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ISSN 1018-5593

European Commission

technical coal research


Coal preparation

Identification of coal characteristics


indicating problems of swelling
during carbonization

European Commission

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Coal preparation

Identification of coal characteristics


indicating problems of swelling
during carbonization
I. Edwards, K. Thomas, F . Nadji, I. Butterfield
University of Newcastle upon Tyne
Newcastle upon Tyne NE1 7RU
United Kingdom

Contract No 7220-EB/839
1 November 1990 to 31 October 1994

Final report

Directorate-General XVII
Energy

1996

EUR 17150 EN

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Luxembourg: Office for Official Publications of the European Communities, 1997


ISBN 92-827-9227-7
ECSC-EC-EAEC, Brussels Luxembourg, 1997
Reproduction is authorized, except for commercial purposes, provided the source is acknowledged
Printed in Luxembourg

CONTENTS
EXECUTIVE SUMMARY

PROJECT OBJECTIVES
Overall Objectives
Specific Objectives

9
11
11

INTRODUCTION

15

EXPERIMENTAL TECHNIQUES AND PROCEDURE


Coals and Solvents Used

23
23

The Dynamic Volumetric Swelling


Specific experimental conditions
Evaluation of diffusion mechanism of pyridine into coals
Evaluation of diffusional parameters for pyridine sorption
Evaluation of molar amounts of solvent sorbed
Oxidation of coals

24
25
28
28
30
31

Solvent Extraction Studies on Coals


Coal extraction
Infra red spectra of coals
Oxygen contents of coal extracts
Size exclusion chromatography of coal extracts

31
31
32
32
33

Thermogravimetry of Coals and Extraction


Residues

34

Dilatometry and permeability measurements

34

Dilatation under pressure

35

Carbonization

35

Surface Area Measurements

36

Gas Diffusion into Coals and semicokes


Gas adsorption capacity
Diffusion rates

37
38
39

RESULTS AND DISCUSSION


Solvent Swelling
Equilibrium swelling ratios
Effect of heat treatment temperature on the solvent swelling of coals in pyridine
Kinetics of solvent swelling of coals
Effect of solvent basicity on the swelling kinetics
and equilibrium swelling of coal in solvents
Effects of steric properties of solvent on the equilibrium
swelling and kinetics of coal solvent swelling
Effect of particle size on the solvent swelling of coal
Effect of oxidation on swelling of coal in pyridine
FTIR of raw and oxidised coals
Effect of oxidation on the solvent swelling of different
particle sizes of coal

41
41
41
44
44

Extraction of Coal
Extraction yields of coal
FTIR of coal extracts
Oxygen contents of extracts
Size exclusion chromatography of coal extracts with THF
as mobile phase

66
66
67
72

Thermogravimetry
Effect of extraction on the temperature of commencement of weight loss
and rate of volatile.
Dilatometry/permeability of semicokes
High pressure dilatometry
Surface Areas of Coals and Semi-Cokes
Gas Diffusion into Coals and Semi-Cokes
Review

75
76
77
78
79
79
83

CONCLUSIONS

85

Specific Conclusions

85

Overall Conclusions

93

References
Tables
Figures

49
53
57
59
61
64

73

95
99
144

EXECUTIVE SUMMARY
During the carbonization of coals in the coke oven some coals generate a very high
internal pressure and swell so excessively that they damage coke oven walls or cause coke
pushing problems known as "stickers". Several methods have been employed over the years
in the assessment of coal for its suitability in the production of metallurgical coke in the coke
oven process. These characterisation methods include the assessment of thermoplastic
properties such as the free swelling index, the Gray-King coke test, the dilatometry,
plastometry and more recently high pressure dilatometry and plastometry. Although these tests
are adequate for assessing the coking properties of coal they have failed to distinguish those
coals that swell excessively during carbonization and those that do not. Hence the need to look
at the problem of predicting dangerously swelling characteristics of coal using a more
fundamental approach.

The aim of the present project is to establish a fundamental

understanding of the relationship between the coal structural properties, the carbonization
mechanism and coke properties for coals which exhibit these properties.

Coal is a complex heterogeneous material and has a macromolecular structure. The


generation of coal thermoplasticity during carbonization involves the initial decomposition of
the macromolecular and "mobile" or extractable phases of coal. Therefore the macromolecular
and mobile phases of coal have been characterised. The microporous structure of semi-cokes
prepared at different temperatures within the plastic phase and resolidification temperature
region were also characterised. These measurements were carried out in order to provide
information on the decomposition of the macromolecular phase to form coke via a
thermoplastic phase.

The characterisation of the coal macromolecular structure involved the use of the
solvent swelling technique. The technique describes the macromolecular phase in terms of the

cross-link density which is determined by the extent of coal swelling in basic solvents. High
swelling in solvents indicate low crosslink density, and low swelling in solvents indicate high
crosslink density. However, since the technique was originally designed for the study of
polymers and had not been fully developed for study of coal it was also considered necessary
to study several factors which might affect the swelling of coal in solvents.

It has been found that several factors affect the swelling of coal in solvents. An
increase in temperature has no marked effect on the extent of swelling of coals in pyridine but
increases the rate of swelling. The apparent activation energy of the solvent swelling increases
with coal rank in conformity with increasing structural stability of coal with increasing rank.
An increase in solvent basicity up to pK^ ~8 (a plateau is reached thereafter) increases the
extent of coal swelling in a solvent and also increases the rate of swelling. Therefore solvents
of high basicity should be used to obtain the maximum swelling of coal. Steric properties of a
solvent affect the extent and rate of coal swelling. The solvent swelling ratio passes through a
maximum with increasing solvent size. This represents a balance between an increase in
swelling ratio required to accommodate the solvent molecule in the macromolecule and a
decrease in the accessibility of larger solvent molecules to the active sites in the coal.
Extraction of coal with solvent before solvent swelling causes a reduction in the extent of
swelling but increases the swelling rate. In addition, the solvent swelling ratio for extracted
coals is only weakly dependent on solvent basicity indicating that hydrogen bonds do not
reform to any great extent after removal of solvent after extraction. This reveals the difference
between raw and extracted coal.

The solvent swelling studies have revealed that the macromolecular structure of
dangerously swelling coals are highly cross-linked by covalent bonds compared to the
macromolecular structure of non-dangerously swelling coals. The swelling in pyridine of coals
heated to different temperatures have also been studied in order to investigate the relative
extents to which heat treatment affects the macromolecular structures of safe and dangerously

swelling coals. The results show that while the crosslink density of the macromolecular
structure of safe coals increase with increasing temperature, the crosslink density of the
dangerously swelling coals decrease with increasing temperature and show minimum values at
a stage during decomposition. This shows that the low rank coals decompose but polymerise
quickly by crosslinking due to their high reactivity whereas the high rank coals decompose and
depolymerise over a wide range of temperatures because of their high stability and low
reactivity. It has also been found that the dangerously swelling coals contain low amounts of
oxygen functionalities and therefore low concentrations of hydrogen bonding interactions when
compared to non-dangerously swelling coals.

Characterisation of the mobile phase involved the extraction of coal with pyridine at its
boiling point. Extraction of the rank range of coals with pyridine showed that the dangerously
swelling coals contain very low amounts of pyridine extractable components i.e. mobile
phase. Using FTIR and size exclusion chromatography data it was shown that pyridine
extracts of dangerously swelling coals were more aliphatic and had lower average molar mass
than the extracts of the non-dangerously swelling coals. Elemental analysis showed that while
the extracts of the dangerously swelling coals contain more oxygen than the corresponding
coals, the extracts of non-dangerously swelling coals contain less oxygen than the
corresponding coals. It is considered that because they are richer in oxygen than their residues
the extracts of the dangerously swelling coals will be more reactive and may react during
carbonization to give rise to highly viscous plastic phase of low permeability which will trap
volatiles and cause high internal pressure and swelling. However, it is considered that the
amount, not the nature of the extractables may be the determining factor since they constitute
only - 2 % of the coal structure. Therefore it is reasonable to conclude that the nature of the
macromolecular phase and the way it decomposes has the major influence in the fluidity of the
system.

Gas diffusion kinetics for oxygen and nitrogen and surface area measurements (CO->

273 K) show that the development of microporosity in coals during carbonization reaches a
maximum at about 600C before decreasing with further increase in temperature. The rates of
diffusion of oxygen and nitrogen into the cokes were slowest for the dangerously swelling coal
indicating that the permeability of these cokes to the transport of gases is low.

The

development of microporosity is lowest for the dangerously swelling coals. It is suggested that
the low microporosity and slow diffusion of gases in the semi-cokes of dangerously swelling
coals cause restriction to the escape of volatiles so that gases cannot escape causing high
internal pressure and dangerous swelling. This is corroborated by the results of a combination
of dilatometry and gas permeability study which shows that the plastic phase of dangerously
swelling coals exhibit very low permeability towards gases compared to the safe coals.

Overall, coals which are described as 'dangerously swelling' in relation to


carbonization in a coke oven have high covalently cross-linked macromolecular structures with
low amounts of 'mobile' phase. This macromolecular structure decomposes involving the
breaking of cross-linking to develop a low fluidity thermoplastic phase which has a low
permeability to the release of volatile. Furthermore the coke formed from the dangerously
swelling coals also has the lowest amount of microporosity and rates of adsorption of gases
into the cokes. This also presents a barrier to the release of volatiles during carbonization.

PROJECT OBJECTIVES
BACKGROUND

It has been apparent from many studies that standard coal characterisation data cannot
be used to predict the dangerously swelling behaviour of coals in coke ovens. Some general
guidelines are available for the occurrence of dangerously swelling properties, e.g dangerously
swelling coals usually have vitrinite reflectance values in the range 1.4-1.65%, and low inert
content.

However, there is insufficient knowledge to predict, unequivocally, swelling

characteristics in the coke oven.

It must be recognised that coal has a macromolecular structure and therefore the
conversion of raw coal to a plastic mass will involve the decomposition of the macromolecule,
with the initial decomposition of functionality, and the various types of crosslinks and noncovalent interactions in the coal. The rate and extent of breakage of the crosslinks which will
depend on the nature and density of the crosslinks may affect the swelling characteristics of the
plastic phase. Therefore, this study has involved an investigation of the relationship between
the macromolecular structure of coals belonging to a wide rank range including safe and known
dangerously swelling coals, by investigating their crosslink densities and non-covalent
interactions, especially hydrogen bonding interactions.

It is also known that coal contains some low molecular weight species which are either
weakly bonded by, for example hydrogen bonding, van der Waal's forces etc, to the
macromolecular structure or are physically trapped in the pore system. The low molar mass
species are also extractable by some solvents e.g. pyridine, and their role in the development
of thermoplasticity of coal is important. In this study, the amount and chemical nature of the
pyridine-extractable materials have been determined in a rank range of coals including
dangerously swelling coals.

It is clear that the excessive swelling and inadequate post plastic contraction of coal
during carbonisation which cause pushing problems and damage coke oven walls occur during
the plastic stage of the coking process. It is therefore not surprising that tests so far developed
to evaluate the dangerously swelling propensity of coals utilise measurements taken during the
plastic phase of the heated coal sample. In a similar manner, this study will involve the
characterisation of semicokes produced at different temperatures from a rank range of coals.
Measurements that will be taken on the semicokes are C0 2 (273 K) surface areas, and the
oxygen and nitrogen capacities as well as the rate of diffusion of these gases into the
semicokes.

One of the characteristics of coal which led to its structure being likened to that of a
polymer is its ability to imbibe solvent and swell. High swelling in a solvent signifies low
crosslink density and vice versa. If a basic solvent e.g. pyridine is used hydrogen bonding
interactions will be disrupted so that the coal structure is opened with the result that the
macromolecular structure swells to an extent determined by the crosslink density. Although
there are many repons of solvent swelling measurements on coal in the literature it appears that
in no case has a correlation been sought between the extent of coal swelling in a solvent and the
dangerously swelling behaviour of the coal during carbonisation. In fact, the only attempt to
compare the solvent swelling of coal and its coking property seems to be that of Sanada and
Honda 1 in which it was found that Gieseler fluidity shows a maximum in the region of coal
rank where solvent swelling shows a maximum and crosslink density a minimum. They 1
therefore concluded that the degree of crosslinking is an important factor in the thermoplastic
properties of coal. In this study, solvent swelling measurements have been carried out on safe
and dangerous coals using pyridine. Prior to this study the solvent swelling technique had not
been well developed completely since the variation of solvent swelling characteristics with
various parameters have not been investigated systematically. Therefore several factors which
are likely to affect the results have also been investigated in order to improve the understanding

10

of the limitations of the technique.

OVERALL OBJECTIVE

The overall objective of the study is to differentiate between safe and dangerously
swelling coals using data from laboratory studies of the semicokes and raw coals.

SPECIFIC OBJECTIVES

Characterisation of coal Structure

Characterisation of coal structure using solvent swelling

The solvent swelling measurements have been carried out in order to study the
macromolecular structure of coals.

The following objectives were included in the

investigation.

1. The variation of solvent swelling ratio of coals in pyridine with rank for a
rank range of coals with emphasis on dangerously swelling coals.

2. The effect of heat treatment temperature on the swelling ratio of coals in pyridine in
an effort to study the changes in the macromolecular structure of coals of different
rank during pyrolysis.

3. The effect of temperature on the swelling ratio of coal in pyridine.

4. The kinetics of coal swelling in pyridine and the effect of coal rank on the
kinetics of solvent swelling in pyridine.
11

5. The effect of solvent basicitv on the extent and kinetics of coal solvent
swelling.

6. The differences in swelling behaviour of raw and extracted coals in order


to examine apparent differences in the macromolecular structure.

7. The effect of solvent steric properties on the extent and kinetics of coal
solvent swelling, and hence establish whether there is a limit to which the coal
macromolecule can swell to accommodate solvent molecules.

8. The effect of oxidation on the solvent swelling of safe and dangerously


swelling coals.

9. The investigation of the effect of particle size on the extent of swelling and kinetics
of raw and oxidised coals.

Determination and characterisation of amounts of the pyridine extractable


materials in coals

The mobile or extractable phase of coal is known to play a vital role in the development
of coal thermoplasticity. Therefore a suite of coals covering a wide range of rank have been
extracted with pyridine in order to study the characteristics of the extractable phase. Also
pyridine extracts have been obtained from coals heated to their softening and maximum
contraction temperatures. The following were included in the objectives.

1.

An investigation of the variation of extractable materials in coals with rank, with


special reference to dangerously swelling coals. Also an investigation of the
variation of extractable materials as carbonisation progresses.
12

Examination of the structural differences in the extracts of different coals using


(a) FTIR spectroscopy, (b) oxygen contents of the coals, extracts and the
residues (c) the molar mass distribution of the extracts using size exclusion
chromatography.

Thermogravimetry of Coal and Extraction Residues

The coals have also been subjected to temperature programmed pyrolysis in order to
determine temperatures of commencement of decomposition, maximum rate of weight loss ,
end of volatile evolution, as well as rate of volatile loss. These parameters have been evaluated
for coals and their pyridine extraction residues.

Dilatometry Tests

The rank range of coals have been subjected to dilatometry tests using the standard as
well as the high pressure dilatometer.

Surface Area of Semicokes

Surface area measurements have been taken on the same coals and semicokes used in
the gas diffusion studies. The aim was to investigate the variation in microporosity of the coals
and semicokes.

Gas Diffusion into Semicokes

In order to investigate the diffusion of gases through semicoke, the coals belonging to a
wide range of rank, and including safe and dangerously swelling coals have been carbonised to

13

450, 500, 600, 800 and 1000C and the diffusion rates of oxygen and nitrogen gases
measured on the cokes and the coals, using a gravimetric technique. Also, the permeability of
the plastic phase of the rank range of coals towards nitrogen have been studied in a
combination with dilatometry tests. The aims of the gas diffusion studies are to,

1. investigate the development of the porous structure with heat treatment temperature,
and

2. investigate the differences in the transport of gases through the porous structure
using the gravimetric method as well as studies involving gas permeability
apparatus incorporated into a standard dilatometer.

14

INTRODUCTION
Metallurgical coke is one of the principal raw materials used in the production of iron
by the blast furnace method of production. Apart from its function as an energy source coke
supplies the reducing gas which convns iron oxides to iron and also provides the permeability
which is necessary for the high performance of the blast furnace2'3.

Coke is produced by the carbonisation of coking coals, and a characteristic feature of


such coals is their ability to soften on heating, become fluid, swell with evolution of volatile
matter, and later shrink on solidification to give a porous structure - semi-coke 4 , which on
further heating undergoes secondary evolution of gas and yields coke. The period between
softening and solidification of coal during carbonisation is known as the plastic phase. This
stage is very important because it is during this plastic phase that porosity and pore wall
material which are considered important in coke structure are formed5.

A critical stage in the plastic phase of coal during carbonisation is the period of swelling
and evolution of volatile matter. This stage is so important in the carbonisation practice that
Foxwell 6 suggests that there can be no production of coke unless there is a pressure set up
within the plastic layer. This pressure. Foxwell6 further suggests, is required to force the fluid
material to engulf the solid matter so as to effect a sort of cementing action which was thought
to be necessary for the production of good coke. These suggestions were based on earlier
work by Blayden et al.7 in which it was demonstrated that the application of external pressure
to non-coking and poorly-coking coals during carbonisation improved the quality of cokes
produced from these coals. Although the pressure and swelling generated in the plastic phase
are important for the formation of good coke there are some coals that generate high swelling
pressures that are capable of damaging coke oven walls. The coals that generate high swelling
pressures that damage coke oven walls are known as dangerously swelling coals.

15

The pressure required in the plastic phase for the production of coke, and the swelling
associated with this pressure are caused by the resistance to the escape of volatiles produced by
pyrolysis 8 . It is suggested that the only mode of escape for trapped volatile matter in the
plastic mass is by diffusion9. The magnitude of the pressure and swelling will depend upon
the rate at which the volatiles escape from the plastic mass. If the resistance to the escape of the
volatiles is so high that the rate of diffusion of gas through the plastic phase is too low, a
pressure build-up will occur in the plastic phase. If excessively high pressure build-up occurs
in the plastic phase the coke oven walls could be damaged or completely destroyed. Therefore
there is a balance to be achieved between the pressure required to produce agglomeration of the
coal particles and excessive pressures which damage the coke ovens or cause pushing
problems. Hence there is an optimum pressure for the production of metallurgical coke.

