1
0.5
1.0
2.5
5.0
0.1
0.5
1
1
1
1
1
1
1
150
150
150
150
150
150
150
Thermal
Thermal
Thermal
Thermal
Thermal
Thermal
Thermal
21
22
23
24
25
26
27
28
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
Calcium fluoride
Calcium fluoride
Calcium fluoride
Calcium chloride
Calcium chloride
Calcium chloride
Calcium chloride
Calcium chloride
1.0
2.5
5.0
0.1
0.5
1.0
2.5
5.0
1
1
1
1
1
1
1
1
150
150
150
150
150
150
150
150
Thermal
Thermal
Thermal
Thermal
Thermal
Thermal
Thermal
Thermal
7
8
28
Time of
Temperature
extraction
of
(hours)
Extraction
(C)
1
90
0.5
Room
temperature
1
150
2
150
3
150
Method of
extraction
Thermal
Ultrasonic
irradiation
Thermal
Thermal
Thermal
Fig. 3.2. Thermal extraction set up

3.2.4. Recovery of extract
The solvent containing extract was subjected to thermal distillation (Fig. 3.3) for
separation of the extract and the solvent. Complete recovery of the solvent was not
possible by distillation. For this reason distillation was continued until volume of solvent
containing dissolved extract reaches approximately 15 ml. After that, the extract was
recovered by evaporating the solvent from the extract in a hot air oven. The weight of the
dried extract was calculated thereafter. The extract obtained is shown in Fig. 3.4.
3.2.5. Analysis of the extract and residue
3.2.5.1. Determination of ash content of the extract and residue: The percentage
of ash in the extract and in the residue was evaluated using the same method as
described in section 3.2.1.3.
3.2.5.2. FT-IR analysis: The FT-IR spectra of the raw coal, residue and extract
after extraction were carried out by a FT-IR spectrophotometer (Perkin Elmer
29
Spectrum 2) at a resolution of 4 cm-1 in the wave number range of 450-4000 cm-1.

50 scans were carried out each time prior to Fourier transformation. Samples of
FT-IR experiments were carried out by KBr pellet method using approximately 5
mg sample in 200 mg of KBr. All spectra were analyzed using Spectra Manager
software.
Fig. 3.3. Thermal distillation set up
Fig. 3.4. Dried Extract in a petridish
30
Chapter: 4
Results & discussions
4.1. Characterization of raw coal sample

4.1. 1. Proximate analysis of raw coal
The proximate analysis of raw coal was performed to determine its characteristics. All
the experiments for proximate analysis were performed at least thrice and the arithmetic
means of the data are given in Table 4.1.
Table 4.1: Proximate analysis of raw coal
Properties
Moisture
Ash
Volatile matter
Fixed carbon
Percentages
(%)
2.290
54.064
10.557
33.089
The proximate analysis shows that this coal sample contains a high amount of ash which
corresponds to mineral matter present in coal sample although moisture and volatile
matter contents are low. The fixed carbon content of this coal is 33.089% which falls
between 25-35%. According to the ASTM standards as reported by National Energy
Technology Laboratory, U.S. Department of Energy, this coal can characterized as
lignite in nature [21].
4.1.2. FT-IR Analysis
FT-IR spectroscopy was performed and is given in Fig. 4.5. In the spectra, noise
indicates the presence of high amount mineral matter in raw coal sample.
31
4.2. Effects of different solvents

Two solvents, Toluene and NMP have been used in the experiments. Percentage of
extracts recovered by thermal extraction of coal for 1 hour of extraction time is
presented in Table 4.2.
Table 4.2: Comparison of percentages of extract recovered from Toluene & NMP
Solvent
Toluene
NMP
Percentages of extract
recovered (%)
0.0495
4.428
From Table 4.2, it can be observed that the percentage of extract recovered in case of
Toluene is much less than that recovered by using NMP. This is why, NMP was chosen
for further experimentation.
Higher percentage of extract recovered in case of NMP is because of the fact that NMP
is a polar solvent. Kim et al. [7] found similar results for polar solvents and reported that
use of polar solvents give higher extraction yield. Toluene, on the other hand, is nonpolar and this little amount of coal extract may be attributed to its non-polar nature. It
has also been reported that bituminous coals can give high extraction yields for nonpolar solvents [5]. But, here, the coal is Lignite in nature as characterized by proximate
analysis, the extract recovered is very which is similar to the results reported by other
researchers [6]. It can be concluded from these results that polar solvents has higher
ability to extract large amount of coal compared to the non-polar solvent for low rank
coals.
4.3. Comparison of methods of extraction

To study the effect of different methods, thermal and ultrasonication were chosen for
extraction of coal samples in the present research work. Figure 4.1 compares
percentages of extract recovered by using thermal extraction at 150C and by using
32
ultrasonic irradiation at room temperature. NMP was used as the extracting solvent for
both the methods of extraction.
5
% of extract recovered
4.5
4
INDEX
INDEX
3.5
3
Thermal extraction
2.5
2
Ultrasonic irradiation
1.5
1
0.5
0
Fig. 4.1: Comparison of percentages of extract recovered by

Thermal extraction & Ultrasonic irradiation
From Fig. 4.1, it can be seen that the percentage of extract recovered in case of thermal
extraction is greater than that recovered by ultrasonic irradiation at room temperature
(Table 4.3). This indicates that thermal energy needs to be supplied for higher yields of
extracts. For this reason, thermal extraction was chosen for the other experiments.
Table 4.3: Comparison of percentages of extract recovered by Thermal extraction

& Ultrasonic irradiation
Method of extraction
Thermal
extraction
4.428
recovered (%)
33
Ultrasonic
irradiation
3.386
4.4. Determination of optimum time of extraction

To study the effect of time on the yield of extract and reduction of ash content in the
extract, raw coal was thermally extracted for 1, 2 and 3 hours with NMP. The
temperatures were maintained at 150C for all the experiments
4.4.1. Comparison of percentages of extract recovered: The percentages of extract
recovered for 1, 2 and 3 hours of extraction time with NMP are given in Figure 4.2.
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
1.0
1.5
2.0
2.5
3.0
Time of extraction (hours)
Fig. 4.2: Percentages of extract recovered

under different times of extraction for fresh NMP
The percentages of extract recovered are nearly same for extraction times of 1 hour and
2 hours. However, for 3 hours of extraction time, percentage of extract increases, but the
increase is not very significant. On the other hand, energy consumption for 3 h heating is
three times more than 1h heating. That is why, 1 hour has been chosen as the optimum
time of extraction for all the experiments.
4.4.2. Comparison of ash reduction in extracts: The reduction of ash content in the
extract for the different times of extraction are shown in Fig. 4.3 It can be seen that in all
three cases ash contents of the extracts lie in the range of 4-6%. These values have
34
fluctuations because the distribution of mineral matter in coal is not uniform. As a result,
it can be said from the results obtained during this study that time of extraction does not
affect ash content in the extracts. The ash content of residue and extracts of coal after
extraction with NMP are compared in Table 4.4.
% reduction of ash content in extract
100
98
96
94
92
90
88
86
84
82
80
1.0
1.5
2.0
2.5
3.0
Fig. 4.3: Percentages of ash removal of extract

under different times of extraction for fresh NMP
Table 4.4: Percentages of extract recovered and ash removed under different times
of extraction for fresh NMP
Time of extraction
1 hour
2 hours
3 hours
recovered (%)
Ash content of extract (%)
4.428
4.268
5.629
4.167
3.571
4.762
Percentage reduction of ash

content in extract (%)
Ash content of residue (%)
92.292
93.395
91.190
54.321
52.778
53.086
35
4.4.3. FT-IR spectra of coal extract and residue obtained using fresh NMP: The FT-IR
spectra of the coal extract obtained by using fresh NMP is given in Fig. 4.4. From the
spectra, peak that appeared at 1675 cm-1and 1124 cm-1denote C=O (carbonyl)
stretching and =C-H bending in alkenes respectively. A peal that appeared at 604 cm-1 is
due to presence of C-H bending in alkynes.
The FT-IR spectra of raw coal and residue obtained after extraction with NMP are
shown in Fig 4.5. The noise in the spectra denotes presence of high amount of mineral
matter in both raw coal as well as residue. In the spectra, peaks obtained at 1592 cm-1and
1034 cm-1, signifies the presence of C-C bond stretching in aromatics and =C-H bend in
alkenes respectively. However, the peaks, which are observed in case of the raw coal
sample have diminished in the spectra obtained for the residue. This denotes that some
of the functional groups present in the raw coal have been extracted by NMP and can be
observed in the extract.
----Fresh NMP
----Reused NMP
Fig. 4.4: FT-IR spectra of coal extracts obtained using fresh and reused NMP
36
----Raw coal
----Residue obtained with NMP
Fig. 4.5: FT-IR spectra of raw coal and residue obtained using NMP
4.5. Comparison of results obtained using reused and fresh (unused) NMP
To study the effect of using reused solvent on thermal extraction, raw coal was extracted
with reused NMP at 150C for 1, 2 and 3 hours.
4.5.1. Comparison of percentages of extract recovered: The percentages of extract
recovered for extraction with reused NMP under different times of extraction are shown
in Fig.4.6. The percentages of extract recovered are comparable for both fresh and
recycled solvents. However, a minor reduction in the percentage of extract recovered are
observed for extraction times of 1 hour and 3 hours. As a result, it can be concluded that
reusing the solvent lowers the ability of NMP to extract coal, but not to a very large
extent.
37
6
For fresh NMP
For reused NMP
5
4
3
2
1
1.0
1.5
2.0
2.5
3.0

under different times of extraction for fresh & reused NMP
4.5.2. Comparison of ash reduction in extracts: The effect of reused NMP on reduction
of ash content in the extract is shown in Fig.4.7. It can be observed that the ash content
of the extract increases for reused solvent i.e., ability of ash removal from coal is
reduced for reused solvent. This could be due to the presence of leached out mineral
matter in recycled solvents used for extraction which is attributed to lower ash removal
in case of recycled solvent compared to fresh solvent. It has been reported previously
that solvent has ability to leach away some amount of mineral matter of coal [19,20].
The ash content of the residue remains almost same as that of the raw coal as shown in
Table 4.5.
38
% reduction of ash content in extract
100
For fresh NMP

For reused NMP
95
90
85
80
75
70
65
60
55
50
1.0
1.5
2.0
2.5
3.0
Fig. 4.7: Percentages of ash removal of extract

under different times of extraction for fresh &reused NMP
Table 4.5: Percentages of extract recovered and ash removed under different times
of extraction for reused NMP
Time of extraction
1 hour
2 hours
3 hours
recovered (%)
4.199
4.440
5.464
13.984
14.700
14.000
74.134
72.810
74.105
54.025
53.211
55.294

4.5.3. Comparison of FT-IR spectra of extracts obtained using fresh and reused NMP:
The FT-IR spectra of the extracts obtained using fresh NMP and reused NMP from
previous experiments are shown in Fig 4.3. From the spectra, it can be observed that the
groups extracted in both the cases are almost similar. The peaks corresponding to
various functional groups are less pronounced in case the extract, obtained using reused
39
solvent. This may be due to the fact that due to reuse, some amount of carbonaceous
matter and minerals from coal may have remained in the matrix of the solvent. This
reduces the solvents ability to extract coal and reduce the ash content of the extract. In
Fig. 2, peaks at 3728 cm-1, 3695 cm-1 and 1031 cm-1are designated as presence of
mineral matter in the extract obtained in case of reused NMP. Rahman et al. [6] have
reported sharp peaks within the range 3600-3700 cm-1and 1000-1100 cm-1are due to
mineral matter in coal which is also observed in the present study.
4.6. Effect of reusing the residue for thermal extraction

The residue formed during thermal extraction of coal by NMP for 1 hour was reused
once again for extraction using fresh NMP as solvent for 1 hour without any additive.
The results are discussed in details below.
4.6.1. Percentages of extract recovered from fresh and reused coal residue: The results
for percentages of extract recovered from fresh coal and reused coal residue are shown
in Fig. 4.8. It can be observed that yield of extract decreases when residue coal is used
from previous experiments. This is because of fact that during thermal extraction of the
coal for the first time, most of the NMP-soluble part of coal already got dissolved and
extracted. Consequently, a smaller quantity of NMP-soluble portion was left behind in
the residue to be extracted by NMP. In this method, the total amount of extract
recovered from the raw coal was 7.70%. The results are summarized in Table 4.6.
% of extract
recovered
5
4
INDEX
Fresh coal
Reused residue
1
0

from fresh &reused residue
40
4.6.2. Percentages of ash reduction in extract: The percentages of ash reduction in

extracts obtained from fresh coal and reused residue are shown in Fig. 4.9. It can be
observed that there is no significant effect reutilization of coal on the percentages of ash
% of ash reduction in extract
reduction.
100
90
80
70
60
50
40
30
20
10
0
INDEX
Fresh coal
Reused residue
Fig. 4.9: Percentages of ash reduction in extract from fresh coal &reused residue
Table 4.6: Percentages of extract recovered and ash removed from fresh coal and
reused residue
Coal used (fresh/residue)
Fresh coal
Residue
recovered (%)
4.428
3.630
4.167
3.448

92.292
93.524
54.321
55.961
4.7. Experimental results for use of additives along with NMP

To study the effect of additives on the extraction of coal with NMP, four different
additives, viz. p-Nitro benzoic acid, Quinoline, Calcium fluoride and Calcium chloride
were used to extract raw coal. Raw coal was extracted for 1 hour at 150C with NMP
41
and different concentrations of the additives. The concentration of the additives in

weight per cent of raw coal are 0.1%, 0.5%, 1.0%, 2.5% and 5%.
4.7.1. p-Nitro benzoic acid:

4.6.1.1. Percentage of extract recovered: The percentages of extract recovered
for various percentages of p-Nitro benzoic acid are shown in Fig. 4.10. It can be
observed that with increase in concentration of this additive, the yield of extract
increases. When additive concentration is minimum, i.e. 0.1% (by weight of
coal), the yield of extract obtained by using p-nitro benzoic acid is nearly same
as that obtained when NMP is used alone. But, for all the higher concentrations
of the additives, the yield of extract is higher than that obtained when no additive
is used. This enhancement of yield of extract takes place due to the fact that pnitro benzoic acid is a polar compound and it enhances the polarity of NMP.
Thus, the combined effects of the polarities of NMP and p-nitro benzoic acid
bring about the increase of yield of extracts.
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
% of additive (p-nitro benzoic acid)
Fig. 4.10: Percentages of extract recovered for

different concentrations of p-nitro benzoic acid
42
4.7.1.2. Ash content of extract: The reduction in ash content of the extract for
different concentrations of p-Nitro benzoic acid is shown in Fig. 4.11. It can be
observed that decrease in ash content of the extracts take place with higher
concentration of additive. The percentage of ash reduction of extract for higher
concentration of this additive is thus, more than that obtained when NMP is used
alone. For lower concentrations of p-nitro benzoic acid, the ash content of the
extract is same as that when no additive is used. Thus, it may be concluded that
with increase in concentration of the additive, the polarity of the solvent
increases and thus, the ability of the solvent to leach away some portion of the
mineral matter also increases. This might have possibly resulted in a reduction of
ash content of the extract.
However, the ash contents of the residues are
comparable with that of the raw coal (Table 4.7).
100
% ash reduction in extract
98
96
94
92
90
88
86
84
82
80
% of additive (p-nitro benzoic acid)
Fig. 4.11: Percentages of ash reduction in extract for

different concentrations of p-nitro benzoic acid
43
Table 4.7: Percentages of extract recovered and ash removed for using p-nitro
benzoic acid as an additive with NMP
Concentration of p-nitro
0%
benzoic acid
(in weight % of raw coal)
4.428
recovered (%)
4.167
Ash content of extract
(%)
Percentage reduction of 92.292
ash content in extract (%)
54.321
Ash content of residue
(%)
0.1%
0.5%
1.0%
2.5%
5%
4.577
4.822
4.935
5.405
7.396
4.348
4.310
2.821
2.934
1.149
91.958
92.028
94.782 94.573 97.874
54.022
49.367
55.229 54.021 53.476
4.7.2. Quinoline:
for various percentages of Quinoline are shown in Fig. 4.12. It is evident from
Fig. 4.10 that the use of Quinoline, inspite of being highly polar is not effective
enough to bring about an increase in the yield of coal extract as an additive (in
low concentrations). Kashimura et al. [13] have reported that 50% (by weight) of
quinoline in a mixture of i-methyl naphthalene, indole and quinoline bring about
an extraction yield of 69% at temperatures of about 360C. Thus, in order to
enhance the extraction yield, the concentration of quinoline should be higher, or,
quinoline itself has to be used as a solvent for extraction.
4.7.2.2. Ash content of extract: The ash content of the extract obtained by using
additive (quinoline) along with NMP is lower than that obtained when no
additive is used. The results are shown in Fig. 4.13. The fluctuations (Table 4.8)
in the values of ash contents of the extracts may be either due to the non-uniform
distribution of ash content in the coal, or, due to the effect of Quinoline. It could
be due to the small quantities of quinoline used, can enhance the effectiveness of
NMP in leaching away some portion of the mineral matter of the extracts.
44
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
% of additive (Quinoline)

different concentrations of Quinoline
100
98
96
94
92
90
88
86
84
82
80
% of additive (Quinoline)

different concentrations of Quinoline
45
Table 4.8: Percentages of extract recovered and ash removed for using Quinoline
as an additive with NMP
Concentration of
0%
Quinoline
4.428
recovered (%)
4.167
(%)
54.321
(%)
0.1%
0.5%
1.0%
2.5%
5%
4.382
4.217
4.239
4.326
4.235
2.857
2.299
3.053
3.274
2.500
91.958
92.028
94.782 94.573 97.874
53.204
54.075
49.972 51.458 48.047
4.7.3. Calcium fluoride:

for various percentages of Calcium fluoride are shown in Fig. 4.14. From Fig.
4.14, it can be seen that the use of calcium fluoride does not enhance the yield of
the extract. When this additive is used, the yield of extract is a little lower than
that obtained by the use of NMP alone. Takahashi et al. [14] have reported that
halide ions as additives in NMP-Carbon disulphide mixture can enhance the
yield of extracts, the maximum yield being given by addition of fluoride salts,
due to high electronegativity. The results obtained during this study are not in
agreement with the results obtained by Takahashi et al. [14]. This may be due to
the interaction between calcium fluoride and NMP, which brings about this
minor difference in yield of extract.
46
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
% of additive (Calcium fluoride)

different concentrations of Calcium fluoride
different concentrations of Calcium fluoride is shown in Fig. 4.15. It can be
observed that for higher concentrations of this additive, the percentage of ash
reduction in the extracts is more than that obtained when NMP is used alone.
Chowdhuri et al. [18] have reported that during demineralization of coal using
saulphuric acid and calcium fluoride, in situ production of hydrogen fluoride
reduces the ash content. Here, it may be possible that calcium fluoride reacts
with the mineral matter of coal to form other compounds, which are left behind
in the residue. However, the lower concentrations of this additive do not
significantly lower the ash content of the extracts (Table 4.9).
47
100
98
96
94
92
90
88
86
84
82
80
% of additive (Calcium fluoride)

different concentrations of Calcium fluoride
Table 4.9: Percentages of extract recovered and ash removed for using Calcium
fluoride as an additive with NMP
Concentration of Calcium
0%
fluoride
4.428
recovered (%)
4.167
(%)
54.321
(%)
0.1%
0.5%
1.0%
2.5%
5%
3.412
3.328
3.938
3.318
3.300
3.752
4.286
1.754
2.778
1.875
93.060
92.072
96.756 97.874 96.532
53.147
52.618
54.056 52.104 53.502
4.7.4. Calcium chloride:

4.7.4.1. Percentage of extract recovered: The yields of extracts for different
concentrations of calcium chloride are shown in Fig. 4.16. It can be observed
from the Fig. 4.14 that increasing concentration of calcium chloride enhances the
48
yield of extracts. This may be attributed to high eletronegativity of calcium

chloride, which increases its reactivity towards coal. Unlike calcium fluoride,
calcium chloride with NMP is effective in enhancing the yield of extract. It may
be due to the fact that calcium chloride interacts less with NMP and reacts with
the cross-linking structure of coal better to form radicals, thus enabling NMP to
penetrate into the structure of coal. However, calcium fluoride, due to its high
reactivity may interact with NMP much before it can start interacting with coal,
resulting in lower yield of extract.
14
12
10
8
6
4
2
0
% of additive (calcium chloride)

different concentrations of Calcium chloride
different concentrations of Calcium chloride is shown in Fig. 4.17. It can be
observed that when calcium chloride is used, the percentage of ash reduction of
the extracts is much lower than that achieved when no additive is used with
NMP. This may be due to reaction of mineral matters with calcium chloride. If
the products of reaction between the additive and the minerals are present in the
extract and are not leached away by the solvent, then it may be possible that
there is an increase in ash content of the extract.
49
100
95
90
85
80
75
70
% of additive (calcium chloride)

different concentrations of Calcium chloride
Table 4.10: Percentages of extract recovered and ash removed for using Calcium
chloride as an additive with NMP
Concentration of Calcium
0%
chloride
4.428
recovered (%)
4.167
(%)
54.321
(%)
0.1%
0.5%
1.0%
2.5%
5%
4.526
4.886
7.207
8.861
13.313
8.504
9.059
7.348
12.017
9.597
84.270
83.244
86.409 77.773 82.249
50.281
51.794
53.175 52.064 48.193
50
4.8. Comparison of the experimental results for the different additives

4.8.1. Comparison of the yields of extracts:
The percentages of extracts recovered by using different concentrations of the four
additives are shown in Fig. 4.18. It can be observed that the yield of extract is the
maximum when Calcium chloride is used as an additive with NMP. The maximum
extract yield is obtained when the concentration of Calcium chloride is 5% by weight of
raw coal. The yields of extract using p-Nitro benzoic acid are comparable with that of
Calcium chloride at additive concentrations of 0.1% and 0.5% by weight of raw coal.
The lowest extraction yield was observed for calcium fluoride among all the additives
used in this research work.
p-Nitro benzoic acid molecule has a nitrogen atom containing a lone pair of electrons
and is a polar compound. It is because of these properties that a higher yield of extract is
obtained by using p-nitro benzoic acid compared to the yield of extract obtained by
using NMP alone. However, higher yield of extract obtained in case of Calcium chloride
can be attributed to the electronegativity of the chlorine atom in it.
14
For p-Nitro benzoic acid

For Quinoline
For Calcium fluoride
For Calcium chloride
12
10
8
6
4
2
0
% of additive
Fig. 4.18: Comparison of percentages of extract recovered for

51
4.8.2. Comparison of ash reduction in the extracts:

From Fig. 4.19, it can be observed that the percentage ash reduction in the extract is
lowest for all the concentrations of Calcium chloride. However, the percentages of ash
reduction are nearly comparable for other additives and lie in the range of 92% to 98%.
100
% ash rduction inextract
95
90
For p-Nitro benzoic acid

For Quinoline
For Calcium fluoride
For Calcium chloride
85
80
75
70
% of additive
Fig. 4.19: Comparison of the percentages of ash reduction in extract for

4.8.3. Comparison of FT-IR results of the extracts for the different additives:
FT-IR spectra of extracts with and without various additives have been compared in
Fig.4.20. From the spectra, we can observe that a peak at 3413 cm-1 is prominent in case
of extract obtained while calcium chloride was used as additive along with NMP. This is
due to O-H stretching of hydroxyl groups. Also, in case of calcium chloride, a peak at
2144 cm-1 corresponding to -CC- in alkynes stretching can be observed. This denotes
that the olefinic group has been extracted by calcium chloride as an additive in the
extraction process. In the range of 450-1600 cm-1, a number of distinct peaks
corresponding to various groups can be observed in case of p-nitro benzoic acid and
calcium chloride. These are not pronounced when NMP is used alone, or with quinoline,
or, calcium fluoride. This denotes that the chemical nature of the additives affects the
52
groups extracted by the solvent. Here, additives prompted NMP to extract those groups,
which NMP alone cannot extract. The higher yield of extract in case of p-nitro benzoic
acid and calcium chloride may be attributed to the fact that more functional groups are
extracted by using these additives. Again, in case of the extract obtained without
additives, a sharp peak at 1124 cm-1 corresponding to =C-H bending in hydrocarbons
was obeserved. This peak is not pronounced for extracts derived using additives. In case
of the extract using Calcium chloride, spectra of -C=O and C=C- have fused together to
give a broad peak at 1658.77 cm-1.
----NMP (no additive)

----Quinoline
----p-Nitro benzoic acid
----Calcium fluoride
----Calcium chloride
Fig. 4.20: Comparison of the FT-IR spectra of the extracts for the different
additives
53
Chapter: 5
Conclusions
___________________________________________
5.1. Conclusions
The effect of addition of p-Nitro benzoic acid, quinoline, calcium fluoride and calcium
chloride on the extraction of coal with NMP was studied during this research work. The
effects of the additives on the reduction of ash content in the extract were also
investigated. Within the limits of the present experimental conditions, the following
conclusions can be made:
(i)
The yield of extract obtained by extraction of coal using NMP by ultrasonic

irradiation at room temperature is lower than that obtained by thermal
extraction of raw coal with NMP at 150C.
(ii)
NMP, being a polar solvent gives a much higher yield of extract compared to
toluene, which is a non-polar solvent because non-polar solvents do not give
high extraction yields for low rank coals. The coal used in this research work
was of low rank and, hence, could not be extracted by Toluene.
(iii)
Thermal extraction of coal with fresh and reused NMP at 150C for different
times of extraction showed that increase in time of extraction from 1 hour to 3
hours does not remarkably increase that yield of coal extracts, but increases
the energy requirement of the process. That is why, 1 hour was chosen as the
time of extraction for all the other experiments.
(iv)
When reused NMP was used for thermal extraction of coal, there was a minor
decrease in the yield of coal extract compared to extraction with fresh NMP
under similar conditions.
54
(v)
When the residue of thermal extraction with NMP is reused for thermal
extraction with the same solvent, the reduction in ash content is coparable
with the ash reduction of fresh raw coal. However, the yield of extract
decreases when the residue is reused.
(vi)
p-Nitro benzoic acid being a polar compound enhances the yield of coal
extracts. But, the extraction yield was further enhanced while Calcium
chloride was used along with NMP. The yield of extract obtained by using 5%
(by weight of coal) of calcium chloride enhances the yield of extract to nearly
double of that of p-nitro benzoic acid under similar conditions.
(vii)
Calcium fluoride, unlike calcium chloride does not enhance the yield of coal
extract when used as an additive with NMP, in spite of the electro-negativity
of the fluoride ion.
(viii) The reduction of ash content of the extracts is also affected by the use of
additives. Calcium fluoride, unlike calcium chloride does not enhance the
yield of extract at all, but the ash content of the extract decreases to almost
half the ash content of the extract when NMP is used alone. Again, when
calcium chloride is used, the ash content of the extract was almost double of
the ash content of the extract obtained by using NMP alone.
(ix)
Quinoline, as an additive has very little effect on the yield of extract, or, the
reduction of ash content of the extract. It can be concluded from the present
study that it should be used as a solvent rather than an additive for extraction
of coal.
5.2. Future prospects of the work