There are several views about the cause or origin of the dangerously swelling
characteristics of coals. Mott10 proposed that the coals which develop high coking pressure
and dangerously swelling characteristics become excessively plastic during carbonization so
that plastic coal blocks gas outlets thereby causing abnormal internal gas pressure with resultant
swelling. Addes and Kaegi 11 are of the opinion that the gases generated within the plastic
layer try to escape but meet some resistance presented by the low permeability, highly viscous
plastic mass resulting in a pressure build-up in the plastic layer. It was also suggested12 that
lack of high fluidity inhibits gas evolution thereby promoting the dangerously swelling
characteristics of coals. Hermann and Schonmuth 13 propose that the inner gas pressure
develops when the tar seams are closed and that this pressure is transmitted by the oven charge
especially when coke fails to detach adequately from heating walls.

The problem caused by the excessive swelling of coal during carbonisation did not
manifest until the introduction of the slot-type coke ovens in the early part of the present
century. Prior to that period coke was produced in the bee-hive oven in which the coal was
free to expand upwards towards the heat source14. The arrangement allowed the pressure
16

developed in the coking mass to be dissipated by the unrestricted expansion without causing
any problem to the structure of the oven. However, the introduction of the slot-type oven,
with its unique heating arrangement, and larger dimensions and full by-product recovery
facilities brought with it some complications in the operation of the oven. The increase in the
oven height, and the use of higher flue temperatures to compensate for increase in oven
capacity created some problems. Secondly the introduction of new techniques such as coal
blending, pre-heating, stamp charging, partial briquetting etc. which were adapted to improve
coke quality15, have also increased the complications in the design and operation parameters of
the coke oven. Although the generation of high coking pressure and excessive swelling during
carbonization is to some extent a property inherent in the coal16, there is no doubt that increase
in the dimension of the oven and introduction of these new coking techniques increase the
tendency of the coal charge to generate excessively high swelling pressures during
carbonisation. The result is that sometimes coke oven walls are distorted or completely
destroyed. Coke pushing problems known as "stickers" are also caused by excessive swelling
and little or no contraction of coal during carbonisation15.

Dangerously swelling coals are characterised by low volatile matter contents (172 5 % ) 1 5 and maximum vitrinite reflectance. R 0 max. of 1.4% and above. Although the
swelling characteristics of a coal during carbonisation is largely determined by the inherent
characteristics of the coal, it can also be influenced by coke plant operating variables.

Hermann and Schonmuth13, and Benedict and Thompson 16 report the effects of coal
rank, inert content and coking variables such as bulk density coking rate, and oil addition on
the swelling and coking pressure generated by low volatile coals and their blends. From these
studies 13 - 16 the following generations can be made:
(1)

Coking pressure increases with coal rank as measured by vitrinite reflectance


and that the increase in coking pressure becomes more rapid above 1.35%
reflectance.
17

(2)

Coking pressure decreases with increase in the inert content of the coal.

(3)

Expansion of coal as measured by the Bethlehem Steel tester relates to coal rank
and inert content in the same way as coking pressure.

In other words

expansion of coal during carbonisation increases with rank and is more rapid
above 1.35% reflectance and decreases with increase in the inert content of the
coal.
(4)

For coal blends, the coking pressure varies with the vitrinite reflectance of the
low volatile coal. The higher the reflectance of the low volatile coal the more its
influence on the coking pressure generated by the coal blend.

(5)

Coking pressure increases with bulk density of the charge.

(6)

Coking pressure increases with coking rate i.e. heating rate.

(7)

Reduction of charge panicle size decrease coking pressure.

(8)

Addition of inerts such as coke breeze anil anthracites reduce the excessive
coking pressure generated by low volatile coking coals1-.

The reasons for the above generalisations are not fully understood. However it may be
concluded that the factor of inert content is related to their lower volatile matter contents.

It has also been found that the techniques of pre-heating and stamp charging which are
usually employed to improve coke quality increase swelling and coking pressure of coal
charge 14 15 . The increase in expansion and coking pressure is due to increase in bulk density
which accompanies pre-heating or stamp charging of coal or blends. It therefore appears that
any factor that increases charge bulk density, e.g. reduction of moisture, will increase coking
pressure.

The adverse economic consequences of excessive swelling exhibited by some coals


during the production of coke in the coke ovenshave led to the development of several test
methods to identify those coals which are likely to exhibit this behaviour during carbonisation.
18

The earliest tests used in testing for dangerously swelling characteristics of coals were
the Kopper's 14 small scale test, the Baum-Heuser test17 and the Nedelmann's 14 test. These
small scale tests were later found to be inadequate for assessing coals for their dangerously
swelling propensity. For example in some instances coals which were known to be "safe"
were labelled "dangerous" based on the results from these tests. The small scale tests failed
probably because they did not take into account the coke oven operational variables which
normally influence the magnitude of the swelling or coking pressure. These variables include
bulk density of charge, moisture content, oven weight, coking rate etc.

Later test methods are the Kopper's large scale test, the Bethlehem tester 18 , the
moveable wall oven 19 ' 20 and most recently the Kopper's-INCAR tests 21 . They employed
variable bulk density, heating rate, etc. However they also had limitations as tests for
dangerously swelling coals because they could not adequately simulate coke oven conditions
especially the two-directional heating arrangement.

A test apparatus that most closely simulates the coke oven is the moveable wall oven. It
is a pilot scale facility, but like the commercial coke ovens the moveable-wall oven has two
parallel heating walls so that the heat transfer characteristics are similar to those of the industrial
size ovens. Since one of the walls is is moveable any expansion or pressure developed by the
coal charge during carbonisation is measured by a load cell which is usually installed on the
moveable wall. Also, contraction and pressure probes inserted through the charging hole and
the door respectively allow the contraction of the charge and the variation of gas pressure
during carbonisation to be monitored as the process proceeds. However, it must be noted that
the moveable-wall oven is a semi-industrial scale equipment and requires large quantities of test
samples as well as long periods of test time. It is therefore not convenient to adopt it as a
routine test for identifying dangerously swelling coals.

A general criticism of the early test methods for dangerously swelling coals is the
19

existence of little or no correlations between any two of them. For example it was reported 22
that only a little conelation exists between results from the moveable-wall oven and those from
the Nedelmann's apparatus. Also, only a very little correlation was found between pressures
recorded in the moveable-wall oven and those obtained from the Kopper's apparatus 14 . Lack
of conelations in these tests is so much that a coal which generated a pressure of 90 kPa in the
Kopper's test was certified safe, while that which generated a pressure of 4kPa in the moveable
wall oven was condemned as unsafe. A different approach is therefore necessary in order to
distinguish between safe and dangerously swelling coals.

It has been established that swelling of coal and coking pressures during coal
carbonisation are generated in the plastic phase10"13. It is therefore not surprising that all the
early test methods for identifying dangerously swelling coals are designed to test for this
property in the plastic phase of the coal. For this reason, little or no effort has been made to
study the problem from the fundamental point of view.

Development of plasticity by coals during carbonisation occurs only when the coal
macromolecular structure has been partially or totally destroyed by heating in an inert
atmosphere. The fact that coal has a cross-linked polymeric structure23 implies that the partial
or total destruction of this structure will involve the breaking down of various types of crosslinks in the structure. The nature and relative abundance of these cross-links determine the rate
at which plasticity is developed, and the rate at which plasticity is generated will directly or
otherwise determine the suitability of the coal in a given coal conversion process. In fact it is
reported1 that maxima in Gieseler fluidity and percentage tar produced from vacuum pyrolysis
of coal occur in coals of minimum cross-link density.

In this work the macromolecular structure of the coal has been probed using the
technique of solvent swelling to study the variation in the nature and relative abundance of the
various types of cross-links in the coal structure with change in rank of the coal. Solvent
20

swelling tests have also been carried out on coals heated to various temperatures in order to
examine the variation of the crosslink density as heating progresses. Pyridine extracts of raw
and heated coals have also been estimated and characterised using the infra red technique, the
size exclusion chromatography, and oxygen analysis. Coals of different rank have been
subjected to thermogravimetric analysis to investigate the rates of gas release, the temperature at
the beginning of gas release, temperature at which maximum rate of volatile release occurs,
temperature at which volatile release stops and the temperature range within which volatile
release occurs. Dilatation of coals of varying rank have been measured under varying
conditions of pressure and heating rate. Also, permeability of the plastic phase has been
studied in combination with dilatometry in order to monitor the variation of the permeability of
the plastic phases of coals of various rank as carbonisation progresses. It is thought that a
combination of data from these tests will provide some information about the differences
between safe and danuerouslv swell in: coals.

21

EXPERIMENTAL TECHNIQUES AND


PROCEDURE
COALS AND SOLVENTS USED

The coals used cover a percentage reflectance range, R0 of 0.47 and 1.82, and are
listed in Table 1 together with their characterisation data. Rawdon, Wearmouth, Oakdale and
Lady Windsor were obtained from British Gas pic, while Pinnacle, Oakgrove and Line Creek
were received from the coal bank of the Carbon Research Group of the University of
Loughborough.

They were all stored in de-oxygenated distilled water.

Hucknall and

Barnburgh were taken from NCRL coal bank. They were stored in lump form in a sealed
plastic bag kept in a freezer and only the interior portions of the lumps were used in this study.
Wentz, Ruhrkhole, Buchanan, Norwich and Saraji were received from the coal bank of the
Carbonisation Department of Spanish National Coal Institute (INCAR) in sealed plastic bags
and were on receipt, stored in a freezer. Those coals stored in water were dried in a vacuum
dessicator but all coals were ground to the required particle size, placed in sample tubes and
stored in vacuum dessicator before use. The coals were supplied with their characterisation
data.

Solvents used were pyridine. 2-chloropyridine. 2-fluoropyridine. -propylamine, nbutylamine, n-hexylamine. n-octylamine. and n-decylamine. Each of these solvents was above
99% pure. The solvents were obtained from Aldrich Chemical Company and their properties
are shown in Tables 2 and.3.

23

THE DYNAMIC VOLUMETRIC

SWELLING

The dynamic volumetric method, as has been mentioned in an earlier chapter, has the
advantage of measuring only the swelling caused by the solvent that has diffused into the bulk
structure of coal. Therefore results obtained from the DVS system do not require any
correction for solvent occluded in the pores.

The apparatus is similar to that described by Aida and Squires24, Figure 1. Essentially
it consists of a sintered bottom glass tube into which a coal sample of known weight is loaded.
A sliding piston placed on top of the coal sample is connected to a transducer. During an
experiment the glass tube containing the sample and piston is positioned in a glass jacket into
which the solvent is introduced at the appropriate time. The glass jacket is surrounded by a
thermostated water bath to control the reaction temperature to 0.1 C. As solvent is taken up
by the sample by sorption, the coal swells, pushing the piston upwards.

The vertical

movement is converted to a voltage change by the transducer and transmitted via an A-D
converter to a computer which records time, swelling, and swelling ratio. The swelling as
recorded by the computer represents the distance moved by the piston and is proportional to the
increase in volume per gram of coal, and therefore to the amount of solvent that has diffused
into the bulk structure of the coal. The final swelling values and swelling ratios are
reproducible to 2% relative. For example, for six measurements on coal under identical
experimental conditions a swelling ratio of 2.100.02 was obtained.

The sintered-bottom glass tube was placed in the glass jacket after which the piston was
lowered into the bottom of the tube and a reading corresponding to that piston position obtained
by means of the computer. 2 g of the coal sample was then loaded into the tube, the piston
placed on top of the coal and a reading corresponding to this piston position obtained. In this
way a factor referred to as packing density and defined as:

24

weight of coal
=

height of coal bed

was obtained for each sample, by compacting the coal bed by continuously dropping the piston
on top of the coal until there was no increase in the packing density. This practice ensured that
uniform packing and equal degree of interparticle contact necessary for reproducibility of
results were achieved. Solvent which had been maintained at the required temperature was
introduced into the glass jacket and the system maintained at the required temperature by means
of a thermostated water bath equipped with water circulating facility.

Swelling ratio is calculated using the equation


Qv = h/h;

where h is height of coal bed at time t, and h is initial height of coal bed.

Specific Experimental Conditions

Determination of Equilibrium Swelling Ratio of Coals in Pyridine

This work was carried out on coals of particle size range 355-600 ,um using pyridine,
and at temperatures of 20 and 60C. H owever, for swelling kinetic studies on those coals that
show relatively high swelling in pyridine swelling measurements were also carried out at 30.
40 and 50C.

Effect of heat-treatment on the swelling ratios of coals

This study was carried out on coals heat-treated to a range of temperatures in the
thermoplastic region of the coal. Pyridine was used as solvent.

Effect of Solvent Basicirv on Solvent Swelling Kinetics of Coal

'

25

For the study of the effect of solvent basicity on the kinetics of solvent swelling of
coals both raw Wearmouth coal and its pyridine extraction residue in the particle size range of
355-600 were used.

The solvents used were pyridine, 2-chloropyridine and 2-

fluoropyridine. The solvents are of varying basicity but they have the same steric properties.
The pkb and molar volumes of these solvents at 20C are shown in Table 2. With the
exception of the swelling of the raw coal in 2-chloropyridine and 2-fluoropyridine which was
carried out at temperatures in the range of 30-70C the rest of this experiment was carried out at
temperatues ranging from 20-6()C.

Effect of Solvent Steric Properties on the Equilibrium Swelling and Kinetics of Solvent
Swelling of Coal

Wearmouth coal of particle size range of 355-600 was used in this study. The
solvents used are -propylamine n-butylamine. n-hcxylamine. n-octylamine and n-decylamine.
These solvents are of the same basicity but different steric properties. The pk^ and molar
volume of the solvents at 20C are listed in Table 3.

Effect of Oxidation on the Solvent Swelling of Coal

Rawdon. Wearmouth, Buchanan and Pinnacle coals in the particle size range of 355600 were used. They were oxidised and sieved again but there was no appreciable
difference in the panicle size range after oxidation. Rawdon and Wearmouth coals of particle
size range 150-212 , 212-250 , 250-355 and 355-600 were also oxidised in
order to investigate the effect of panicle size on the solvent swelling of oxidised coal. Pyridine
was used as solvent and the experiment was carried out at 20C.

26

Effect of Particle Size on the Equilibrium Swelling and Kinetics of Coal Solvent Swelling

Rawdon and Wearmouth coals of particle size ranges 150-212 , 212-250 , 250355 and 355-600 were used. The swelling experiments were carried out in pyridine at
20C.

Effect of Extraction on the Solvent Swelling

Coals used were Rawdon, Wearmouth, Ruhrkhole, Buchanan and Pinnacle in the
particle size range of 355-600 extracted with pyridine. The solvent swelling of the
extraction residue was also carried out with pyridine. 2-chloropyridine, and 2-fluoropyridine
for extracted Wearmouth coal at temperatures ranging from 20 to 6()C.

Evaluation of Diffusion Mechanism of Pyridine into Coals

The diffusional coefficient, n. is evaluated using the empirical Equation ^


Mt

= kt n

Me
A graph of ln(Mt/Me) against In t for the first 25% of the swelling allows the value of for the
initial swelling to be determined. For example, = 1/2 for Fickian diffusion, = 1 for Case
11 diffusion which involves a well defined solvent front. Values of in the range 0.5 - 1 are
described as anomalous while values of > 1 are termed Super Case 11.
Evaluation of Diffusion Parameters for Pyridine Sorption into Coals

For a Fickian diffusion into a spherical particle the total amount of diffusing substance
entering or leaving the sphere at long times is described by26:

27

M.

6
= 1 - -

Mc

l/n2

exp ( - D r A t W )

n=i

The solution for the equation for short times is:


. M,

Me

/Dt '^
( 2)
a '

= 6

.
~
-'/2 + 2 ierfc
n=i

na -,
1 -3
V(Dt)

Dt
2
a

In Equations 4 and 5, Mt and M e are mass uptakes at times t, and at equilibrium respectively, a
is the particle radius and D the diffusion coefficient. Equations 4 and 5 are based on the
assumption that the particle radius does not change during the diffusion process. However, the
assumption does not hold for solvent swelling of coals.

Reanangement of equation 4 gives:


M,
1 -
Mc

6
-

n=i

l/n2

exp (-Dn27t2t/a2)

Since the series of Equation 6 converge quickly then only the first term is important and a
graph of ln[(Me - M t )/M c | against t will give a straight line with slope equal to D7t2/a2 from
which D/a2 can be calculated. However, a graph of In|(Mc - Mt)/Mc] against t for theoretical
Fickian diffusion is shown in Figure 2. The graph is slightly curved at the very low values of t
due to the importance of the higher terms at such low t values. On the other hand, the graph is
a straight line for swelling ratios above 50% and the best least-squares straight-line fit for the
data >50% swelling gives a value of D/a2 very close to the theoretical value. This is due to the
rapid convergence of the series of Equation 6: the higher terms in the series expansion
becoming insignificant. This leads to the conclusion that for Fickian diffusion into non-porous
spherical particles a graph of ln[(Mc - Mt)/McJ against t approximates to a straight line with
gradient D7t2/a2. However this approximation is good above about 50% swelling.

For small times equation 5 approximates to:

28

M.

D'/2t ''-

M,.

7t1/2a

so that a graph of M/M e against t ^ will give a straight line with gradient 6D Vrc '2a from
which D/a2 the diffusional parameter can be calculated. The diffusional parameter is calculated
instead of the diffusion coefficient because a particle size range of the coal samples is used as
opposed to a specific particle size. Secondly, the particle radius changes as the swelling
progresses and so does not remain constant during the process.

The Case II diffusion process into a spherical

particle is described by the

equation 2 5 - 2 7 .

^...(..J-O3
Mc

Ca'

where C 0 is the equilibrium solvent concentration and k0 the relaxation constant. The
corresponding graph of ln[(Mc - M t )/M c | against t is shown in Figure 3 and is, as expected
non-linear.

The swelling process can be empirically described in a simple manner if diffusional


limitations are ignored: and in that case it would be assumed that the coal is reacting with the
solvent, it follows, therefore, that:
ds

dt

= k [solventi" [coal reaction sites|n

Since solvent concentration is always well in excess and essentially constant


ds

dt

= k1 [coal reaction sites]"1

10

29

If the reaction is first order, m = 1 and the fraction of reaction sites available for reaction at time
t is (QVgq-QVj), where QV

and QVt are equilibrium swelling ratio and swelling ratio at time t

respectively. Hence a graph of ln(l - QV/Qeq) against time will give a straight line if the
swelling is a first order process.

In subsequent chapters the solvent mass uptake at time t, M t , and equilibrium solvent
mass uptake, M e , have been replaced by the swelling at time t, S t , and equilibrium swelling,
S e respectively because in the Dynamic Volumetric Swelling (DVS) method only the solvent
that diffuses into the coal structure causes swelling, and the amount of solvent uptake is
proportional to the swelling.

It must be recognised that Equations 4 and 5 describe diffusion systems where the kinetics
are governed by the Fickian mechanism and would not be applicable to anomalous sorption
process the mathematical theory of which has not been well developed, or the Case II process
in which the mechanism of diffusion is different.

Solvent sorption into glassy polymers contains contributions from both concentration
gradient controlled diffusion and relaxation controlled swelling. The relative contributions of
these two processes may van' with temperature, particle size, etc. A mathematical model has
been proposed 27 28 involving linear superposition of phenomenologically independent first
order relaxation terms on a Fickian diffusion equation.

The model yields kinetic and

equilibrium values describing the individual contributions of the diffusion and relaxation
processes.

Evaluation of molar amounts of solvent sorbed by coal

In the studies of solvent properties on the solvent swelling of coals, the molar amounts of
solvent absorbed by coal was calculated using the equation29,
30

mmol absorbed
g of dry coal

Q-1
Vp

11

1000

where V is the molar volume of the solvent, Q is the swelling ratio of the coal in the
solvent, and is the density of coal.

Oxidation of coals

The coals were oxidised in a fan-assisted oven. Each of the samples chosen for
oxidation studies was spread in a metallic tray that had been wrapped with aluminium foil and
kept in the oven at a temperature of 2()0C for 24 hours. The oxidised coal was then left to
cool to room temperature in a vacuum dessicator. Oxidised coals were analysed for oxygen
and studied using the solvent swelling technique and infra red spectroscopy.

SOLVENT EXTRACTION STUDIES IN COALS

Coal extraction

A Sohxlet extractor was used for the extraction of the coals. Extraction of all the coals
studied was carried out with pyridine at its boiling point under nitrogen. The particle size range
of 355-600 was used. The extracts were isolated from solutions by means of a rotary
evaporator and further dried for 24 hours in a vacuum desiccator using a pump.

About 4 g of coal was placed in a previously weighed Whatman extraction thimble and
extracted with pyridine in a Sohxlet extractor until the solvent became clear. Coal residues
were Sohxlet-washed for 6 hours with pentane to remove pyridine, dried in vacuum at room
temperature for 24 hours, and weighed.

31

The weight of extract was obtained by difference and the extraction yield calculated
using the equation30.
Extraction yield (wt% d.a.f.)
total extract
(residue - ash + total extract)

100

12

Reproducibility was about 1%.

Infra red spectra of extracts

The apparatus used was a Nicolet 20PC FTIR spectrometer. Semi-quantitative FTIR
spectra were obtained on finely ground coal extracts pressed into KBr discs. To obtain
sample-KBr discs exactly 1.83 mg of each extract was mixed with exactly 320 mg of KBr and
ground in a mini agate mortar for K) mins. transferred to a sample tube and dried for 24 hours
in a dessicator using a vacuum pump. In order to minimise the effect of water absorption by
KBr, each sample-KBr mixture was pressed into a disc and spectra obtained immediately using
the Nicolet instrument. For each sample an average was obtained from thirty two scans.
Extracts of both raw and extracted coals were studied.

Oxygen content of coal extracts

Oxygen contents of the extracts were determined using a Carlo Erba CHN EA 1108
Elemental Analvser.

32

Size Exclusion Chromatography of coal extracts

The pyridine extracts of coals were analysed by size exclusion chromatography in order
to obtain some knowledge about the differences in the molar mass distribution as a function of
coal rank.

The size exclusion chromatographic (s.e.c) technique separates molecules on the basis
of their ability to penetrate a porous gel. As the solute passes through the column in the mobile
phase smaller molecules enter the stationary phase while large molecules that can not enter the
pores are confined to the mobile phase so that they are excluded31. The overall effect is that
large molecules travel with the mobile phase and are eluted before the smaller molecules which
are retarded by the porosity of the gel. the limit being the permeation limit. Therefore large
molecules give low retention volumes while small molecules give higher retention volumes.

Calibration graphs 3 1 3 2 are usually required in order to obtain the molar mass
distribution of material when using the s.e.c. The variation of retention volume of the extracts
with rank of parent coal shows the molar mass distribution of the extracts. Extracts of both
raw and heat-treated coals were studied. Each of tetrahydrofuran (THF) and chloroform was
used as a mobile phase.

The apparatus used consists of an h.p.l.c. pump, a valve system with a 20 system
loop, a column of 60 cm length packed with a neutral (polytsyrene/divinylbenzene)
macroporous gel of particle size 10 and average pore diameter 10 nm. a UV monitor, an
electronic flowmeter and a chart recorder. The diagram of the s.e.c apparatus is shown in
Figure 4.

Exactly 2.7 mg of each extract was dissolved in 1 ml of THF and 20 of the solution
injected into the column. It was observed that the extracts were not 100% soluble in THF,
only about 95% of each extract dissolved in THF. The reproducibility for the retention volume
33

is 1%.

THERMOGRAVIMETRY

OF COALS AND EXTRACTION

RESIDUES

The instrument used was a Stanton Redcroft STA-780 series thermal analyser. Each of
the coal samples was ground to -212 particle size and 30 mg heated at a fixed heating rate
to a final temperature of 900C in a stream of nitrogen flowing at the rate of 50 cm 3 per minute.
The coal samples and the coal extraction residues were analysed at a heating rate of 5C min 1 .
However, in order to study the effect of heating rate on the characteristic tempertures and rate
of devolatilisation a representative group of six coals have also been, in addition, analysed at
10, 15. 20, and 25C.

DILATOMETRY AND PERMEABILITY MEASLREMENTS

A standard Ruhr dilatometer was used for dilatometer tests but was modified so as to
allow the instrument to be used for the study of the changes in the permeability of the sample
throughout the carbonization process. A 1/8" feed gas line into the coal sample has been fixed
onto the base of the dilatometer tube, through the base of the furnace, and sealed. The mould
plug has also been modified so as to forni a pencil with a hole in the bottom which locates over
the gas pipe

The permeability changes of the coal samples were measured simultaneously with the
standard dilatometrie properties. The rate o\' flow of nitrogen gas was used as a measure of
permeability. Values of gas flow were obtained from a Cole-Parmer float type flow meter and
were recorded together with values of corresponding temperatures.

A graph of gas flow against temperaure was used as a measure of degree of


permeability change throughout the coking process. Samples were heated from room
34

temperature to 650C at 3K/min.

MEASUREMENT OF DILATATION UNDER ELEVATED PRESSURES

The high pressure dilatometer used is a version of the dilatometer described in BS 1016
Part 12 with the only difference being a modification to allow tests to be carried out at various
elevated pressures. Essentially the apparatus comprised of a stainless steel pressure vessel and
has three independant Eurotherm furnace temperature controllers controlling the top middle and
bottom zones of the furnace. A Baskerville and Lindsay pressure release valve controlled by
presetting a limit on the pressure gauge ensures the system was safeguarded against excessive
pressures. The length transducer and thermocouple are connected to a Bryans 26000 A3 X-Y
plotter. The Sclumberger transducer is connected to the Y-axis and a K-type thermocouple is
connected to the X-axis.

The system was flushed out with nitrogen (oxygen free) gas and the pressure was set
using a pressure gauge. The dilatometer tube and piston, thermocouple and length transducer
were then lowered into a vertically positioned cylindrical furnace. This pencil was then
subjected to heating rate of 3 K/min up to 823K. The samples were studied over a range of 0
to 6MPa.

From the dilatometer trace, the values of softening temperature (Tj), temperature of
maximum contraction (T2). resolidification temperature (T3), percentage contraction (%C) and
percentage dilatation (%D) can be obtained.

CARBONISATION

Coals were ground to pass through a 212 sieve, placed in a silica boat, and
carbonised in a horizontal tube furnace under argon at a heating rate of 3C min -1 to the
35

required temperature. The sample was held at the final heat treatment temperature for one hour.
All the c oals shown in Table 1 were c arbonised to 450, 500, 600, 800 and 1000C. The
semicokes produc ed were all c rushed to pass through 600 sieve before gas diffusion and
surface area measurements were taken on them.

SURFACE AREA MEASUREMENTS

Surface area measurements were made on the coals and semi-c okes by the gravimetric
method using the McBain apparatus and carbon dioxide as adsrbate. A schematic diagram of
the apparatus is shown in Figure 5. Essentially the apparatus c onsists of four main units, (a)
the vac uum system made up of a rotary pump (Eduards, model E04K) and an oil vapour
diffusion pump (Edwards model E2M2). (b) the gas inlet system consisting of a needle value.
(c) a mercury manometer, (d) sample tubes into whic h aluminium foil buc kets c ontaining the
sample are suspended using a pre-calibrated silic a spring.

About 200 mg of eac h sample was weighed into an aluminium foil buc ket whic h was
then suspended into the sample tube using a silica spring. The apparatus was then evac uated
with the pumps while the samples were being heated at 373 using isomantles surrounding
each tube. Evac uation of the apparatus and heating of the samples were c ontinued for four
hours in order to remove any material that may have been adsorbed on the surface. The sample
tubes were then immersed in ic e (273 K) and the adsrbate gas (c arbon dioxide) introduc ed
into the apparatus after whic h the apparatus was left overnight. By varying the manometer
readings and measuring the spring extension using a cathetometer the amount of gas adsorbed
at a given relative pressure was obtained up to pressures of 0.1 MPa.

The results were.c alc ulated by applying the adsorption data to the DubininRadushkevich (D-R) equation 33 34

36

log W = log W - D log 2 (p/p0)

13

where W0 is the total volume of micropores in the sample, and W the volume of micropore that
has been filled at a relative pressure of p/p. By plotting log W against log2 (p/p) and
extrapolating the linear portion of the D-R plot to log 2 (p/p) = 0 the micropore volume and
hence total number of gas molecules adsorbed was obtained, so that surface area, A was
calculated using the equation:

A = Nmxa L
where N m =

14

monolayer capaci ty/mmol g_1

= cross-sectional area of 1 molecule of carbon dioxide i.e. 2 K)"19 m2

Avogadro number (6.022 IO23 molecules)

Reproducibility was about 5 m2g-'

GAS DIFFUSION INTO COALS AND SEMICOKES

The apparatus used for measuring the gas uptake of coals and semi-cokes by the
gravimetric method is shown in Figure 6. Essentially it consists of five components:

(a)

microbalance head

(b)

a glass sample bucket that hangs on the balance and surrounded by a glass tube
through the bottom of which gas is let into the sample by means of a tap. The
tube is positioned within an isomantle for outgassing the sample at 100C.

(c)

a data recording and data collection system consisting of a digital balance


controller, standard chart recorder and an Olivetti computer.

(d)

a standard glass vacuum rig.

(e)

an evacuating system comprising a rotary pump and a diffusion pump. The two
pumps are the same types described in the case of the VlcBain apparatus.
37

The gases whose capacity and diffusion rates were studied are oxygen and nitrogen.
The gases were 99.9% pure and were dried before introducing into the sample tube by passing
through dehydrated silica gel.

About 150 mg of sample is weighed into the glass sample bucket and the rig evacuated.
The sample is then heated under vacuum for one hour to remove any adsorbed moisture after
which the isomantle and pumps are switched off before helium flowing at the rate of 100 c.c
min-1 is introduced into the sample tube through the top of the tube. Another stream of helium
also flowing at the same rate is passed into the tube through a tap at the bottom and allowed to
flow until a constant weight is achieved. The stream of helium flowing through the bottom of
the tube is then replaced with oxygen or nitrogen also flowing at the rate of 100 c c min-1 and
allowed to flow until a constant weight is achieved. The weight against time were recorded and
stored in the computer for data analysis.

Gas adsorption capacity

The gas adsorption capacity of a microporous carbon gives the volume of a particular
gas taken up by one gram of the outgassed carbon when exposed to that gas. The gas capacitv
is calculated using the equation:

MG - M Hc + C G

1000

Capacityc =

MHc

where

MG

15
PG

final

mass of sample in nitrogen or oxygen.

MHe =

final

mass of sample in helium.

BC

buoyancy conection for nitrogen or oxygen

pG

density of nitrogen or oxygen.

38

The buoyancy correction factor corrects the gas uptake for the change in buoyancy of the
bucket and sample caused by introduction of the adsrbate gas after a baseline had been
obtained in helium. The buoyancy effect varies with weight of sample and is obtained by
plotting MHC - MG against weight of sample and taking the value on the y axis conesponding to
the weight of sample in the gas used. Buoyancy correction graphs for oxygen and nitrogen are
shown in Figure 7. Reproducibility was 1.2%.

Gas Diffusion rates

Gas diffusion through coals and semi-cokes can be studied by investigating the uptake
of gas in the particles using the unsteady state diffusion of molecules into or out of the material.
The equations that describe the non-steady state gas uptake in a sphere for a Fickian process are
Equations 4 and 4. Diffusional parameters for the diffusion of oxygen and nitrogen into the
semicokes were obtained using the approximate solutions of Equation 4 as described in a
previous section. The reproducibility was approximately 2%.

39

RESULTS AND DISCUSSION


SOLVENT SWELLING

Equilibrium Swelling Ratios

A typical graph of swelling ratio versus time for swelling of coal in pyridine at 20C is
shown in Figure 8. This graph is characterised by an initial period of rapid swelling followed
by a progressive decrease in the rate of swelling as equilibrium is approached. Values of the
equilibrium swelling ratios obtained at 20C and 60C for the complete rank range of coals
studied are shown in Table 4.

At 20C high equilibrium swelling ratios of 2.17, 2.26, 2.3, 2.10 and 1.80 were
obtained for low rank coals of vitrinite reflectance 0.47-0.91%. Two medium rank coals of
vitrinite reflectance 1.20% gave swelling ratios of 1.32 and 1.30 respectively, while the higher
rank coals of vitrinite reflectance 1.33-1.82% gave swelling ratios ranging from 1.00 to 1.09 in
pyridine. It is apparent that there is a maximum equilibrium swelling ratio at a rank of about
702 in the British Coal Classification Scheme (Vitrinite Reflectance 0.65%). This equilibrium
swelling ratio then decreases gradually with increasing rank to Wentz ( 0.95%), after which the
decrease becomes very rapid until low values are obtained for the high rank coals with vitrinite
reflectance in the range of 1.33 to 1.82%.

The swelling of coal in basic solvents is thought to be a consequence of the disruption


of hydrogen bonds in the coal structure by the basic solvent 35 36 . Disruption of hydrogen
bonds opens up the coal structure. The strongly basic character of pyridine enables it to break
virtually all die hydrogen bonds in coal, replacing coal-coal hydrogen bonds with coal-pyridine
hydrogen bonds so that the coal swells if these coal-coal hydrogen bonds were active

41

crosslinks36 The ability of pyridine to disrupt all the hydrogen bonds in coal results in the
swelling of coal tending to attain maximum value in pyridine37. The limit of the swelling is
however determined by the covalent cross-link density. High swelling ratio indicates low
crosslink density, and vice versa.

The trend shown in Figure 9 therefore suggests that after the maximum equilibrium
swelling ratio has been attained at a rank corresponding to R 0 ~ 0.65 or 702 in the British Coal
classification scheme the swelling ratio decreases with increase in rank showing that covalent
crosslink density increases with coal rank.

Table 5 provides further details of the equilibrium swelling ratios in the range 20-60C
for the coals the kinetic aspects of which were studied in detail. It is apparent that there is little
variation in equilibrium swelling ratio in this temperature range. However, a number of the
coals appear to reach maximum at about 40C. However, for the coals studied in detail which
have a relatively low crosslink density, the swelling ratio varies by less than - 1 5 % . Hence this
is relatively small compared with the swelling ratios.

Values of equilibrium swelling ratios obtained for coals in pyridine at 60C show that
while there is a slight decrease for coals in the percentage reflectance range of 0.47 to 1.337c.
there are increases for those coals in the percentage reflectance range of 1.42 to 1.82. These
differences are highlighted in Figures 9 and 10. However these effects do not alter the overall
trends of equilibrium swelling ratio with coal rank.

The slight decrease in the equilibrium swelling ratio of the low rank coals at 60C in
pyridine compared with the values at 20C is noteworthy because earlier studies by Sanada and
Honda38, though on pyridine-extracted coal showed an increase in equilibrium swelling ratio
with temperature. Suuberg et al. 39 also reported diminished swelling in pyridine of coals dried
at 60 and 100C and suggested that thermallv induced crosslinkase could occur at these
42

relatively low temperatures. However, the coals used in the present study, though showing
trends similar to those of Suuberg 39 were neither extracted with pyridine nor dried at 60 or
100C, but were merely dried at 20C in vacuum. Therefore the decrease in their equilibrium
swelling value when measured at 60C needs to be explained.

The slight decrease in equilibrium swelling ratio observed in this study may have been
caused by irreversible shrinkage of the coal structure that occurs due to the thermally induced
loss of capillary condensed water as well as water attached to polar groups in the coal
structure 40 " 44 .

The decrease in swelling ratio at 60C caused by thermally-induced water loss


decreases with increase in coal rank. The trend suggests that the amount of water loss and the
shrinkage in coal structure caused by the water loss decreases with increase in coal rank. This
is in agreement with the findings of Mahajan and Walker 45 that hydrophylic sites in coal
decrease with increase in coal rank. In general, low rank coals have higher moisture and also
higher oxygen contents.

Obviously the major structural factors determining the swelling of coal in a basic
solvent are the hydrogen bonding interactions and the covalent crosslink density. However,
other intermolecular interactions such as - aromatic interactions may exert some minor
effects. The slight increase in the swelling ratios at 60CC in pyridine of higher rank coals of
reflectance 1.42% and above is probably caused by the thermal dissociation of - aromatic
interactions which may have become significant due to increased aromaticity of the coals in that
rank region as compared to the lower rank coals. The fact that the swelling of these coals in
pyridine at 60C slightly increases with rank suggests that the - aromatic interactions
increase with coal rank46. This is not unexpected in view of the fact that coal aromaticity
increases with rank47.