In this research work, NMP was used as a solvent to extract coal. But NMP is a costly
solvent and greatly increases the expenses of the process. NMP was used here because of
its polar nature and ability to extract coal. Hence, in order to make the process costeffective, less expensive solvent can be explored in future research works which should
be of polar in nature and at the same time has ability of extract coal.
The use of calcium chloride as an additive can be investigated for this solvent. It was
observed higher amount of calcium chloride enhances the yield of extract it does not
55
bring down ash content of the extract to a significantly low value. Calcium fluoride, on
the other hand, decreases the ash content to a large extent, although it does not enhance
the yield of extract. Therefore, the effects of both these two additives together at different
percentages can be investigated for a suitable solvent. For such an experiment, the
concentrations of the two additives can be determined by optimization techniques to
reach a suitable compromise between the yield of extract and the reduction in ash content
of the extract of coal. The use of quinoline as an additive must be discarded as it does not
affect the extraction yield in low concentrations.
56
References
________________________________________________
1.
Speight, J.G., Handbook of coal analysis. Vol. 166. 2005: John Wiley & Sons.
2.
Sarkar, S., Fuels and combustion. 1974: Universities Press.
3.
Larsen, J.W. Organic chemistry of coal. 1978 .
4.
Speight, J.G., The chemistry and technology of coal: CRC Press.
5.
Okuyama, N., et al., Hyper-coal process to produce the ash-free coal.Fuel Processing
Technology, 2004.85(8): p. 947-967.
6.
Rahman, M., A. Samanta, and R. Gupta, Production and characterization of ash-free

coal from low-rank Canadian coal by solvent extraction.Fuel Processing
Technology.115: p. 88-98.
7.
Do Kim, S., et al., Production of low ash coal by thermal extraction with N-methyl-2pyrrolidinone.Korean Journal of Chemical Engineering, 2008.25(4): p. 758-763.
8.
Li, C., et al., Coal dissolution by heat treatments in N-methyl-2-pyrrolidinone, 1, 4, 5, 8,

9, 10-hexahydroanthracene, and their mixed solvents: A large synergistic effect of the
mixed solvents.Energy & fuels, 2000.14(1): p. 190-196.
9.
Yoshida, T., et al., Effect of extraction condition on HyperCoal production (2) effect of
polar solvents under hot filtration.Fuel Processing Technology, 2004.86(1): p. 61-72.
10.
Yoshida, T., et al., The effect of extraction condition on HyperCoal production (1) under
room-temperature filtration.Fuel, 2002.81(11): p. 1463-1469.
11.
Shui, H., Z. Wang, and J. Gao, Examination of the role of CS 2 in the CS 2/NMP mixed
solvents to coal extraction.Fuel Processing Technology, 2006.87(3): p. 185-190.
12.
Makgato, M.H., et al., Alkali-assisted coal extraction with polar aprotic solvents.Fuel
Processing Technology, 2009.90(4): p. 591-598.
13.
Kashimura, N., T. Takanohashi, and I. Saito, Upgrading the solvent used for the thermal
extraction of sub-bituminous coal.Energy & fuels, 2006.20(5): p. 2063-2066.
14.
Takahashi, K., et al., Effect of addition of various salts on coal extraction with carbon
disulfide/N-methyl-2-pyrrolidinone mixed solvent.Energy & fuels, 2001.15(1): p. 141146.
15.
Pande, S. and D.K. Sharma, Studies of kinetics of diffusion of N-methyl-2-pyrrolidone

(NMP), ethylenediamine (EDA), and NMP+ EDA (1: 1, vol/vol) mixed solvent system in
chinakuri coal by solvent swelling techniques.Energy & fuels, 2001.15(5): p. 1063-1068.
57
16.
Timpe, R.C., C.L. Knudson, and P. Mack, Beneficiation of a bituminous coal and a
lignite coal by agglomeration using novel binding oils. Amer. Chem. Soc. Div. Fuel
Chem. Preprints, 1988. 33(2): p. 352-358.
17.
Steel, K.M. and J.W. Patrick, The production of ultra clean coal by chemical
demineralisation.Fuel, 2001.80(14): p. 2019-2023.
18.
Choudhury, R. and A.K. Bhaktavatsalam, Beneficiation of Indian coal by chemical

techniques.Energy conversion and management, 1997.38(2): p. 173-178.
19.
Saha, B., Mondal, C., Removal of Ash content from Indian Coal by Using Solvents,
International Journal of Modern Engineering Research, Vol. 3, Issue. 1, 2013, 133-138
20.
Saha, B., Mondal, C.,Studies on Role of Solvents on Reduction of Ash from Indian Coal,
The Journal of Chemical Science. Photon, 107 (2013), 187-191
21.
https://www.netl.doe.gov/.../energy%20analysis/.../QGESS_DetailCoalSpecsDetailed
Coal Specifications. January 2012, National Energy Technology Laboratory, U.S.
Department of Energy.
58
List of publications
___________________________________________
1. Ghosh. S., Mondal, C., Beneficiation of Coals: A Review, International Journal

of Engineering Sciences & Research Technology, June, 2014. 3(6), 800-804
[Ghosh, 3(6): June, 2014]
ISSN: 2277-9655
Scientific Journal Impact Factor: 3.449
(ISRA), Impact Factor: 1.852
IJESRT
INTERNATIONAL JOURNAL OF ENGINEERING SCIENCES & RESEARCH
TECHNOLOGY
Beneficiation of Coals: A Review
*
Shashwata Ghosh *, Dr. Chanchal Mondal