43

It is clear that those coals that swell in pyridine at 20C, Figure 9, contain significant
amounts of hydrogen bonding crosslinks, and also have a good degree of open structure
characterised by low covalent crosslink density which allows the structure to swell when the
hydrogen bonding is disrupted by pyridine. However, the extent of hydrogen bonding and
covalent crosslink density would van' from coal to coal. On the other hand the high rank coals
that have not swollen at 20C in pyridine contain relatively small amounts of hydrogen
bonding, and more importantly, they must be highly covalently crosslinked.

Effect of heat treatment temperature on swelling of coals in solvent

For each coal swelling ratio showed a maximum value at a given heat treatment
temperature, (see Table 6 ). However, while some coals showed the maximum value near the
softening temperature, others showed their maxumum swelling values near the maximum
contraction temperature. Overall, the heat-treatment temperature at which the maximum
swelling occurs increases with increasing coal rank. This reflects the increasing thermal
stability of coal with increasing rank. Low rank coals initially have a low crosslink density
which increases, i.e crosslinks are formed during heat treatment. High rank (dangerously
swelling coals) have high crosslink densities which decompose to produce low crosslink
densities during the thermoplastic phase.

The trend shown by swelling ratio with heat treatment temperature of coal shows that
the coal macromolecular structure changes as the coal is heated. The trend suggests that the
decomposition of the dangerously swelling coals is highly dependent on the structural stability
of the coal.

Kinetics of Solvent Swelling of Coals

Values of the diffusional exponent in Table 5 show that the swelling of Rawdon coal in
pyridine at 20C is a Fickian diffusion process. A graph of ln((Se-St)/Se) against time for the
44

process is shown in Figure 11. The graph is slightly curved in the initial swelling region but is
linear in the region where the swelling is greater than 50%. The initial curvature is
characteristic of Fickian diffusion and is due to the contribution of the higher terms in the
summation of the infinite series given in Equation 4. The linear portion in the region >50%
swelling is a consequence of a rapidly convergent series which at high values of t in the series
of Equation 4 leads to the high terms being insignificant. This is consistent with the shape of
Figure 2 which is a theoretical Fickian diffusion curve. Also a graph of S t /S e against the
square root of time is shown in Figure 12. This shows that the data are consistent with a
Fickian mechanism with the gradient of the graph being 6D1/2M1/2a for M t /M e < 0.25.

A theoretical Case 11 diffusion curve shown in Figure 3 is consistent with Equation 8.


At low values of t corresponding to M t /M e < 0.3 the graph is linear with respect to time, but at
high values of time the higher terms in the expansion of the equation become relatively more
important and they affect the linearity of the graph. Also an empirical relationship, Mt/Me = 1 e_kl, has been proposed for relaxation controlled swelling process. A graph of Mt/Me against t
is linear for small time with a gradient approximately equal to 1, (0.92 for M t /M e < 0.25).
Therefore there are similarities between a moving boundary Case 11 situation and a relaxation
controlled swelling process at small times.

Graphs of ln((Se-St)/Se) against time for the swelling in pyridine of Rawdon coal at
50 C and Wearmouth coal at 30 C are shown in Figures 13 and 14 respectively. Diffusional
exponents shown in Table 5 indicate that the diffusion processes are anomalous and Case 11
respectively. However, it is clear that Figures 13 and 14 are straight lines. Therefore the
graph of ln((Se-St)/Se) against time is an experimentally-determined first order rate law which
applies to the process irrespective of the initial diffusion mechanism. The results are consistent
with the swelling controlled by the relaxation process occurring in solvent swelling. It is
possible that die diffusion mechanism changes to Fickian at some stage in the swelling process.

45

Other coals, namely, Barnburgh, Hucknall, and Wentz also gave straight lines for the
plots of ln((Se-St)/Se) against time for all the temperatures at which they were studied. The
solvent swelling data obtained at temperatures between 20-60C were analysed to evaluate the
rates, k/s' 1 , diffusional exponent, n, activation energy and the pre-exponential factor. The
diffusional exponent which indicates diffusion mechanism was evaluated by applying Equation
3 to the data obtained from the initial stages of the swelling process. The coals investigated
showed a range of values for n, (0.96 - 1.20). Rate constants were obtained using the
appropriate solution to Equation 4. Rate constants obtained using the graph of ln(QV -QVt)
against time as deduced from Equation 9 are the same as those obtained from the approximate
solutions of Equation 4. Also diffusional parameters D/a2 have been calculated for swelling of
Rawdon coal using the short term and long tenn approximate solutions for Equations 4 and 5.
The rate constants, ratio of the diffusional parameters for Rawdon. diffusional exponents and
the swelling ratios are shown in Table 5. It is clear that although the extent of swelling does
not vary greatly with temperature, the rates vary greatly with temperature. The ratios of the
diffusional parameters calculated from the later parts of the process to those calculated from
initial parts of the swelling process for Rawdon coal give values of approximately 2. However
the activation energies for both the initial ( M t /M e < 0.25) and final ( M t /M e > 50%) are
similar. The differences in the rates of swelling are accounted for by differences in the
exponential factor. Arrhenius plots for the swelling of the five coals in pyridine are shown in
Figure 15. The apparent activation energies obtained for the coals range from 31.6 to
44.9kJmol 1 ' showing a trend of increase with coal rank in accordance with increasing
chemical stability of coal with rank.

The diffusion mechanism for swelling of Rawdon coal at temperatures of 20-40C is


Fickian but anomalous for 50 and 60C. On the other hand it is Case 11 for Barnburgh,
Hucknall, Wearmouth, and Wentz coals at all the temperatures studied. Therefore the diffusion
mechanism of pyridine into these four coals is independent of temperature within the
temperature range of 20-60C. It is clear that the diffusion mechanism and hence structure of
46

Rawdon coal is significantly different from those of the other coals.

Since the diffusion mechanism for Rawdon coal in the temperature range 20-40C is
Fickian it would be expected that the values of the diffusional parameter, D/a2, obtained from
the long and short term approximate solutions would be similar. However, as has already been
mentioned they differ by a factor of ~2 at each temperature, with the values for the long term
being higher. This shows that the diffusion coefficient varies through the initial stages of the
diffusion process, increasing as the coal swells. The increase in diffusion coefficient as the
coal swells is probably as a result of opening up of the coal structure during the swelling
process. This non-conformity to the expected behaviour is probably connected with the
complexity of the coal-pyridine system as well as the approximations in the treatment of the
solvent swelling data. For example, the diffusion process in the coal pyridine system is
associated with swelling and chemical reaction. Secondly, the particles are not spherical but
are of varying shapes and consist of a range of particle sizes that change during the swelling
process. It is also clear that the suggested variation of diffusion coefficient with swelling
implies a modification of the accessibility of coal to the solvent as the coal structure changes
with swelling. These associated phenomena cause the coal-pyridine diffusion process to
deviate from the ideal situation described by Equations 4 and 5.

Coals have a porous structure and it is reasonable to expect that the porous structure
will influence the kinetics of solvent swelling. Adsorption isotherms of the coals studied
showed that they are largely microporous. Secondly, it might be thought that pyridineextractable materials will affect the activity of solvent and thereby affect the solvent swelling
kinetics. However, C 0 2 (273 K) surface areas, pyridine extraction yields and swelling ratio
ranges for the coals are shown in Table 7. Also shown in Table 7 are the apparent activation
energies obtained from Arrhenius plots. Figure 15. as well as the pre-exponential factors.
These data, shown in Table 7, indicate that there is no simple relationship between surface
area, pyridine extraction yield, swelling ratio and the kinetic parameters of the solvent swelling
of the coals in pyridine. Evidently, differences in microporosity have not affected the extent
47

and rate of swelling of these coals in pyridine. The pyridine extract yields are low and the
solvent used in the solvent swelling experiment is in large excess, therefore, the extracts do not
affect the solvent activity.

The apparent activation energies show a trend of increase with increasing coal rank.
The trend is expected in view of the increase in chemical stability of coal with increase in rank.
The values of the apparent activation energies are for combined processes of diffusion,
disruption of coal-coal hydrogen bonding by pyridine, structural relaxation and the swelling of
coal. It will be ambiguous to assign the rate-determining step of the swelling process to
diffusion, relaxation or chemical reaction. However, the increase in apparent activation energy
with rank shows that structural stability increases with coal rank.

The apparent activation energies reported in Table 7 are lower than those reported by
Otake and Suuberg 48 for coals of similar rank.

It must, however, be realised that these

authors evaluated the activation energies using the assumption that the reciprocal of the time
taken to achieve a particular extent of swelling is proportional to the diffusion coefficient in a
Fickian process and to the relaxation time constant in a Case II process. Apparently the
activation energy calculated on the basis of this assumption will account only for the chosen
extent of the solvent swelling process.

From the study of the kinetics of solvent swelling of these five coals it is clear that: (i)
The solvent swelling process obeys an experimentally-determined first order rate law for S e /S t
> 0.5 irrespective of whether the diffusion mechanism is Fickian. anomalous, or Case II. ii)
The rate law is similar for all the diffusion mechanisms determined from the initial swelling
though it also applies to the later part of the process where the mechanism may also change,
iii) In the Fickian diffusi - the diffusion coefficient increases with time and extent of swelling
probably because of uV

oening of the coal structure that occurs as swelling progresses, iv)

The apparent activation energy for the overall process increases with coal rank in agreement
48

with the fact that coal stability increases with rank.

Overall, the dangerously swelling coals, unlike the safe coals, showed very low
swelling ratios in pyridine, and this is consistent with very high crosslink density.

Effect of Solvent Basicity on the Swelling Kinetics and Equilibrium Swelling


of Coal in Solvents

The swelling ratio versus time graphs for the swelling of Wearmouth coal in pyridine,
2-chloropyridine and 2-fluoropyridine at 30 C are shown in Figure 16. The solvents were
chosen because of their similar size, shape, and steric properties but different basicity,
therefore eliminating these steric factors. The data in Table 8 show that the rate of swelling
decreases with decrease in solvent basicity. The equilibrium swelling ratio also decreases with
decreasing solvent basicity. This indicates that the basicity of the solvent is an important factor
in breaking the hydrogen bonds present in the coals. It is apparent that the less basic the
substituted pyridine the fewer the hydrogen bonds which are broken. A graph of ln((SeSt)/Se) against time for swelling of Wearmouth coal in 2-chloropyridine and 2-fluoropyridine
respectively are shown in Figures 17 and 18. It is clear that the swelling of the coal in the
substituted pyridines obeys the experimentally-determined first order rate law.

Swelling ratios of the extracted coal do not vary significantly in the substituted
pyridines, however the values are lower than those for the raw coals, showing that there is a
significant difference between the macromolecular structure of the raw and extracted coals.

The rate constants and swelling ratios for the swelling of raw and extracted Wearmouth
coal in pyridine, 2-chloropyridine, and 2-fluoropyridine at various temperatures are shown in
Table 8. Also shown in Table 8 are the values for the diffusional exponents for the raw
Wearmouth coal at the various temperatures. Diffusional exponents were not calculated for the
49

swelling of extracted Wearmouth coal in these solvents because the initial swelling process was
very rapid, as indicated in Figure 19, preventing the accurate determination of the diffusional
exponents for the initial uptake of solvent. It is clear that the rate constants for the coal is
strongly influenced by solvent basicity and temperature. On the other hand, for the pyridineextracted coal only small variation in the rate constants occur with temperature. Arrhenius plots
for the swelling of the coal in the three pyridines are shown in Figure 20. The apparent
activation energies are 37. 31 and 24 kJ mol"1 for pyridine, 2-chloropyridine, and 2fluoropyridine respectively for the raw coal. In contrast, apparent activation energies for the
extracted coal in the three solvents are similar (-10 kJ mol1) for each of the pyridines. This
indicates that solvent basicity is a major factor in determining the extent of solvent swelling in
raw coals. This arises from the need to break the hydrogen bonds in coal in order to cause
swelling. In contrast, in pyridine extracted coals, the hydrogen bonds have been broken in the
extraction process. It is apparent that the hydrogen bonds have not re-formed after the removal
of the solvent at the end of the extraction process. The solvent swelling of the raw and
extracted coal are determined by the covalent crosslink density. Hence the rates of solvent
swelling of extracted coal are not affected by the basicity since the breaking of hydrogen bonds
are not involved to any significant extent.

The molar quantities of each of the pyridines absorbed by raw and extracted
Wearmouth coal have been calculated using the Equation 11. In the calculation, Wearmouth
coal was assigned a dry density of 1.3 g cm 3 because it falls within the rank range of coals
with that value of dry density. The extracted Wearmouth coal was also assumed to have the
same dry density value. Values of pKb, molar volumes of solvents, and the molar amounts of
each solvent absorbed by the raw and extracted coal are shown in Table 9. Also shown in
Table 9 are the activation energies and pre-exponential factors for the swelling of the raw and
extracted coal in each solvent. Since the molar volume of the solvents are similar, the molar
quantities absorbed is not unduly affected by the size of the solvent molecule.

50

Swelling of coal in pyridine and other amines involves the disruption of hydrogen
bonds in the coal and the formation of new bonds between the solvent and oxygen
functionalities in coal. Pyridine is capable of disrupting or breaking nearly all hydrogen bonds
in coal because of its strong basic character 36 .

Therefore, when coal which contains

significant amount of hydrogen bonding is exposed to pyridine these hydrogen bonds are
broken so that the coal swells to a limit primarily determined by its covalent crosslink density.
A solvent will disrupt only those coal-coal hydrogen bonds the bond strength of which are
weaker than those of coal-solvent hydrogen bonds 36 . Solvents having basicities lower than
that of pyridine will disrupt only the weaker hydrogen bonds so that those of higher bond
strength are left intact. This creates a situation where the number of hydrogen bonds broken by
the solvent is lower than that broken by pyridine. Therefore the solvent of lower basicity will
leave the coal with some hydrogen bonding interactions in addition to the covalent crosslinks.
Therefore the swelling ratio obtained in the solvent of lower basicity is lower than that obtained
in pyridine. This suggestion is corroborated by the equilibrium swelling ratios shown in Table
8 for raw Wearmouth coal.

The values of the diffusional exponents shown in Table 8 indicate that while the initial
mechanism of diffusion of pyridine into Wearmouth coal is Case II, the initial mechanism is
anomalous for the diffusion of 2-chloropyridine and 2-fluoropyridine. It is also clear from
Table 8 that the higher the pK^ of a solvent and hence the lower rate and extent of swelling, the
closer the initial diffusion mechanism for this coal approaches Fickian.

In a solvent swelling study of coals using straight-chain amines of same basicity but
different steric properties Green and West 29 found that the molar quantity of solvent absorbed
by each coal was almost constant for all amines, suggesting that all the absorbed amine
interacted with specific sites in the coal. However, their results show that the swelling ratio
increased with molar volume of amine. Contrary to the results of Green and West 29 the
present study reported here shows that although the molar volumes of the solvents are not very
different there is no correlation between molar volume of solvent and swelling ratio Table 9.
51

Also the coal absorbed different molar quantities of each solvent, the quantity absorbed
increasing with solvent basicity 49 . The increase with solvent basicity of molar quantity
absorbed suggests that the number of hydrogen bonding sites reacting with solvent molecules
increases with solvent basicity50 and this further explains the observed increase in equilibrium
swelling with basicity of solvent.

A comparison of the results of the present study and those reported by Green and
West29 suggests that while steric effects determine the swelling ratio for solvents of the same
basicity, differences in basicity determine the swelling ratio in solvents of the same steric
properties. Secondly, the number of specific sites for reaction with the solvent in any given
coal increases with basicity of solvent.

The apparent activation energies of 37.42.5. 31.71.0 and 24.11.6kJ mol 1


obtained for pyridine, 2-chloropyridine. and 2-fluoropyridine show that solvents of lower
basicity interact with weaker hydrogen bonds. Therefore strongly basic solvents interact with a
wider range of hydrogen bond strengths thereby causing larger reductions in the crosslink
density. Therefore coals give higher swelling in solvents of higher basicity.

Swelling of pyridine-extracted Wearmouth coal in pyridine. 2-chloropyridine, and 2fluoropyridine also obeys the experimentally-determined first order rate law for S c /S t > 50%,
Figure 19. The swelling ratios and the rate constants for the swelling are shown in Table 8.
The swelling ratios and the amounts of each solvent absorbed at 30C as well as the activation
energy and the pre-exponential factors for the swelling in each solvent are shown in Table 9.

It is apparent that the swelling ratio is not markedly affected by the basicity of the
solvent in contrast to the trend observed in the raw coal. The activation energies and the preexponential factors for the three solvents are very similar. The activation energies are much
lower (-10 kJ mol1) than for the raw coals suggesting a different type of interaction. The
52

structural differences between the raw and extracted coals manifested itself in the differences in
the rate constants, swelling ratios, activation energies and pre-exponential factors observed in
their swelling in the three solvents. The solvent swelling of the extracted coal does not vary
greatly with the basicity of the pyridines. This suggests that the formation of hydrogen bonds
in the extracted coal on pyridine removal is limited. This suggestion is supported by the faster
rates of swelling and lower activation energies for the extracted coal which also show no
marked dependence on the basicity of the solvent. The extent of swelling of the raw coal in
pyridine is significantly higher than that for extracted coal which indicates structural changes
involving probably covalent crosslinking and - interactions. The reduced swelling in
pyridine of the extracted coal may be caused by increased covalent crosslink density if the
extraction process causes decomposition. Secondly, collapse of the macromolecular structure
due to removal of soluble material leads to formation of strong - interactions which may act
as effective crosslinks. Although it is difficult to distinguish between the two possibilities but
Larsen et al. 51 favour the latter proposal.

Effects

of Steric Properties of Solvent on the Equilibrium

Swelling

and

Kinetics of Coal Solvent Swelling

Table 10 gives the equilibrium swelling ratios for Wearmouth coal in straight chain
amines. Considering the solvent swelling ratios obtained at 30C. it shows that a maximum is
reached at n-hexylamine.