Chemical Engineering Department, Jadavpur University, India
sashwata0910@gmail.com
Abstract
Coal is an important fossil fuel and is used as a major source of energy in power plants and blast furnaces.
But, Indian coals contain a large amount of impurities, particularly ash forming mineral matter, which interfere with
proper combustion of coal and decreases its calorific value. Industrial uses demand coal with minimum ash content
so that it can be efficiently used in metallurgical, or, power plants. This paper reviews the removal of ash-forming
minerals of coal using chemical techniques and also the extraction of coal by the use of various solvents. Solvents,
like N-Methyl-2-pyrrolidone (NMP), 1-methyl naphthalene, Dimethylformamide (DMF), Dimethyl sulfoxide
(DMSO) can be used to reduce the ash content of coal. However, polar solvents have been proved to extract greater
amounts of coal and reduce ash to a greater extent than non-polar solvents, particularly for lower rank, or, subbituminous coals. However, if non-polar solvents are used, then traces of polar additives can also increase the
extraction of coal as well as cause greater reduction of the ash content. The degree of ash reduction not only depends
on the solvent used, but also on the extraction temperature, time and rank of coal.
Keywords: coal, ash, minerals, solvents, rank of coal, extraction
Introduction
Coal is an important source of energy and is
used in many industries like coal-fired thermal power
plants. Coal is also converted into coke, which is
used as a fuel as well as a reducing agent in smelting
iron ore in a blast furnace. But the presence of a high
percentage of ash-forming minerals in coal is
disadvantageous. These minerals are converted into
ash during combustion of coal. These are inherent
mineral matter and Indian coals consist of high
percentage of such minerals. The mineral matter
mainly consists of aluminosilicates apart from pyrites
and few other compounds. The presence of high ash
not only interfere with the effective utilization of
coals due to heat losses, but the disposal of large
amounts of ash is also a problem.
Many studies have been conducted to reduce
the ash content of coal by the use of various solvents.
Studies have also been made to increase the
percentage of coal extracted. The effects of various
parameters like temperature, pressure, effects of
additives, etc. have been studied. The main aim of
this review is to determine the various parameters
which decrease the ash content of coal as well as
increase the extraction of coal. The effects of the
various chemicals used in these studies provide
important clues as to how ash content of coal can be

reduced to a significantly low percentage.
Coal beneficiation by chemical treatment

Coal beneficiation by agglomeration techniques
Beneficiation of bituminous and lignite
coals can be done by agglomeration using binding
oils containing either p-xylene, or deodorized rectisol
naphtha and the reduction in ash content has been
studied with respect to particle size, mixing speed,
mixing time, oil to coal ratio and oil characteristics. It
has been observed that the ash reduction of 320 mesh
bituminous coal was more than that of 200 mesh coal
showing reductions of 17% and 14%, respectively
(Timpe et al.). Thus, the ash reduction of smaller
sized particles is greater than that of the larger ones.
Higher mixing speeds and longer mixing times has
been reported to have removed greater percentage of
ash, but smaller flocs are formed, which are difficult
to handle. Hot water dried lignite shows greater
removal of ash compared to as received lignite
(Timpe et al.). However, this method does not
remove ash to a much larger extent as done by other
chemicals.
http: // www.ijesrt.com(C)International Journal of Engineering Sciences & Research Technology

[800-804]
[Ghosh, 3(6): June, 2014]
Rank of coal in relation to extraction

For higher rank Bituminous coals, it has
been observed that the extraction yields increase with
an increase in temperature and there is a peak
temperature at which a maximum extraction yield is
obtained. Beyond this peak temperature, the
extraction rate again drops. This is related to the
thermal relaxation of molecules. At the peak
temperatures, relatively small molecules may be
released from the cross-linking coal structure to the
solvent (Okuyama et al., 2004).
For lower rank coals, like sub-bituminous
and lignite coals, the extraction yield has been
observed to increase with increase in temperature. A
suitable solvent and high temperature of about 673K
gives an extraction yield of over 70% and very low,
or, negligible ash content (Rahman et al., 2013), as
shown in figure 1. In figure 1, BD, BL and POP are
lignite coals, while CV and GEN are sub-bituminous
coals. A higher proportion of vitrinite and lower
value of MMVR (mean maximum vitrinite
reflectance) has been reported to have given higher
extraction yield as lower MMVR values signify
higher reactivity of coal (Rahman et al., 2013).
Figure:
ISSN: 2277-9655
temperature of coal. When the coal softening point is
closer and closer to the extraction temperature, the
coal extraction becomes higher and higher (Okuyama
et al., 2004). At the softening point, the structure
becomes relaxed and beyond the softening point, the
coal is restructured by cross-linking, which results in
a decrease in extraction yield (Kim et al., 2007). This
is possibly due to the enhanced coalsolvent
interaction at this temperature and consequently,
higher solvent induced thermal relaxation of coal
molecules is occurring and releasing mainly small
molecules and free radicals from the cross-linking
coal structure to the solvent (Okuyama et al., 2004).
In figure 2, Kideko and Roto south are sub-bituinous
coals, while Sunhwa is a Bituminous coal (Kim et al.,
2007).
Figure:
Fig. 2: Variation of extraction yield with temperature

(Kim et al., 2007)
Fig. 1: Effect of coal type on extraction yield using

hydrotreated solvent SB with 1 h of
holding time at 673 K. (Rahman et al., 2013)
Effect of temperature and pressure on extraction

of coal
For higher rank coals, like Bituminous coals,
it has been observed that the extraction yields
increase with an increase in temperature and there is
a peak temperature at which a maximum extraction
yield is obtained, as shown in figure 2. Beyond this
peak temperature, the extraction rate again drops. The
peak temperature at which the extraction yield
becomes maximum has been related to the softening
For lower rank coals, such as lignite and

sub-bituminous coals, there is no softening
temperature at which the coal structure becomes
relaxed and so a polar solvent is required to
breakdown the structure (Kim et al., 2007).
The ash content of coal extracts from both
Bituminous as well as sub-bituminous coals decrease
as the extraction temperature increases (Kim et al.,
2007).
The initial applied pressure has no
significant effect on the extraction yield and ash
reduction; the extraction yield and ash reduction can
be enhanced more by increasing extraction
temperature rather than the initial pressure (Kim et
al., 2007), as shown in figure 3.

[800-804]
[Ghosh, 3(6): June, 2014]
Figure:
Fig. 3: Variation of extraction yield with initial