A typical graph of ln((Se-St)/Se) against time for the swelling of coal in the amines is
shown in Figure 21. The rate constants, diffusional exponents, and the swelling ratios
obtained for each of n-butylamine. n-hexylamine, and n-octylamine at different temperatures
are shown in Table 10. Rate constants decrease with increasing amine size, showing that
smaller molecules diffuse into the coal structure more rapidly than the larger molecules.
Diffusional exponents calculated from the initial part of the solvent swelling curve also increase
53

with solvent size, becoming Case 11 for the larger amines. The pK b , molar volumes of
solvents, molar quantities of solvents absorbed, swelling ratio at 30C, and the activation
energy of the swelling process in each solvent are shown in Table 11. The result shows that
initially the extent of swelling increases with solvent molecular size. However there appears to
be a limit to which the coal macromolecule can swell to accommodate large solvent molecules.
The results suggest that the extent of swelling will level off or begin to decrease when that limit
is attained due to restriction to the diffusion and accessibility of the solvent molecule into the
coal structure. The apparent activation energy for the swelling increases with solvent steric size
indicating that there is an energy barrier for the process which increases as the solvent steric
size increases. Clearly, solvent size is a factor in determining the equilibrium swelling ratio
and solvent swelling kinetics. Also the mechanism of solvent swelling varies with the size of
the solvent molecule, becoming Case 11 for longer chain amines.

The ability of a basic solvent to disrupt hydrogen bonds in coal and thereby cause
swelling of coal depends on the basicity of the solvent. However, for the swelling of coal in
straight chain amines of similar basicity but different steric properties it will be inappropriate to
ascribe any differences to the basicity of the solvents. Differences in the solvent swelling
behaviour of coal in these solvents will occur as a result of the differences in solvent steric
properties. A trend of increasing swelling ratio with increasing molar volume of solvent
(amines) has been reported for three coals29.

Aida and Squires24 also reported the steric effects on the swelling of Illinois No. 6 coal
caused by primary amines of different chain lengths. It was shown 24 that the coal gave
swelling ratios of 2.45, 2.64 and 2.19 in -propylamine, n-butylamine. and n-hexylamine
respectively. However, no explanation was given as to why maximum swelling ratio was
obtained in n-butylamine. They 24 also showed that primary and secondary amines are more
effective swelling solvents for coal than tertiary amines.

If solvent basicity is the only property of solvent that affects swelling the coal would
54

give the same swelling ratio in the five solvents used in this study. Table 10 shows that the
swelling ratio of Wearmouth coal in the amines increases from -propylamine, through nbutylamine to n-hexylamine, and then decreases from n-octylamine to n-decylamine. It is clear
that the swelling of the coal increases with amine size up to n-hexylamine, but the trend
changes for amines of higher size.

The differences in the equilibrium swelling ratios can be explained in terms of the
ability or the tendency of the coal macromolecular network to swell in an effort to accommodate
the large molecules.

The tendency of coal macromolecular network to undergo a

transformation from a glassy to a rubbery state in the presence of amines has been
demonstrated by Brenner52 who also attributed this transformation to the breaking of inter
chain hydrogen bonds by the amine. It has been suggested that breaking of these hydrogen
bonds allows the macromolecular chains of the coal network to re-orient and extend themselves
as the solvent is absorbed29. Therefore, for a given coal the extent to which the chains will re
orient themselves when the hydrogen bonds arc broken will depend upon the number of
hydrogen bonds broken and the covalent crosslink density.

The swelling of Wearmouth coal in -propylamine has been caused by breaking of a


certain number of coal inter-chain hydrogen bonds by the solvent. If the steric properties of
these five solvents were the same the coal would have given the same swelling ratio in all the
five amines since their basicities are similar. It is hereby suggested that the higher swelling
recorded in n-hexylamine and n-octylamine is due to the rearrangement of the macromolecular
chains of the coal in order to accommodate the larger molecules. It should be expected that the
swelling ratio of the coal would be higher in n-octylamine and n-decylamine than n-hexylamine
since the macromolecular chains are expected to extend more to accommodate the larger noctylamine and n-decylamine molecules. But the similarity in the extent to which the coal
swelled in n-hexylamine and n-octylamine suggests that the coal macromolecular chains
extended to about the same extent in the two solvents. In fact the coal macromolecular
55

structure extended to a lower extent in n-decylamine. Table 11 shows that the molar amounts
of solvent absorbed by the coal is highest for -propylamine. This is not surprising because it
has the highest accessibility into the coal structure because of its small size. However, the
swelling of the coal in -propylamine is the lowest due to the fact that the coal macromolecular
structure had to extend only to a low extent to accommodate the small n-propylamine
molecules. Table 11 also shows that the coal absorbs about the same molar amounts of each of
n-butylamine and n-hexylamine but absorbs a lower amount of n-octylamine, and much less of
n-decylamine. It is clear that the lower amounts of n-octylamine and n-decylamine absorbed by
the coal is due to the inability of the coal macromolecular structure to extend further to
accommodate the large molecules or the inaccessibility of some coal-coal hydrogen bonds to
large solvent molecules as a result of steric effects.

It is clear from the extents of swelling of the coal in these solvents that increase in
amine size tends to increase the extent to which the coal network extends to accommodate the
amines, giving rise to increase in swelling with amine size. However, there may be. for each
coal, a critical amine size above which increase in amine size will not produce any increase in
swelling. Earlier workers29 predicted from a graph of swelling ratio versus molar volume of
amines, a swelling ratio of 5.8 for Rawhide coal in n-octadecylamine but wondered whether
the existence of covalent crosslinks may not limit the extent to which the coal can expand in
view of the large molecular size of this solvent. They therefore suggested that the swelling
ratio may level off at some critical amine size. The present study demonstrates that a large
increase in amine size may result in a decrease in swelling if the size of the molecule is so high
that it is highly restricted by steric effects from being absorbed by the coal structure as
observed in n-decylamine.

The swelling of Wearmouth coal in these amines also obeys the experimentally
determined first order rate law for Se/St > 50% as shown in Figure 21. Rate constants increase
with decreasing amine size and with temperature. Apparent activation energies obtained for
56

swelling of the coal in three of the amines show a trend of increase with amine size,

n-octylamine > n-hexylamine > n-butylamine

This shows that the barrier for the activated process increases with increasing size of the amine.

It is apparent from this study that although increasing amine size increases the swelling
of coal, it appears that there must be, for each coal, a critical amine size above which increasing
amine size will not increase the swelling of the coal. Secondly, the steric properties of an
amine have significant effects on the kinetics of coal swelling in the solvent. Therefore
molecular size of the solvent must be considered when choosing solvents for coal solvent
swelling studies.

It is interesting to note that the coal swells in pyridine to the maximum extent observed
in the straight chain amines. It is apparent that pyridine has the appropriate balance of basicity
and steric properties to swell coal to its maximum extent.

Effect of Particle Size on the Solvent Swelling of Coal

Table 12 shows the swelling ratios, the diffusional exponents and the rate constants for
the swelling of various panicle size ranges of Rawdon and Wearmouth coals in pyridine. For
Wearmouth coal there is little or no significant difference in the swelling ratios of the various
particle sizes. The same is true for Rawdon coal. Hence it is apparent that particle size is not a
factor which needs to be considered when studying the solvent swelling of coal.

In all the particle size ranges the diffusional exponent remains the same. It was found
that n was in the ranges (0.45-0.51) for Rawdon and (1.02-1.10) for Wearmouth. It is
apparent that within the particle size range studied ((150 - 212 .urn) to (355 - 600 )) the
57

diffusion mechanism is not affected by the particle size. On the other hand the rate constant
increases with decrease in particle size for both coals.

The results also show that the swelling ratios for Rawdon are more strongly dependent
on particle size compared with the Wearmouth coal. This can be explained by the different
mechanisms. Fickian rates are proportional to the reciprocal of the square of the particle size
while the relaxation controlled process is proportional to the reciprocal of the particle size.
Neither of these relationships is followed precisely since there are a number of assumptions
which are not strictly valid in the theoretical descriptions. These results indicate that the
swelling ratio does not vary greatly with particle size. H ence, it is appropriate to select a single
particle size for comparing swelling ratios.

It is shown that the rate constants increase with decrease in particle size for both coals.
The trend can be explained by the fact that the smaller the particle size of the sample the shorter
the time taken by solvent to get to the centre of the particle giving rise to a shorter equilibrium
time. Although the swelling ratios did not vary so much with particle size there is a discernible
trend of slight decrease in swelling ratio with particle size. Enscore et al. 27 determined the
mechanisms of n-hexane sorption into two different particle sizes of polystyrene spheres (184
diameter and 5340 diameter) and found that it was Fickian for the small particle size and
Case II for the large particle size. These findings do not apply to Wearmouth coal as the
diffusional exponent, n. indicates Case II mechanism for the particle size ranges studied.
There are several reasons to explain the constant nature of the diffusional exponent for pyridine
sorption into the particle size ranges shown for Wearmouth coal. Probably the particle size
ranges are not wide enough to show any changes in the diffusion mechanism. It may also be
that the combined processes of diffusion, chemical reaction and swelling involved in the coalpyridine system are more complex compared with the simple polystyrene-n-hexane systems
studied by Enscore et al.27 to give a change in diffusion mechanism with particle size. It is not
surprising that Rawdon coal showed Fickian diffusion for all the particle size ranges because
even the largest particle size has been previously shown to exhibit Fickian mechanism during

58

pyridine sorption53.

Effect of Oxidation on Swelling of Coal in Pyridine

The oxygen contents and swelling ratios in pyridine at 20C for the raw and oxidised
Rawdon, Wearmouth, Buchanan and Pinnacle coals are shown in Table 13. Also shown in
Table 13 are the values for Wearmouth coal heat-treated in an inert atmosphere to the same
temperature of oxidation for twenty four hours. It is clear that oxidation, as expected,
increases the oxygen content of these coals. In addition, oxidation increases their swelling
ratio in pyridine. On the other hand the oxygen content and swelling ratio of the blank
(Wearmouth coal heated in vacuum for 24 lirs. at 2(K)C) were not affected.

The swelling ratio in pyridine and the oxygen contents for the raw and oxidised coals
are also shown in Table 13. The swelling ratio in pyridine as well as oxygen contents of coal
increased as a result of oxidation. Each of these oxidised coals showed a two-stage process
during swelling in pyridine, as illustrated in Figures 22 and 23. It is clear that the coal
macromolecule is affected by oxidation.

The activation energy for the first stage in the swelling process of oxidised Wearmouth
coal is 60 kJ mol1 and that of the second stage is 65 kJ mol1. The pre-exponential factors are
1.77 107 and 4.47 IO8 s-1 respectively. The increase in rate is mainly related to the
increase in pre-exponential factor.

The swelling in pyridine of the Wearmouth coal heat-treated to simulate temperature


effects in the absence of oxygen shows only a one-stage process like the raw coal. Figure 24.
with an activation energy of 43 kJmol 1 . and pre-exponential factor of 7.3 IO3 s"1. The
rates, diffusional exponents and swelling ratios for the heat-treated and oxidised Wearmouth
coal are in Table 14. Values of the pre-exponential factors show that the improved accessibility
59

between the reacting species are higher for the second stage giving rise to higher reaction rates
irrespective of the slightly higher activation energy involved. This is probably due to the
difference in structure of the material at the later staee but could be a change in solvent
accessibility. It is apparent that heating of coal in the absence of oxygen does not significantly
affect the coal macromolecular structure to the extent it does in the presence of oxygen. The
very similar solvent swelling ratios for raw and heat treated Wearmouth coal indicates that the
crosslink densities are very similar. In other words, the changes in the coal macromolecular
structure were caused by oxidation. However, heat treatment does produce a small overall
increase in the solvent swelling and halves the rate of swelling for temperatures in the range 20
- 60C. Clearly, there are some minor changes in the coal structure.

Buchanan and Pinnacle coals which exhibit dangerously swelling characteristics during
carbonisation in the coke oven were also investigated. These coals exhibit very low solvent
swelling ratios which increase slightly with increase in temperature. On oxidation the swelling
ratios increased dramatically by -0.8. These results are consistent with a decrease in the
crosslink density with oxidation. It is possible that oxidation has broken some covalent
crosslinks thereby causing a decrease in the covalent crosslink density which has reduced
structural constraints to the swelling of the coal in pyridine.

The values of the apparent activation energies for the swelling of the oxidised coal
shows that the oxygen functionalities in the oxidised coal are more chemically stable than those
in the parent coal. In addition, slower swelling rates and higher activation energies for the
swelling in pyridine are observed. This is not surprising since the coal may have been oxidised
to higher temperatures than it experienced during formation.

It is not very clear why the swelling of the oxidised Wearmouth coal in pyridine
showed a two-stage process. It is possible that the first stage serves to open up the structure so
that swelling proceeds faster at a later stage. Another possibility is that if the outer parts of the
60

coal particles are more oxidised than the inner parts, the outer parts would contain more
oxidised coal and perhaps a greater extent of hydrogen bonding. This would give rise to a
situation where the outer parts of the particles will swell at a slower rate than the inner parts of
the particle, giving rise to a two-stage swelling process.

In order to further understand the structural differences that led to differences in the
solvent swelling of raw and oxidised coals FTIR spectra have been obtained on both raw and
oxidised coals. The idea to oxidise the coals at 200C stemmed from the fact that oxidation of
coals at temperatures above 170C is known to cause a drastic decrease in the aliphatic
structures and increase in oxygen-functional groups 54 56 . Esters and ether groups which
were usually prominent in low temperature oxidised coals to cause increase in crosslinkage and
loss of coking properties 57 ' 58 were not detected in coals oxidised at temperatures above
170oC54-56

Fourier-Transform Infra-red Spectra of Raw and Oxidised Coals

Infra red spectroscopy has been used to study the changes that occur in coal structure at
the molecular level as a result of oxidation in an effort to discern the causes of the differences in
the solvent swelling behaviour of coals of different rank. Wearmouth and Buchanan coals
have been chosen for this study because they vary significantly in rank. Wearmouth has a rank
of 502 in the British Coal Classification scheme, whereas Buchanan has a rank of 301a and is
known to be a dangerously swelling coal in coke oven carbonisation.

The FTIR spectra of most coals show several resolved bands between 2800 and 3000
cm"1 and a well resolved band between 3000 and 3100 c m ' l The former are assigned to the
aliphatic C- stretching modes of methyl or methylene groups while the later is assigned to the
aromatic C- stretching mode 59 60 . The FTIR spectra of the raw and oxidised coals show
similar absorption bands in this region. On deconvolution the bands assigned to the aliphatic
C- stretching can be resolved into six bands which appear at 2830, 2853. 2870, 2890, 2925,
61

and 2960 cm-'. In accordance with an earlier work by Griffiths et al

the bands at 2853

2870, and 2890 cm-1 have been assigned to the aliphatic C- symmetric stretching of
methylene, methyl, and tertiary CH groups respectively, while the 2925 and 2960 cm-1 bands
are respectively assigned to asymmetric C- stretching of methylene and methyl groups. The
band at 2830 cnr 1 is assigned to the C- stretching vibration of the methoxy group.

The infra-red spectra of the raw and oxidised Wearmouth and Buchanan coals are
shown in Figures 25. 26. 27 and 28. It is clear that these spectra exhibit the characteristic
absorption bands of coal. Although it is difficult to visually detect differences between the
spectra of raw and oxidised coals, it is possible to highlight differences using the difference
spectra, ( see Figures 29 and 30) obtained by subtracting the spectral data of raw coals from
those of the oxidised coals. The original spectra were obtained from specimen containing equal
amounts of sample in equal amounts of KBr. therefore the comparison is valid.

The difference spectra, show negative peaks at 2920 and 1450 cnr 1 indicating decrease
in aliphatic groups as a result of oxidation, a prominent positive peak at 1700 cnr 1 show a
general increase in carbonyl groups, an increase in carboxylate ions is indicated by the positive
peaks at 1580 and 1395 cm-1. Also negative peaks at 1600 cnr 1 and 3050 cnr 1 show a
decrease in aromatic structures while the positive peak at 3500 cnr 1 indicates increase in
hydroxyl groups.

The method of Christy et al.62, and Sobkowiak and Painter63 has been used to analyse
the bands which comprise the C- aliphatic stretching mode. The area under each band has
been taken as the area of the corresponding functional group in the sample. Keuhn et al 64
showed that the selection of individual n(C-H) stretching mode shows a better correlation with
coal rank than if the complete set of the n(C-H) aliphatic are considered as a whole. Brown59,
and Durie et al 6: \ obtained values of aromatic to aliphatic ratios using the intensities of the
aliphatic C- stretching band at 2923 cnr 1 and the aromatic C- stretching band at 3050 cnr 1
62

The areas corresponding to the various functional groups are shown in Tabic 15. It is
clear that both total aliphatic bands as well as aliphatic to aromatic ratios are reduced by
oxidation. While raw Wearmouth coal has an aliphatic to aromatic ratio of 3.17, the oxidised
coal has a value of 1.32. Similarly, the raw and oxidised Buchanan coals have aliphatic to
aromatic ratios of 0.78 and 0.36 respectively. An increase in the swelling of these oxidised
coals in pyridine also indicates that the crosslink density has decreased due to the destruction of
aliphatic crosslinks. Obviously, the aliphatic contents of coal are drastically reduced by
oxidation.

Changes also occur in the oxygen functional groups. Table 15 shows that the band due
to hydrogen bonded OH groups in the 3100 - 3600 cnr 1 of the spectra 59 65 ' 66 is increased by
oxidation in both coals. It will be recalled that in order to eliminate the effect of moisture
adsorption on the KBr disc each ground mixture of coal and KBr was evacuated for 24 hours
using a vacuum pump and pressed into pellet only at the time of measurement of the spectra.

The bands due to several oxygen functional groups such as the carboxylate ion.
ketones, quiones, carboxyl groups, and esters 6 7 - 6 9 also increase with oxidation.

The

solvent swelling studies show that the swelling ratio increases on oxidation for all four coals
studied. This is indicative of a decrease in crosslink density on oxidation. Taking these facts
into consideration it is apparent that aliphatic covalent crosslinks are being broken during
oxidation. It is also clear from Table 15 that oxidation increased the oxygen functional groups.
Increase in oxygen functional groups led to increase in hydrogen bonding interactions.