applied pressure (Kim et al., 2007)
Effect of polar and non-polar solvents on

extraction of coal
For higher rank coals, like Bituminous coals,
it has been reported that non-polar aprotic solvents
like 1-methylnaphthalene can give satisfactory yields
of about 70% by weight (daf) and ash content
reduced to several hundreds of ppm at 340-360
(Okuyama et al., 2004). However, it has also been
observed that if a hydrogen donating solvent like
tetralin is used, the extraction rate becomes more than
that obtained when an aprotic solvent like the former
is used at the same extraction temperature. This has
been attributed to intermolecular hydrogen transfer
from the solvent to the coal to stabilize small
thermally decomposed molecules from coal and coalsoftening phenomenon brings about this process
(Okuyama et al., 2004). Polar solvents, like NMP
have been reported to have given extraction yields of
above 60% for Bituminous coals at temperatures
above 350 (Kim et al., 2007).
However, in case of lower rank coals, such
as lignite and sub-bituminous coals, there is no
softening temperature at which the coal structure
becomes relaxed and so a polar solvent is required to
breakdown the structure (Kim et al., 2007). In case of
sub-bituminous coals, it has been observed a polar
solvent like NMP can give an extraction yield of over
80% at a temperature of about 400 (Kim et al.,
2007). Hydrotreated aromatic hydrocarbons have
given higher extraction yields for low rank coals than
1-methyl naphthalene because the latter contains
polar components (Rahman et al., 2013). NMP has
been reported a better solvent than non-polar ones for
the low rank coals which have much of polar sites (Li
et al., 2000).
ISSN: 2277-9655
Beneficiation by the use of inorganic chemicals
Beneficiation of Bituminous coals has also
been done with aqueous HF followed by HNO3 at
temperatures of about 65. It has been observed that
HF, if used alone reduces the ash content to about
2.6% by weight, while further treatment with HNO 3
reduced the ash content to about 0.6% by weight
(Steel-Patrick, 2001). It was reported that prior to
treatment with HNO3, compounds such as AlF3,
NaAlF4, CaF2, MgF2 formed during leaching and
pyrites (FeS2) does not react with HF. If HNO 3 is
used, then the fluoride ions react with the H + ion of
HNO3 to form HF. However, HNO3 only reacts with
pyrites above a particular HNO3 concentration, which
suggests that it reacts with the organic coal structure
to a certain extent (Steel-Patrick, 2001). Some
amount of sulphur in the coal has also been observed
to have decreased.
Effect of hot filtration and room temperature
filtration on extraction
Coals of various ranks have been extracted
with a variety of organic solvents, viz tetralin, 1methyl naphthalene, dimethyl naphthalene and light
cycle oil (LCO), which is a by-product of cracking of
vacuum gas oil to gasoline. It has been observed that
high extraction yields can be obtained if a suitably
high extraction temperature is maintained; but, if the
separation of residue and solution is conducted at
room temperature, the extraction yields will not
achieve the required specification of Hyper-coal.
Figure:
Fig. 4: Flow diagram of the Hyper-coal process

(Okuyama et al., 2004)
The term Hyper-coal refers to ash-free coal

(Okuyama et al., 2004). This has been attributed to
the separation conducted at room temperature as the
extract components soluble at high temperature might
have deposited while quenching and decreased the
percentage of coal extract (Yoshida et al., 2001).
Hence, filtration after extraction should be performed

[800-804]
[Ghosh, 3(6): June, 2014]
at a high temperature in order to maintain a

satisfactory extraction yield.
Beneficiation by mixtures of solvents
Beneficiation of coal by mixtures of solvent,
like CS2:NMP (in the ratio 1:1) has been reported to
have given a higher extraction yield than that
obtained when NMP is used alone. NMP is a polar
solvent, but when CS2 is added, a synergistic effect is
obtained. It has been reported that with the CS2
addition, the viscosity of the solvent mixture
decreases and the ability of the mixed solvent to
penetrate the cross-link coal structure increases, so
that the mixed solvent can interact with the solventsoluble molecules, such that the extraction yield
increases (Shui et al., 2004). Large synergistic effects
have been observed for coals used with NMP/HHA
(1,4,5,8,9,10-Hexahydroanthracene) mixed solvents
and using the mixed solvents, the dissolution yields
increased, the extent of synergistic effect being
highly dependent on the kind of coal used (Li et al.,
2000). It has been reported that hydrogen donation
from HHA to the coal coal radiacals is the key
reaction (Li et al., 2000).
Effect of various additives
It has been observed that addition of strong
bases, like NaOH, or, sodium tertiary butoxide can
increase the degree of dissolution of coal in solvents
like NMP, DMF, etc. Depending on the extraction
conditions, carbon extraction efficiencies of up to
90% have been obtained, (Makgato et al., 2008) as
shown in figure 5. Sodium, or, potassium hydroxide
is added as a solution with water. However, the
addition of water has been observed to be detrimental
for DMF due to base catalysed hydrolysis of DMF to
dimethyl amine and formic acid in presence of water.
Addition of sodium sulfide addition has been
observed to have further reduced the ash content of
the extracted coal. It has also been reported that as
the NaOH/Na2S molar ratio became high, the coal
extraction also increased (Makgato et al., 2008).
The addition of a small amount of polar
compound such as methanol to nitrogen-containing
polar solvent has been observed to have greatly
increased the thermal extraction yield for subbituminous coals at 360 (Kashimura et al., 2006).
Addition of salts like lithium and
tetrabutylammonium salts with various anions to
polar aprotic solvents, or, solvent mixtures have also
been observed to have increased the extraction yield
for several coals. The yields increase in the order F>Cl->Br->I-, implying that smaller ions with large
electronegativity are responsible for increase in
ISSN: 2277-9655
yields. Hard bases like F- & Cl- attract proton and
since, the solvent is polar and aprotic, these anions
will not be solvated and can interact with some hard
acidic sites in the coal (Takahashi, 2001). However,
soft bases, like Br- & I- get solvated in the soft acid
like CS2-NMP mixture and cannot interact with the
coal (Takahashi, 2001). It has also been reported that
hard bases, like acetate ion can increase the
extraction yield. It has also been reorted that the
addition of alkali metal salts, like LiCl can increase
the polarity of the solvents-salt solutions and increase
the extraction of coal.
It has been observed that if the polar
components of an industrial solvent like CMNO
(crude methyl naphthalene oil) be separated, The
extraction yields obtained with the extracted polar
materials are 20-30% higher than that with CMNO
(Kashimura et al., 2006). It has been reported that
the major polar component of CMNO was quinoline
and the minor constituents were isoquinoline, indole
and methylquinoline. It has also been observed that
indole has a greater ability to extract coal constituents
compared to quinoline. But if both are used with a
non-polar solvent, then a higher extraction yield
compared to quinoline-nonpolar solvent mixture is
obtained (Kashimura et al., 2006).
Figure:
Fig. 5: The effect of solvent nature on the extraction

efficiency at ambient conditions.
Solvent:coal:KOH=100:10:1.56 on a mass basis.
(Makgato et al., 2008)
Conclusion
Ash in coal and can be successfully reduced
to a much lesser quantity by the use of proper
solvents. Both polar and non-polar solvents can be
used for the extraction of higher rank Bituminous
coals. But for lower rank coals, like lignite, or, subbituminous coals, polar solvents are required to break
down the structure for greater dissolution of coal.

[800-804]
[Ghosh, 3(6): June, 2014]
The extent of coal dissolution depends not only

on the nature of solvent, but also on the rank of coal
used, the extraction temperature and extraction time.
The extraction temperature is again related to the
softening temperature in case of Bituminous coals.
But for lower rank coals, the extraction is not related
to the softening temperature; extraction yield
increases with increasing temperature, but a polar
solvent is required to breakdown the structure.
Pressure alone has no influence in the percentage of
coal extracted, or, percentage of ash removed.
The filtration of residue and extract after
extraction should be performed at a high temperature
near the extraction temperature to ensure a high
extraction yield, otherwise components soluble at a
high temperature may be deposited while quenching
at lower temperature.
The addition of certain additives, like polar
compounds can increase the extraction yield from the
coal. Addition of salts may also increase the
percentage of ash removed by reacting with the
inorganic compounds present in the coal and the
products formed during rection may be precipitated,
thereby decreasing the ash content of the extracted
coal.
Acknowledgements
I am grateful to Dr. Chanchal Mondal,
Associate
Professor,
Chemical
Engineering
Department, Jadavpur University for giving me an
opportunity to take up the project on coal
beneficiation. I am also grateful to Dr. A. Bhowal,
Head, Chemical Engineering Department, Jadavpur
University and all the faculty members of Jadavpur
University for allotting this valuable project to me.
References
1.
2.
3.
Kashimura, N., Takanohashi,T., Saito,I.,

Upgrading the Solvent Used for the Thermal
Extraction of Sub-Bituminous Coal, Energy
& Fuels 2006, 20, 2063-2066
Kim,S.D., Woo,K.J., Jeong, S.K., Rhim, Y.J.,
Lee, S.H., Production of low ash coal by
thermal extraction with N-methyl-2pyrrolidinone, Korean J. Chem. Eng., 25(4),
758-763 (2008)
Li, C., Ashida, S., Iino, M., Coal Dissolution
by Heat Treatments in N-Methyl-2pyrrolidinone,
1,4,5,8,9,10Hexahydroanthracene, and Their Mixed
Solvents: A Large Synergistic Effect of the
Mixed Solvents, Energy & Fuels 2000, 14,
190-196
ISSN: 2277-9655
4.
Makgato, M.H., Moitsheki, L.J., Shoko, L.,

Kgobane, B.L., Morgan, D.L., Focke, W.W.,
Alkali assisted coal extraction with polar
aprotic
solvents,
Fuel
Processing
Technology
(2009),
doi:10.1016/j.fuproc.2008.12.016
5. Okuyama, N., Komatsu, N., Shigehisa, T.,
Kaneko, T., Tsuruya, S., Hyper-coal process
to produce ash-free coal, Fuel Processing
Technology 85(2004), 947-967
6. Rahman, M., Samanta, A., Gupta, R.,
Production and characterization of ash free
coal from low-rank Canadian coal by
solvent
extraction,
Fuel
Processing
Technology 115 (2013), 8898
7. Shui, H., Wang, Z., Gao, J., Examination of
the role of CS2 in the CS2/NMP mixed
solvents to coal extraction, Fuel Processing
Technology 87 (2006), 185 190
8. Steel, K.M., Patrick, J.W., The production of
ultra
clean
coal
by
chemical
demineralization, Fuel 80(2001), 2019-2013
9. Takahashi, K., Noringa, K., Masui, Y., Iino,
M., Effect of addition of various salts on
coal extraction with carbon disulfide/Nmethyl-2-pyrrolidinone
mixed
solvent,
Energy & Fuels, 2001, 15, 141-146
10. Timpe, R.C., Knudson, C.L., Mack, P.,
Beneficiation of a Bituminous and a Lignite
coal by Agglomeration using novel binding
oils
11. Yoshida, T., Takanohashi, T., Sakanishi, K.,
Saito, I., Fujita, M., Mashimo, K., The effect
of extraction condition on hyper-coal
production (1)-under room-temperature
filtration, Fuel, 81, 2002, 1463-1469
12. Yoshida, T., Li, C., Takanohashi, T.,
Matsumura, A., Sato. S., Saito, I., Effect of
extraction
condition
on
hyper-coal
production (1)-effect of polar solvents under
hot filtration, Fuel Processing Technology,
86, 2004, 61-72
Author Biblography
Shashwata Ghosh
Shahshwata Ghosh is a student of Master of
Engineering (M.E.) in Chemical Engineering at
Jadavpur University, Kolkata.
Email: sashwata0910@gmail.com
Dr. Chanchal Mondal
Dr. Chanchal Mondal is an Associate Professor,
Department of Chemical Engineering, Jadavpur
University, Kolkata.

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EFFECT OF ADDITIVES FOR BENEFICIATION OF

INDIAN COAL BY SOLVENT EXTRACTION

Under the guidance of

Department of Chemical Engineering

Declaration of originality and compliance of academic ethics

To whom it may concern

1.2. Types of coal

1.3. Uses of coal

1.4. Chemical composition of coal

1.5 Proximate analysis of coal

1.6. Ultimate analysis of coal

1.7. Disadvantages of ash content of coal

1.8. Beneficiation of coal

1.9. Background of the project

1.10. Problem statement

1.12. Originality of the work

Chapter 2 LITERATURE REVIEW

2.1. The chemical structure of coal

2.2. Solvent extraction of coals

2.3. Effect of rank of coal on solvent extraction

2.4. Effect of temperature and pressure on extraction of coal

2.5. Effect of nature of solvents on extraction of coal

2.6. Effect of hot filtration and room temperature filtration

2.8. Effect of various additives on extraction of coals with

2.9. Kinetics of diffusion of solvent into the coal structure

2.10. FT-IR Analysis of raw, residue and extracted coals

TABLE OF CONTENTS (Contd)

2.11. Coal beneficiation by agglomeration techniques

2.12. Beneficiation by the use of inorganic chemicals

2.13. Reduction of ash content of coal with solvents without

Chapter 3 EXPERIMENTAL MATERIALS & PROCEDURE

3.2. Experimental procedure

3.2.1. Proximate analysis of coal sample

3.2.2. Thermal extraction of coals

3.2.3. Extraction of coal by Ultrasonic irradiation

3.2.4. Recovery of extract

3.2.5. Analysis of the extract and residue

Chapter 4 RESULTS & DISCUSSIONS

4.1. 1. Proximate analysis of raw coal

4.1.2. FT-IR Analysis

4.2. Effects of different solvents

4.3. Comparison of methods of extraction

4.4. Determination of optimum time of extraction

4.4.1. Comparison of percentages of extract recovered

4.4.2. Comparison of ash reduction in extracts

4.4.3. FT-IR spectra of coal extract and residue obtained

TABLE OF CONTENTS (Contd)

4.5.3. Comparison of FT-IR spectra of extracts obtained

4.7.1.1. Percentage of extract recovered

4.7.1.2. Ash content of extract

4.7.2.1. Percentage of extract recovered

4.7.2.2. Ash content of extract

4.7.3. Calcium fluoride

4.7.3.1. Percentage of extract recovered

4.7.3.2. Ash content of extract

4.7.4. Calcium chloride

4.7.4.1. Percentage of extract recovered

4.8.2. Comparison of ash reduction in the extracts

4.8.3. Comparison of FT-IR results of the extracts for the

5.2. Future prospects of the work

Particulars of all experiments

Proximate analysis of raw coal

Comparison of percentages of extract recovered from Toluene

Comparison of percentages of extract recovered by Thermal