Buchanan and Pinnacle coals swell dangerously during carbonisation but do not swell
in pyridine. Evidently, swelling of oxidised Buchanan and oxidised Pinnacle coals in pyridine
was caused by the reduction of aliphatic crosslinks as a result of oxidation. Therefore the
density of covalent crosslinks is a major difference between high rank and low rank coals.

63

Dangerously swelling coals have a high crosslink density, and therefore it is proposed that this
is a structural factor which is of significance in assessing the carbonisation characteristics of
coals.

Within the rank range of coals used in this study, those coals that are lower in rank than
Buchanan do not swell dangerously during carbonisation in the coke oven. These coals swell
in pyridine at 20C because they have low covalent crosslink densities as well as significant
amounts of hydrogen bonding interactions which would be disrupted by pyridine. The
observation that Buchanan coal and those of higher rank do not swell in pyridine at 20C
indicates that they have high covalent crosslink densities. Buchanan and Pinnacle are known to
be dangerously swelling coals in carbonisation, and they swell in pyridine like nondangerously swelling coals after oxidation has reduced their covalent crosslink density and
introduced some hydrogen bonding interactions. This shows that the macromolecular structure
of the dangerously swelling coals differs from that of non-dangerously swelling coals in being
highly covalenti) crosslinked. This result corroborates that of Alvarez et al. 70 who measured
the changes in swelling and contraction of a rank range of coals caused by oxidation at 140C.
using the Koppers-INCAR apparatus and found that after 36 hours of oxidation two
dangerously swelling coals did not show any dangerously swelling behaviours.

Effect of Oxidation on the Solvent Swelling of different Particle Sizes of Coal

The swelling ratio in pyridine of different particle sizes of oxidised Rawdon and
Wearmouth coals are higher than those of the corresponding particle sizes of raw coals. The
various oxidised particle sizes of Rawdon also show a two-stage process during swelling in
pyridine. Rate constants for oxidised Wearmouth are higher than those for oxidised Rawdon.
The rate constants for oxidised Wearmouth coal increase with decrease in particle size.
However, for oxidised Rawdon coal, the smallest particle size ranges studied (212-250 ,
and 150-212 ) the rate constants for the first and second stages are similar. In fact it
appears that the swelling process for these small particle size ranges of the oxidised Rawdon
64

coal begin to approach a one-stage process. This effect is not significant in oxidised
Wearmouth coal. It is noteworthy that although the oxygen content, after oxidation increases
with decrease in particle size for both coals the percentage increase in oxygen due to oxidation
shows a different trend. While the percentage increase in oxygen content on oxidation
increases progressively but gradually with decrease in particle size for Wearmouth coal. For
Rawdon it decreases from particle size range 355-600 to 250-355 and remains constant
with decrease in particle size. The reason for this trend is not clear. It is also apparent from
Table 16, that the relative increase in oxygen content after oxidation is significantly higher in
Wearmouth coal than in Rawdon coal. Probably, due to its lower oxygen content than
Rawdon, Wearmouth coal has more oxidisable entities than Rawdon.

Table 17 shows the extent of swelling at which the second stage of the swelling begins
for each particle size. Also shown in Table 17 are the depths of penetration of the solvent
before the beginning of the second stage for each particle size. This calculation of the depth of
penetration was based on the assumption of a well-defined solvent front.

The extent of swelling at which the second stage begins increases with decrease in
particle size. The depth of penetration of the oxidation decreases with particle size for Rawdon
coal but does not show any clear trend for Wearmouth coal. In fact, it is almost constant for
Wearmouth coal. This suggests that the oxidation of the two coals involve two different
mechanisms. For Wearmouth coal the constant depth of penetration suggests that oxidation is
proceeding with a well-defined front. It is noteworthy that Wearmouth coal exhibited a Case
11 diffusion mechanism (well-defined solvent front ) during solvent swelling in pyridine.
Therefore it is not surprising that oxidation occurs by an oxidation front moving towards the
centre of the coal particle. The trend shown by the depth of oxidation in Rawdon coal suggests
that the oxidation front is not well-defined as in Wearmouth coal.

65

EXTRACTION STUDIES ON COAL

Extraction Yields of Coal

The percentage yields of the pyridine extraction for the rank range of coals are shown in
Table 18. It is clear that the extraction yield decreases as coal rank increases, as shown in
Figure 32. This shows that the pyridine soluble components of coal which are thought to be
responsible for coal fluidity during carbonisation decrease as coal rank increases. Variation of
extraction yield with coal fluidity is shown in Figure 34. It is clear that extract yield shows
maximum values for coals that show maximum fluidity. However, there are other factors
which may also affect the development of fluidity in the thermoplastic phase.

It is clear that for the rank range of coals studied extraction yield initially increases with
rank, reaching a maximum in the vitrinite reflectance range of -0.8% and decreases rapidly
thereafter with increase in rank, reaching minimum values in the high reflectance region from
1.33% reflectance, as shown in Figure 32. The pyridine extraction yield is low and almost
constant within the volatile matter range of 15.4-21.1% (daf). but increases thereafter with
increase in volatile matter. Figure 33. This is expected from structural consideration, since
extractable material is likely to be volatile. It is striking that pyridine extractability shows a
similar trend with coal rank as does swelling ratio in pyridine. The extraction yield is high for
coals that show high values of fluidity. Figure 6.34. The trend in the variation of extraction
yields with coal fluidity is in agreement with the findings of Wynne-Jones et al. 71 who
showed for several coals that the maximum yield of pyridine extracts of coals coincided with
maximum coal fluidity. It is clear that the low volatile, low fluidity bituminous coals which
exhibit dangerous swelling characteristics during carbonisation contain very low amounts of
pyridine extractable materials.

It is thought that the liquid fraction in the pyrolysing system produced by the pyridine
66

extractables determines the fluidity of the system 72 " 74 . It is apparent that the coals which
swell excessively in the coke oven during carbonisation exhibit low fluidity and have
correspondingly very low contents of pyridine extractables. The decomposition of the highly
crosslinked macromolecular structure in association with very small amount of mobile phase
leads to the development of a thermoplastic phase of very low fluidity and low permeability.

FTIR of coal extracts

The infra-red spectra of the coal extracts have been studied in order to provide
information regarding the composition of the extracts. The spectra are stacked in order of
increasing rank with that from coal of the highest rank at the bottom in Figures 35 and 36.
Although the spectra feature the characteristic absorption bands expected in the spectra of coal
extracts it is clear that there are variations in the relative intensities of the absorption bands in
the spectra of extracts from different coals.

The FTIR spectra of the coal extracts show similar absorption bands in the same
regions as the coals. Band assignments are the same as in the previous section although minor
shifts occur as expected. On deconvolution of the 2800 - 3000 cm-1 region of the spectra it can
be resolved into six bands which appear at 2X30. 2853. 2870. 2890. 2925. and 2960 cm"'.

The infra-red spectra of pyridine extracts of coals show that the absorption peaks at
2850 and 2925 cnr 1 assigned to the aliphatic CH 2 and CH 3 stretching modes are better
resolved in the extracts of high rank coals from Buchanan to Lady Windsor than in the lower
rank coals ranging from Line Creek to Rawdon. Figure 35 also shows that the aromatic CH
stretching band at 3050 cnr 1 is more prominent in the spectra of extracts of the coals ranging
from Rawdon to Line Creek, almost negligible in the extracts of Buchanan, Saraji and
Oakgrove, but appear again in spectra of the extracts of higher rank coals Oakdale, Norwich
and Lady Windsor. The peales at 1454 and 1375 cm"1 which are due to the aliphatic CH 3 and
67

CH 2 bending modes are very prominent in the spectra of extracts from Buchanan, Saraji and
Oakdale compared to Oakdale, Norwich and Lady Windsor. These peaks are very small in the
spectra of extracts from the low rank coals from Rawdon to Line Creek. It is also evident from
Figure 36 that the aromatic ring vibration absorption peaks at 1600 cnr 1 are very low in the
spectra of extracts of Buchanan, Saraji and Oakgrove compared to the extracts of other coals
both higher and lower rank. Hence the extracts of these three coals are more aliphatic than
those of others.

Specific regions of the FTIR spectra of the extracts have been deconvoluted in order to
obtain information on band intensities for the extracts. Using the aliphatic C- asymmetric
stretching bands at 2923 and 2960 cnr1 and the aromatic C- stretching band at 3050 cnr 1 it is
shown in Table 20 that the areas of the aromatic stretching band do not show any trend with
coal rank. On the other hand the areas for the asymmetric C- stretching of methylene groups
are low for low rank coals from Rawdon to Line Creek but high for the extracts of higher rank
coals ranging from Buchanan to Lady Windsor. Sobkowiak et al. 78 have shown, using the
nuclear magnetic resonance technique that hydrogen content as aromatic C- in the pyridine
extract of coals shows no trend with coal rank for coals of 70.3 -87.8 % C. They also showed
that the percentage hydrogen content as aliphatic C- decreases with increase in rank of the
parent coal though the decrease was not continuous with rank increase. However, the present
study reported here covers a wider range of coal rank and shows that for coals higher in rank
than those studied by Sobkowiak et al.78 the C- aliphatic of the extracts are higher than those
of the extracts of lower rank coals.

Figure 37 and Table 20 show that while the percentage of the area of the methylene CH asymmetric stretching frequency increases in the higher rank coals, the percentage of the
area of the methyl C- asymmetric stretching decreases. This indicates that for the extracts of
the high rank coals the length of the aliphatic chain probably increases with rank.

The aliphatic to aromatic ratios of the extracts obtained using the aliphatic asymmetric
68

C- stretching vibration, shows no clear trend with coal rank for low rank coals from Rawdon
to Line Creek but increases with coal rank for higher rank coals and shows maximum values
for Buchanan, Saraji, and Oakgrove (Vitrinite reflectance 1.33-1.42 %). This is illustrated in
Figure 6.31. The aliphatic to aromatic ratios based on the methyl C- asymmetric stretching
frequency shows the same trend with rank of parent coal although the ratios are lower. Using
infra red spectra Durie et al. 79 showed that the aromatic to aliphatic ratios of pyridine coal
extracts increase with increase in coal rank for coals of 81.7-89 % C though the increase was
not continuous. In other words, the aliphatic to aromatic ratios decrease with increase in coal
rank for the coals studied. Again it must be highlighted that they studied only a narrow region
of coal rank. The present study shows that the aliphatic to aromatic ratio increases with
increasing rank for the pyridine extracts of coals which are higher in rank than those studied by
Durie et al 79 .

Although the areas for the asymmetric C- stretching for methylene and methyl groups
do not show any clear trend with coal rank for low rank coals from Rawdon to Line Creek, it is
clear that the values are higher for high rank coals from Buchanan to Lady Windsor.

The FTIR spectral region from 700-900 cnr 1 has been deconvolved in order to study
the aromatic C- out-of-plane deformation modes. It was necessary to fit as many as nine
peaks in some cases in order to obtain a good fit. The pyridine band at 704 cnr 1 was
eliminated from each spectra

Also the bands at 720. 830. and 840 cm-1 assigned to the

rocking modes of aliphatic CH 2 groups 63 75 were not required except for the spectra of
Buchanan, Saraji. and Oakgrove which have the 720 cnr 1 band. Table 21 shows the areas
obtained for the bands at 750, 770. 801, and 816 cnr 1 which correspond to absorptions by
five, four, three, and two adjacent aromatic C- groups respectively: and the areas for the
bands at 860, 874, and 888 cm" 1 each of which corresponds to an isolated C- group in a
different chemical environment 61 63 76 . The higher the wavenumber of the vibrational band,
the greater the substitution of the aromatic ring which it represents.
69

There is no clear trend between the area of any of these bands with coal rank. Rather it
is possible to separate the spectra into five different groups based on the similarities between
members of each group according to the data in Table 21. The groups comprise of Rawdon,
Barnburgh, H ucknall, Wearmouth and Wentz in group a; Ruhrkhole and Line Creek in group
b; Buchanan, Saraji, and Oakgrove in group c; Oakdale and Norwich in group d; and Lady
Windsor which is quite different from others. It is clear that Buchanan, Saraji, and Oakgrove
have the least peak areas for these aromatic contents as estimated from the n(C-H )arom
intensity. In other words , they are more aliphatic, and this supports the earlier findings in this
work that they have the highest aliphatic to aromatic ratios. The grouping of the spectra
according to similarity based on the data of Table 21 is also observed in Figure 39 (a), (b), (c),
(d) and (e) where the spectra have been stacked according to the groups. It is clear that there is
no marked difference between members of the same group. The spectra also show that extracts
of Buchanan. Saraji, and Oakgrove show the lowest intensity.

It is clear that the spectra of the extracts of Buchanan, Saraji. and Oakgrove differ from
others in that they show a distinct band at 720 cnr 1 . The band can be assigned to the rocking
modes of the methylene C-. This band is very small or entirely absent in the spectra of the
extracts of other coals. This observation lends further support to the conclusion that the
pyridine extracts of these three coals are more aliphatic than those of the others.

The region of absorbance of oxygen functional groups in the FTIR spectra of the coal
extracts (1550-1800 cm' 1 ) is dominated by the broad band at 1600 cnr 1 , but on deconvolution
of this region of the spectra it is resolved into four bands at 1600. 1655. 1700, and 1720 cnr 1 .
The areas of the bands at 1655. 1700. and 1720 cnr' have been standardised using the band at
1600 cnr 1 as an internal standard. In accordance with previous work 60 ' 75 77 the bands have
been assigned to n(C=0) of conjugated carbonyls {e.g. quiones), carboxylic acids, and
esters respectively. Table 22 shows that the area for the conjugated carbonyls increase with

70

coal rank.

It is clear that the areas of the bands at 1700 and 1720 cm-1 corresponding to carbonyls
of carboxylic acids and esters respectively do not show any trend with rank of parent coal.
However, the area of the band at 1655 cm-1 corresponding to conjugated carbonyls (e.g.
quiones) show an increase with rank of parent coal, Figure 40. This trend contrasts with a
trend of decrease in total oxygen content with increase in coal rank observed for the extracts.
Probably, the extracts of lower rank coals contain more of their oxygen in the groups that do
not absorb in the C=0 absorption region. It is apparent that the extracts of high rank coals
starting from vitrinite reflectance of 1.33 % have a higher percentage of their oxygen content in
form of conjugated carbonyls, e.g. quiones. It is clear that the extracts of the dangerously
swelling coals Buchanan. Saraji. and Oakgrove are more aliphatic than those of the other coals,
and also have more of their oxygen content in the form of conjugated carbonyls. probably
quiones.

Total areas for the oxygen functional group bands show a trend of increase with coal
rank in contrast to a trend of decrease with increasing coal rank shown by values determined by
elemental analysis. This may be as a result of the fact that the major part of the oxygen
contents of the extracts of the lower rank coals occur in other forms that do not absorb in the
n(C-O) stretching vibration region considered in the FTIR spectra. This is supported by the
appearance of high intensity bands in the n(C-O) stretching vibration region in the extracts from
the low rank coals.

Care must be taken in the use of the curve resolution data. An example of this comes
from the curve resolution of the FTIR spectra in the d(C-H)bend region where H ucknall shows
distinct differences based on curve resolution but the FTIR spectrum does not look out of place
when compared with coals of similar rank, see Figure 39(a).

The C- stretching and deformation peaks obtained from extracts of coals heated to

71

softening point are shown in Table 23. There seems to be no relationship between areas of the
aromatic and aromatic bands and coal rank. The data also does not show any difference for
dangerously swelling coals. Obviously the decomposition of coal is a very complex process,
involving various pyrolytic and condensation reactions the combined effect of which may not
show any trend with coal rank.

Oxygen Contents of Extracts

Oxygen contents of coals, extracts, and residues are shown in Table 24. They decrease
with increase in coal rank. Figures 41-43. Oxygen content of extracts increases compared with
those of the corresponding coals, Figure 44. However, oxygen contents of the lower rank
coals are higher than those of their extracts whereas for the higher rank coals it is the opposite.

It is clear that while low rank coals in the reflectance range 0.47 to 1.20% show
negative values for (% oxygen in extract - % oxygen in coal), coals of higher rank from 1.33 to
1.82% reflectance show positive values, Figure 45. This trend suggests that the extractable
"mobile" phase of the lower rank coals contain less oxygen than the macromolecular phase
while reverse is the case for the high rank coals. In other words, the extractable mobile phase
of the high rank coals from reflectance of 1.33% and above contain more oxygen than their
macromolecular phase while the extractable phase of those low rank coals below -1.2%
reflectance contain less oxygen than their macromolecular phase. The mobile phase of the
higher rank coals may then be more reactive than the corresponding macromolecular phase
since they are richer in oxygen. The reactivities and relative amounts of the macromolecular
structure and the extracts are important in determining the softening and decomposition
temperatures of the coals. This is of major significance in the development of the thermoplastic
phase. If they are more reactive they will react very fast on heating and even undergo
crosslinking reactions early in the carbonisation process with the result that they will not
develop a high degree of thermoplasticity. Hence these high rank coals produce highly viscous
72

thermoplastic phases which do not allow easy escape of volatiles thereby causing high internal
pressure and excessive swelling during carbonisation in the coke ovens. However it is likely
that the lower functional group concentration as shown by the lower oxygen contents and the
lower total amounts of extracts in high rank coals are the major influences on the
thermoplasticity. However the quantity of the mobile phase needs to be considered in
conjunction with chemical and physical characteristics of the mobile phase.

For lower rank coals the mobile phase of which have lower or about the same oxygen
content with the macromolecular phase, the two phases may be of the same order of reactivity
so that they can react and crosslink in the thermoplastic phase leading to the eventual formation
of semicoke.

Values of the oxygen contents of residues and extracts of coals heated to their softening
and maximum contraction temperatures. Table 25, show that they give the same trend with
rank as those of the raw coals. This is illustrated in Figures 46(a) and 46(b). This shows that
up to these temperatures the compositions of the macromolecule and the extractable phase do
not change greatly indicating only small amounts of decomposition. It is also clear that there is
no definite relationship between oxygen contents of the extracts of the coals heated to their
softening and maximum contraction temperatures and those of the raw coals. Obviously,
decomposition products are chemically different from the raw materials.

Size Exclusion Chromatography of Coal Extracts

Retention volume in tetrahydrofuran (THF) of the extracts from various coals are
shown in Table 26. It is apparent that a weak trend exists. ( see Figure 47 ) of increase in
retention volume of the extracts with reflectance of the parent coal. Extracts from coals of
higher rank show higher values of retention time which is a reflection of lower molecular sizes.
It is clear from Figure 47 that extracts from coals of high rank from about 1.33% and above
73

show the highest values of retention time. Therefore extracts from coals of this rank have the
lowest molar mass distributions in the rank range of coals studied. Earlier studies 71 have
shown that coals having maximum molar mass of extracts also show maximum fluidity. It is
therefore not surprising that coals of reflectance 1.33% and above which show low fluidity
also have extracts of low molar mass. It is possible that the decomposition of the higher molar
mass extracts to smaller units gives rise to greater amount of liquid fraction that promotes
fluidity in the coals having extracts of high molar mass distribution. Whereas low molar mass
extracts on decomposition produce limited amount of lower molar mass species and hence low
amounts of liquid fraction and low fluidity.

It is clear from the extraction studies that within the rank range of coals studied those
having reflectance of 1.33% and above have very low quantities of pyridine-extractable
materials. Extracts from some of those coals within the reflectance range of 1.33-1.82% are
more aliphatic than the extracts from other coals. Extracts of coals within this range of rank
contain more oxygen than the corresponding coals while the remaining have lower oxygen
contents than their parent coals. The molar mass of the extracts from this rank range are low
compared to those of others. It is noteworthy that dangerously swelling coals are found within
this rank range of coals.

Table 26 also shows the retention volumes in tetrahydrofuran of pyridine extracts of


coals, and extracts of the coals heated to their softening and maximum contraction
temperatures. The data show that the retention volumes of the extracts of coals heated to the
softening point are higher than those of the extracts of raw coals. On the other hand the
retention volumes of the extracts of those coals heated to maximum contraction temperatures
are lowest. This suggests that at the softening point, the extracts decompose and later
polymerise near the maximum contraction temperature.

The retention volumes in chlorofonn. ( see Table 27 ) show a different trend. It is clear
74

that the retention volume decreases with increasing heat treatment temperature. This shows that
there is a continous decomposition of the extracts as temperature of the coal increases. This
trend appears to be more credible than that obtained in tetrahydrofuran. It is also clear that the
extracts of the dangerously swelling coals show high retention volume in chloroform. The
same trend is maintained in the extracts of the heated coals.

THERMOGRAVIMETRY

The thermogravimerry data obtained from a wide range of coals are shown in Tables 28
and 29. Four characteristic thermogravimetric temperatures and rate of volatile loss in
milligrams per minute are shown for five coals at heating rates of 5, 10, 15, 20, 25 and 40C
per min, Table 28. The rates of decomposition and temperatures of initial decomposition for
5C mirr 1 heating rate for extracted and raw coals covering a wide rank range are shown in
Table 29. Also shown in Table 29 are the softening temperatures for the rank range of coals.

The temperature at which decomposition begins increases with rank. Lower rank coals
contain higher amounts of hydrogen-bonding interactions which dissociate at low temperatures
to cause initial softening and evolution of volatile matter at lower temperatures. Secondly, the
lower rank coals are more reactive because of higher oxygen contents so they decompose more
easily and at lower temperatures than do the high rank coals. The higher rank coals are highly
covalently crosslinked, and these crosslinks have to be broken in order to bring about initial
softening.

The temperature at which volatile release ends increases with coal rank. Higher rank
coals have very low oxygen contents and hence lower hydrogen-bonding interactions. Higher
rank coals therefore, have more stable structures which require more thermal energy for their
decomposition than would be required by lower rank coals.

For heating rates of 5 and 10C/min the temperature range of weight loss decreases
75

with increase in rank, reaches a minimum and then increases with rank. On the other hand, it
shows a trend of increase with rank for heating rates of 15, 20 and 25C. The high values for
lower rank coals at the heating rates of 5 and 10C may be due to prolonged release of volatiles
caused by the high values of volatile content as well as the low temperature at which it starts.
The high value for high rank coals may have been caused by the prolonged decomposition of
the coal caused by high crosslink density and chemical stability. At higher heating rates the
chemical stability of the coal seems to be the overriding factor.

Rate of volatile loss decreases with increase in coal rank as would be expected from the
decreasing volatile matter content because volatile matter, oxygen functionality and hydrogen
bonding interactions are all decreasing with increase in coal rank, so that the coals are
becoming more chemically stable and less reactive. Secondly, increase in covalent crosslink
density with coal rank may also result in a higher stability.

It is clear that all the characteristic thermogravimetric temperatures as well as rate of


volatile loss are dependent upon coal rank, increase as the coal rank increases due to the
increase in chemical stability of the system.

Effect of Extraction on the Temperature of Commencement of Weight Loss and


Rate of Loss of Volatiles at a heating rate of 5 C C.

The aim of studying the thermogravimetric properties of extracted coal is to establish


the role of the macromolecular structure on the thermal decomposition of both safe and
dangerously swelling coals.

The temperature at which release of volatile matter begins increases with coal rank for
both extracted and raw coals although the value for extracted coals are higher. The difference
is larger with low rank coals than for higher rank coals. This observation is expected because
76

the removal of extractable materials of coal will leave the coal with mainly covalent crosslinks
and some non-covalent interactions that may have reformed on removal of solvent. Extractable
materials which usually are the sources of the initial volatiles are absent. Under such situation
only the thermal breakage of covalent crosslinks will cause volatile release and this occurs at
high temperatures than it would if extractables are not removed from the coal. The increase in
temperature of initial decomposition due to extraction is more pronounced in lower rank coals
because they contain higher amounts of extractable materials the effect of the removal of which
will be more pronounced than in the higher rank coals that have lower amounts of extractables.

The rate of weight loss decreases with increase in coal rank for both raw and extracted
coals, but the rates are higher for extracted than for raw coals. The increase in rate of volatile
loss as a result of extraction is caused by the reduction in the additional structural stability
conferred upon the coal by the original hydrogen bonding interactions. These original
hydrogen bonding interactions are virtually absent in the extracted coals. It is also possible that
the extractable material in the raw coal participates in crosslinking reactions during pyrolysis
thereby producing large molecules which would cause a delay in the decomposition of the coal.
This effect will be absent in extracted coal, hence the increased rate of decomposition observed
for extracted coal. It is clear that rates and temperatures of decomposition do not show any
special characteristics of dangerously swelling coals.

Dilatometry/permeability of semicokes

Tables 30 and 31 show the dilatometrie and permeability data obtained from the rank
range of coals. The dilatometry data did not show any differences between safe and
dangerously swelling coals. The data show that the permeability of the semicokes continue to
increase even after the plastic phase has re-solidified.

In other words the porosity of the

semicokes continue to change in the secondary devolatilisation region. Figures 48(a) to 48(h)
show the variation of permeability with temperature for Rawdon, Wearmouth, Wentz,
77

Buchanan, and Saraji coals. These graphs show that the permeability of the coal charge
decreases with increasing temperature after softening and attains minimum values and increases
again as temperature increases. It is clear from Table 31 that the temperature after the minimum
at which the permeability starts to increase is rank dependent. It increases with increase in the
rank of the parent coal and are in the range of the temperature of maximum contraction. It is
also shown in Figure 48(h) that the rate of increase of permeability after the minimum value
increases with rank of parent coal, with the dangerously swelling coals Buchanan and Saraji
showing very slow increase in permeability after the minimum values. This shows that escape
of volatiles are markedly restricted in the plastic phase of the dangerously swelling coals, and
this property gives rise to accummulation of volatiles which results in high internal pressure
and swelling pressures that may be capable of damaging coke oven walls.

High pressure dilatometry

Table 32 shows the variation (if dilatometrie parameters with applied pressure for a rank
range of coals. The data shows that there are different effects of pressure on the dilatation of
coals and the effect appears to be different for coals of different rank. Apan from Rawdon. the
dilatation of which is negative and is more or less independent of pressure the dilatation of the
other low rank coals decrease with increasing pressure. On the other hand the dilatation of the
higher rank coals from vitrinite reflectance of 1.33 increase with increase in applied pressure
and show maximum values at varying values of applied pressure. The pressure at which the
maxima occurs is in the region of 15-25 bar. It appears that dangerously swelling coals are
characterised by such maxima in dilatation with pressure.

The dilatation of coals at elevated pressures is controlled by two factors. Increase in


pressure decreases the volume of gases thereby causing a decrease in the swelling of the plastic
layer. On the other hand, increase in pressure increases the residence time of the volatiles so
that they undergo secondary decomposition which leads to increase in fluidity and swelling 80 .
As already mentioned elsewhere the low rank coals show a gradual decrease in dilatation with
78

increase in pressure while each of the dangerously swelling coals shows a maximum dilatation
at a given value of pressure. This indicates that for the dangerously swelling coals there is a
particular range of pressure within which the effect of increased residence time is more
predominant than the effect of reduced volume of volatiles, whereas the effect of the decrease
in gas volume controls the dilatation of the low rank coals for all the pressures at which the
dilatations were measured.

SURFACE AREA OF COALS AND SEMI-COKES

The C 0 2 (273 K) surface areas of the coals and semi-cokes are shown in Table 33. It
is clear that surface areas of the coals and semi-cokes are dependent upon the rank of the parent
coal. The surface areas increase with heat treatment temperature and attain maximum values at
about 600C and then decrease with increase in temperature.

This shows that open

microporosity development during carbonisation attains a maximum value at about 600 C. For
the raw coals as well as the semicokes there is a trend of decrease in the surface area with
increase in rank. The gas capacities and diffusion rates reach a minimum in the medium rank
range except in the HTT 50()C semicokes. Again, the maximum surface area for the lowest
rank coals Rawdon, Barnburgh and Hucknall do not show maximum values for HTT 600'C
but for HTT 800C. There appears to be a close relationship between surface area ( C O T .
273K) and gas capacity and diffusion kinetics into the semicokes. The data also show that
microporosity in the semicokes show lower values for the dangerously swelling coals.

GAS DIFFUSION INTO COALS AND SEMICOKES

The two gases, oxygen and nitrogen used in this study are slightly different in
molecular dimensions. Oxygen has a molecular diameter of 0.346 nm while the molecular
diameter of nitrogen is 0.364 nm. A typical uptake versus time curve for oxygen uptake by
semicoke is shown in Figure 49. It is characterised by initial rapid uptake, followed by
79

progressive decrease in rate of uptake until equilibrium is attained.

Oxygen capacities of semicokes prepared at 450, 500, 600 and 800C are shown in
Table 34. Coals and semicokes prepared at 1000C did not take up significant quantities of
oxygen. The pore sizes of the coals and semicokes of 1000C are sufficiently small that the
oxygen molecule cannot diffuse into them. Table 34 shows that for the semicokes made at
450C only those of the low rank coals Rawdon, Barnburgh, Hucknall, Wearmouth and Wentz
take up oxygen, and the capacity decreases with increase in coal rank. For the rest of the
semicokes the oxygen capacity also decreases with increase in rank of parent coal except that of
600 and 800C semicokes in which minimum values tend to occur in the region of rank
comprising of Buchanan, Saraji and Oakgrove, see Figure 50. Also, for all coals there appears
to be a trend of maximum capacity at 600C semicokes except for the low rank coals Rawdon,
Barnburgh and Hucknall. With the exception of these three coals there appears to be a general
trend of increase in microporosity of the semicokes as heat treatment temperature (HTT)
increases with maximum values occurring at HTT of 600C after which the microporosity
begins to decrease.

A high capacity for oxygen implies high microporosity and if the semicoke shows high
microporosity it means that it has enough channels through which volatiles can escape by
diffusion during carbonisation. If the semicoke has enough channels for escape of volatiles by
diffusion, accumulation of gases and high internal pressure will not occur. However, if the
semicoke is of low porosity, volatiles will have inadequate amount of channels through which
they could escape by diffusion, and under such a situation a large amount of the volatiles will
be retained in the macroporosity. resulting in high internal pressure and high swelling
pressures.

Those coals the semicokes of which have ven' low gas capacities will have a higher
resistance to the diffusion of gases and will exhibit high internal pressure during carbonization.
80

Therefore those coals are likely to develop excessive swelling during carbonization.

Nitrogen capacities for the semi-cokes are shown in Table.35. The coals as well as the
semi-cokes produced at 1000C did not show any significant adsorption capacity for oxygen or
nitrogen. The semi-cokes produced at 450, 500, and 600C from Rawdon, Barnburgh,
Hucknall, Wearmouth and Wentz did not adsorb nitrogen. Those produced at 600C adsorbed
both oxygen and nitrogen with the exception of those from Buchanan and Pinnacle which
adsorbed only oxygen. This is consistent with the restricted access of nitrogen to the porous
structure.

The fact that only HTT 600C semicokes showed capacities for nitrogen indicates that
pore structure development during carbonization of coals occurs in such a way that the plastic
phase exhibits maximum microporosity at the temperature of about 600C. The fact that
semicokes of HTT 450, 500 and 1000C do not take up nitrogen but take up oxygen shows
that their pore diameters are so small that they are inaccessible to nitrogen. It is clear that for
the HTT 600C semicokes which take up both gases, the oxygen capacity is higher for each
semicoke, showing that the porosity accessible to oxygen is higher than that accessible to
nitrogen due to the larger molecular diameter of nitrogen. This indicates a well-defined narrow
microporous structure with molecular sieving effects. Nitrogen capacity also shows the same
trend with rank as oxygen capacity. Figure 51. Nitrogen capacity of the semicokes also
decreases with increase in rank of parent coal, and shows minimum values for the dangerously
swelling coals, see Figure 51.

A typical graph of ln((Me-Mt)/Me) against time for oxygen uptake into the semicokes is
shown in Figure 52. It is clear that the shape of the graph is consistent with that of the
theoretical Fickian curve, see Figure 2. Similar graphs were obtained for nitrogen diffusion
into those semicokes which showed some adsorption capacity for nitrogen. Also application of
the empirical diffusion equation to the uptake data gives values of diffusional exponent of about
81

0.5, Figure 53. It is clear that the diffusion of oxygen and nitrogen into these semicokes is a
Fickian diffusion process.

It was demonstrated by Schrter and co-workers 81 in a study of the influence of pore


structure on the diffusion of Krypton into activated carbons that for spherical particles under
conditions for removed from equilibrium the diffusional parameter increases with increasing
pore diameter. A similar observation was also noted by Juntgen et al. 82 . It is therefore clear
that higher diffusional parameters indicate larger pore diameters.

The diffusion rates denoted by the diffusional parameter D/a2 for the diffusion of the
gases into the semi-cokes are shown in Table 36 for oxygen and Table 37 for nitrogen. The
diffusion rates for oxygen are higher than those for nitrogen. The trend is not surprising in
view of the larger molecular size of nitrogen. The diffusional parameter for oxygen decrease
with increase in coal rank. Figures 54. The diffusional parameters for nitrogen also show a
trend of decrease with increase in coal rank. Figure 55. with minimum values occurring in the
mid rank region where dangerously swelling characteristics are observed. However, it is clear
that oxygen diffusion rates are higher than those of nitrogen, due to differences in their
molecular size. Hence it is apparent that molecular sieving effects are occuring.

Pore structure of cokes derived from coals which exhibit dangerously swelling
properties show some distinct differences. The cokes have low adsorption capacities and the
diffusion of gases into the structure is slow in comparison to the cokes derived from lower
rank coals. As is normal in coal science the trend has some anomalies. Oakdale is the
exception but the dangerously swelling characteristics of this coal are not known. Buchanan
and Pinnacle are the coals which exhibit the most severe dangerously swelling characteristics.

It is clear that because of the low diffusional parameters associated with small pore
sizes those coals the semicokes of which show low diffusional parameters will develop plastic
phases of low permeability during carbonization. The low permeability of the plastic phase
82

will give rise to accumulation of volatiles due to the restrictions in their escape. This will cause
high internal pressure and excessive swelling.

Review

The dangerously swelling behaviour of coal is caused by the restricted escape of


volatiles through the plastic layer and coke during carbonisation in the coke oven 38 ' 39 . The
restriction causes accumulation of gases in the macroporosity with consequent generation of
internal pressure which causes excessive swelling.

It is the high viscosity and low

permeability of the plastic layer of these coals which is involved in the restriction to the escape
of gases.

Dangerously swelling coals develop a plastic layer of low fluidity during

carbonisation unlike the "safe" coals which develop a highly fluid plastic layer during
carbonisation.

Coal consists of the macromolecular phase and the extractable phase, and the pyridineextractable component is thought to be involved in the development of fluidity during
carbonisation.

This study reveals that the macromolecular structure of the dangerously

swelling coals are highly crosslinked. Secondly, the dangerously swelling coals contain very
low amounts (~ 2 %) of pyridine extractable materials.

Although the nature of the extracts do not vary greatly with coal rank, it is easily
discernible that the extracts of the dangerously swelling coals
(1)

are more aliphatic than those of other coals in the rank range studied

(2)

have low molar mass distribution

(3)

have more oxygen than their parent coals in contrast to the lower rank coals that
have less oxygen than their parent coals

In view of the fact that the extracts of the dangerously swelling coals constitute only
83

about 2% of the coal and their composition only varies to a limited extent, it is clear that the
amount of extract rather than its nature affects the dangerously swelling property of coals.
Secondly, because the macromolecular phase makes up about 98 % of the dangerously
swelling coals it is suggested that the nature of the macromolecular phase and the way in which
it decomposes is a major factor in determining the dangerously swelling properties of coals.
Therefore the decomposition of the highly crosslinked macromolecular structure with a small
amount of extractable phase leads to the formation of highly viscous plastic phase which shows
low permeability to the escape of volatiles.

The low microporosity, low surface area, and low gas diffusion rates measured on the
semicokes of the dangerously swelling coals, when compared with the values obtained from
the semicokes of other coals show that the semicoke / coke structures in dangerously swelling
coals are capable of restricting the escape of volatiles. This restriction to the escape of volatiles
will cause high internal pressure and excessive swelling.

A recent study 83 84 of the variation in the pressure exerted by several coals on the
walls of a laboratory test oven shows that Pinnacle. Buchanan, and Oakgrove coals are among
the coals that generated the four highest wall and internal gas pressures recorded in the test.
These three coals are known to exhibit dangerously swelling characteristics in industrial
carbonisation. The results of the wall pressure tests therefore corroborate the findings from the
present study which has highlighted the distinct characteristics of dangerously swelling coals
includine these three coals.

84

CONCLUSIONS
This study was aimed at identifying the fundamental properties of coals that exhibit
dangerously swelling characteristics during carbonisation in the coke oven. In pursuit of that
objective the project was approached from two view points, namely, the study of coal
structure; and the study of the pore structure development in the plastic stage of coal
carbonisation. The specific conclusions drawn from the results obtained have been presented
in line with this approach.

SPECIFIC

CONCLUSIONS

Characterisation of Coal Structure

Coals are complex heterogeneous materials and this presents a major difficulty as far as
structural characterisation is concerned. Basic coal characterisation involves the the following:
ultimate and proximate analysis, petrology, caking and swelling properties, calorific value and
ash analysis. This has been shown to be insufficient for the characterisation of dangerously
swelling characteristics in carbonization in the coke oven. A more detailed characterisation of
the coal structure is required. A more detailed characterisation of coal structure was divided
*

into two parts, namely, study of the coal macromolecular structure using the solvent swelling
technique, and the estimation of the quantity and characterisation of the extractable materials in
the coal.
Characterisation of the Coal Macromolecular Structure using Solvent Swelling

The study of coal macromolecular structure involved the use of the solvent swelling
technique.

The solvent swelling technique was originally designed for the study of

conventional polymers, and had previously not been well developed for the study of coals. It

85

was therefore considered necessary to develop and establish the technique for the study of coal
by way of studying the effects of the various experimental variables on the solvent swelling of
coal. It is thought that standardisation of the experimental conditions is necessary if
reproducible and comparable results are to be obtained. The specific conclusions drawn from
the study of the effects of the changes in the experimental variables are presented below:

1. The effects of temperature on the swelling ratio

Increase in temperature has a relatively small effect on the extent of swelling of coals in
pyridine. An increase in temperature slightly decreases extent of swelling of low rank coals,
but slightly increases extent of swelling of high rank coals in pyridine. However, these slight
variations in the swelling ratio do not affect the overall trend shown by swelling ratio with
rank.

2. The effect of temperature on the kinetics of solvent swelling

The rate of coal swelling in pyndine increases with increasing temperature. The solvent
swelling versus time graphs obey an experimentally determined first order rate law for swelling
>50% irrespective of the mechanism of solvent diffusion into the coal. The rates of swelling
decrease with increase in coal rank. Also the activation energy of the swelling process
increases with coal rank showing that the structural stability of coal is rank dependent.

3. The effect of solvent basicity on the solvent swelling of coal

The rate and extent of coal swelling increase with solvent basicity. Also the mechanism
of solvent sorption into coal is dependent on solvent basicity. It is clear that a wide range of
hydrogen bond strengths exist in coal and the extent to which the hydrogen bonds are broken
depends on the basicity of the solvent. The wider range of bond strengths disrupted the higher
86

the swelling of the coal in that solvent. Therefore, to obtain the maximum value of'swelling on
a coal only strongly basic solvents are recommended. Solvents of lower basicity will only
break the weaker hydrogen bonding, leaving the coal with an apparent higher cross-link
density than it would have if all the hydrogen bonding had been disrupted. This situation
results in a lower swelling in the solvent. It is therefore recommended that only solvents of
high basicity should be used in order that all the hydrogen bonds are broken and that the extent
of swelling is determined by the covalent cross linked density.

4. Differences in the solvent swelling behaviour of raw and extracted coals

Raw and extracted coals show different solvent swelling behaviour. The raw coal
shows higher swelling ratios in pyridine compared with the extracted coal. On the other hand
the rate of swelling is higher for the extracted coal. The reduced swelling and increased rate of
swelling for the extracted coal in pyridine indicate structural differences between raw and
extracted coals. The extent of swelling of the extracted coal in the substituted pyridines is
virtually independent of the basicity. This suggests that extraction with pyridine alters the
original hydrogen bonding in the coal, and it is probable that only a small fraction of the
original hydrogen bonds reform on removal of pyridine. It is also possible that extraction at
the boiling point of pyridine causes slight decomposition which is enough to give rise to
increase in cross-link density. A collapse of the coal structure on removal of pyridine could
also cause an increase in - interactions which can act as effective non-covalent crosslinks,
resulting in diminished swelling in solvents. The results suggest that the solvent extraction
process has modified the macromolecular structure of the coal. Therefore it is most appropriate
for the solvent swelling studies to be carried out on the raw coal despite the problems
associated with such measurements.

87

5. Effect of solvent steric properties on solvent swelling of coal

The steric properties of the solvent significantly affects the solvent swelling of coal.
The rate of swelling increases with decrease in molecular size of solvent. The extent of
swelling increases with molecular size of solvent reaching a maximum and then decreases with
further increase in the size of the molecule. The maximum swelling ratio obtained for the suite
of straight chain amines is very similar to that obtained for pyridine. This supports the
proposal that pyridine breaks virtually all the hydrogen bonds in coal. This shows that
although the coal macromolecule extends and re-orientates itself when the hydrogen bonding is
disrupted in order to accommodate the solvent molecule, there appears to be a limit to the ability
of the coal macromolecule to swell. This ability will be dependent on the molecular size of
solvent and also the density of crosslinks. It is therefore very important to consider solvent
steric properties when selecting solvents for solvent swelling studies on coal. It is apparent
that pyridine is a suitable solvent for the study of the solvent swelling of coal in that it appears
to swell the coal to its maximum extent.

6. The effect of particle size on the solvent swelling of raw and oxidised coal

For raw coals only a slight decrease in swelling ratio is observed with decrease in
particle size. Rate constants increase with decrease in particle size while the diffusional
exponent remains the same. For oxidised coal, swelling in pyridine is a two-stage process
with the second stage being faster than the first stage. Swelling ratio also shows a slight
decrease with particle size. It is clear that there is a significant difference between the structures
of raw and oxidised coals. Therefore coals for solvent swelling studies must be adequately
protected from oxidation.

Oxidation causes an increase in solvent swelling ratio corresponding to a decrease in


cross-linked density. This change in the macromolecular structure is associated with a decrease
in the aliphatic/aromatic ratio and an increase in the OH and C=0 functionalities.
88

7. The variation of the swelling ratio with coal rank

The low rank coals in the suite of coals studied have high swelling ratios in pyridine.
Although a maximum value occurs at a reflectance of about 0.77 there is a trend of decrease in
swelling ratio with increases in rank. This shows that covalent cross-link density increases
with rank. Since the dangerously swelling coals do not swell in pyridine, it may be concluded
that they have highly covalent crosslinked structures.

8. The effect of heating on the swelling ratios of coals in pyridine

The low rank coals undergo progressive crosslinking reactions during decomposition,
resulting in progressive increase in their crosslink density. On the other hand the dangerously
swelling coals decompose during pyrolysis in such a way that their crosslink densities decrease
initially, reaching maximum values before crosslinking reactions begin and eventually result in
re-solidification. Clearly, different mechanisms are involved in the decomposition of safe and
dangerously swelling coals.

9. Macromolecular structure of oxidised and dangerously swellinu coals

Raw and oxidised coals which do not exhibit dangerously swelling characteristics
during carbonization in the coke oven usually swell extensively in pyridine. On the other hand
while raw dangerously swelling coal does not swell in pyridine they do swell after oxidation.
Swelling in pyridine of oxidised dangerously swelling coal is caused bv a decrease in covalent
crosslinks. The infrared spectra suggest that this is due to reduction in aliphatic crosslinkages.
Therefore the structural difference between the macromolecular structure of safe and
dangerously swelling coals is associated with the amounts of covalent crosslinks and then
decomposition during carbonisation. Dangerously swelling coals have a high cross-link

89

density and this is associated with low volatiles, oxygen and hydrogen contents.

Determination and Characterisation of Pyridine-Extractable Components of


Coal

The concentration of the pyridine-soluble component of coal shows a maximum value


at a reflectance of 0.77 and above this reflectance value decreases with increase in coal rank
until it attains a very low, but almost constant values in the reflectance region of dangerously
swelling coals. The dangerously swelling coals Buchanan, Saraji, Oakdale, and Norwich have
very low amounts of pyridine extractables. Although the oxygen content of the extracts show a
trend of decrease with increase in coal rank in a similar manner to the raw coals the extracts of
the dangerously swelling coals contain more oxygen than the parent coals. On the other hand
extracts of the non-dangerously swelling coals contain less oxygen than the parent coals.
Extracts of the dangerously swelling coals are more aliphatic and have lower molar mass
distribution than those of the lower rank coals. There does not seem to be any clear differences
in the aromatic and aliphatic contents of extracts of heat treated coals. Extracts of the coals
heated to their softening and maximum contraction temperatures contain less oxygen than those
of the raw coals. Evidently, some of the oxygen has been lost in volatile gases. Like those of
the raw coals, extracts of the dangerously swelling coals that were heat treated to their
softening and maximum contraction temperatures have lower molar mass distributions than
those of the safe coals.

In general the study of coal structure using solvent swelling and solvent extraction
techniques reveals that dangerously swelling coals have a highly crosslinked macromolecular
structure. In addition dangerously swelling coals contain low amounts of extractable materials
which contain more oxygen than the corresponding coals, are more aliphatic and of low
molecular mass distribution compared with non-dangerously swelling coals.

90

In dangerously swelling coals the higher oxygen content of the extracts suggest that the
extracts are more reactive than the macromolecular phase. The reverse situation is true for the
lower rank safe coals where the macromolecular phase has a higher oxygen content. This
corresponds with the differences in the changes in crosslinking with heat treatment
temperature. In the case where the macromolecular phase has high oxygen content, and higher
than the corresponding mobile phase, crosslinking increases with heat treatment temperature.
In the case where the macromolecular structure has a low oxygen content, the phase must
decompose with the accompanying decrease in crosslink density before eventual crosslinking
when carbonisation is complete. The higher reactivity of the mobile phase is likely to result in
"pore blocking" which is likely to lead to low permeability.

Thermogravimetry of Coals and Extraction Residues

The temperatures of initial decomposition, maximum weight loss and rate of weight
loss all depend on coal rank. They also vary with heating rate. There is no relationship
between the thermogravimetric data and dangerously swelling properties of coal.

Dangerously swelling coals are more stable and the decomposition temperatures of the
raw and extracted coals are very similar. The low rank coals have lower decomposition
temperatures than the extracted coals. This corresponds to the larger amounts of extract found
in the low rank coals.

High pressure dilatometry

As a result of their ability to restrict the escape of gases dangerously swelling coals
encourage secondar)' decomposition which results in the increase in the volume of trapped
volatiles thereby increasing coking pressure.

91

Development of Porous Structure


Variation in Microporosity (C0 2 , 273 K surface area)

Surface areas (C0 2 , 273 K) of the semi-cokes show that those of the dangerously
swelling coals have low values. This confirms that microporous structure of the cokes derived
from the dangerously swelling coals is less extensive.

Gas Permeability of semicokes

The dangerously swelling coals exhibit low permeability to gases compared to the safe
coals. This property is probably the main cause of high coking pressures.

Gas Transport through Porosity of Semicokes

The gas capacities of the semi-cokes show that micropore volume increases as
temperature increases and reaches a maximum at 6()()C. though for low rank coals Rawdon.
Barnburgh and Hucknall it reaches a maximum at 800C. The gas capacities also decreases
with increase in rank of parent coal showing low values for the dangerously swelling coals.
The rate of gas transport also decreases with increase in coal rank for each carbonization
temperature, but also shows a maximum value at 600C for each coal. It is therefore clear that
the semi-cokes of the dangerously swelling coals are very low in microporosity and diffusion
of gases into the cokes is slow. This indicates that molecular sieving occurs in these carbons.
Therefore gases cannot easily escape by diffusion but will be trapped by the coke and this will
cause a high internal pressure and excessive swelling during the carbonization process.

92

OVERALL

1.

CONCLUSIONS

The various experimental factors which affect the extent of swelling of coal in solvents

have been established. Therefore solvent swelling measurements of coal can now be made
under standard conditions and comparisons of the cross-linked density can be obtained. It is
clear from the results of this study that temperature and particle size have little or no significant
effects on the equilibrium swelling ratios. They affect only the rates of the process. On the
other hand solvent properties such as basicity and steric properties affect both the extent and
rates of solvent swelling. It is also recommended that for solvent swelling studies in basic
solvents those solvents of high basicity e.g. pyridine, are preferred because they can break
almost all hydrogen bonds in coal. Solvent molecular size should not be too high otherwise
diffusion and accessibility into the coal structure may be impaired. Pyridine is considered to be
the most appropriate solvent. Also coal samples to be used in solvent swelling studies must be
protected from oxidation since the macromolecular structures of raw and oxidised coals are
essentially different.

2.

This study reveals some of the fundamental characteristics of dangerously swelling

coals. They have a macromolecular structure that contain high density of covalent crosslinks
and low amounts of hydrogen bonding interactions. They also contain very small amounts of
extractable material which are richer in oxygen and more aliphatic than the macromolecular
phase. The extracts also have a lower average molar mass than the non-dangerously swelling
coals.

However it must be recognised that the extractable materials are about only 2% of the
coal structure of the dangerously swelling coals. Therefore it is possible that it is the ven' low
amounts rather than the nature of these extractables that affect the dangerously swelling
characteristics of coals. Moreover, the macromolecular phase of the dangerously swelling
coals make up about 98% of the coal structure, therefore the nature of the macromolecular
93

structure as well as the way in which it decomposes during carbonisation may be a major
factor.

During carbonization the dangerously swelling coals produce a coke which shows
molecular sieving characteristics and therefore impairs escape of volatiles by diffusion. This
leads to high internal pressure and excessive swelling during the carbonization of coal in coke
ovens. Therefore a detailed characterisation of the macromolecular and mobile phases of the
coals provides an insight into the carbonization characteristics of the coal. Further work is
required to obtain a detailed understanding of the differences in swelling pressures obtained for
dangerously swelling coals.

94

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33.

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1958. 219.

34

Marsh H ., Carbon 1987. 25. 49.

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Larsen J.W.. Green T.K. and Kovac J.. J. Org. Chem. 1985. 50, 4729.

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41.

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42.

Deevi S.C. and Suuberg E.M., Fuel 1987, 66, 454.

43.

Gorbaty M.L., Fuel 1987, 57, 796.

44.

Evans D.G., Fuel 1973, 52, 155.

45.

Mahajan O.P. and Walker P.L.Jr., Fuel 1971, 50, 308.

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Nishioka M. and Larsen J.W., Energy and Fuels 1990, 4, 101.

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Ndaji F.E. and Thomas K.M., Proc. of the 7 t h Int. Conf. on Coal Science. 1993,
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51

Larsen J.W. and Muhammadi M.. Energy and Fuels 1990,4.107.

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57.

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58.

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98

Table 1

Coals used and their Characterisation Data

Maceral Analysis

Proximate Analysis
% Reflectance

Volatile Matter

Ash

(d.a.f.)
Rawdon

0.47

37.1

5.62

66

12

22

Barnburgh

0.65

38.5

4.9

78

10

12

Hucknall

0.77

38.7

3.8

78

13

Wearmouth

0.85

35.9

4.2

74

12

14

Pittsburgh No. 8

0.87

32.1

16.0

n.s

n.s

n.s

Wentz

0.92

31.8

5.9

81

15

Ruhrkohle

1.20

23.4

7.4

73

14

Line Creek

1.20

23.3

10.2

n.s

n.s

n.s

Woodside

1.26

28.3

8.1

n.s

n.s

n.s

PD

1.32

20.6

9.8

n.s

n.s

n.s

Buchanan

1.33

21.1

7.4

84

10

CC

1.39

21.4

9.3

n.s

n.s

n.s

Saraji

1.42

19.1

9.5

75

19

Oakgrove

1.42

21.7

9.X

n.s.

n.s.

n.s

Oakdale

1.46

19.7

10.0

65

35

1.48

18.6

10.0

n.s

n.s

n.s

Norwich

1.49

17.8

9.2

77

13

Pinnacle

1.55

17.2

5.2

n.s.

n.s.

n.s

Ladv Windsor

1.82

15.4

8.9

70

30

n.s. = not supplied.

99

Table 2

Properties of Solvents used in the Studv of the Effects of Solvent


Basicitv on Coal Solvent Swelling

Solvent

pkb

Molar Volume (cm3 mob1)

pyridine

8.6

80.9

2-chloropyridine

13.5

94.6

2-fluoropyridine

14.4

86.1

100

Table 3

Properties of Solvents used in the Studv of the Effects of Solvent


Steric Properties on the Solvent Swelling of Coal

Solvent

pkb

Molar Volume (cm3 mob1)

n-propylamine

3.3

82.2

n-butylamine

3.2

98.8

n-hexylamine

3.4

132.1

n-octylamine

3.4

165.3

n-decvlamine

3.6

199.8

101

Table 4
Equilibrium Swelling Ratios of Coals at 20 and 60C
Coal

Reflectance / %

Swelling Ratio in Pyridine


20C

60C

Rawdon

0.47

2.17

2.06

Barnburgh

0.65

2.26

2.16

Hucknall

0.77

2.13

2.03

Wearmouth

0.85

2.10

2.04

Wentz

0.92

1.80

1.77

Ruhrkohle

1.20

1.32

1.30

Line Creek

1.20

1.30

1.26

Buchanan

1.33

1.09

1.05

Saraji

1.42

1.00

1.04

Oakgrove

1.46

1.02

1.18

Oakdale

1.46

1.02

1.18

Norwich

1.49

1.03

1.20

Pinnacle

1.55

1.01

1.17

Lady Windsor

1.82

1.02

1.21

102

Table 5
Rate Constants. Ratios of Diffusional Coefficents*
Diffusional Exponents and Swelling Ratios
Coal

Temp.
(C)

Rawdon

Di/D2

(s- )

Swelling
Ratio

20

4.84x10-4

1.98

30

7.09x10-4

40

2.17

1.98

0.51
0.54

1.31x10-3

2.26

0.54

2.21

50

1.62x10-3

2.23

0.66

2.13

60

2.23x10-3

2.32

0.66

2.06

20

2.64x10-4

0.97

2.26

30
40

3.34x10-4

1.01

2.09

5.57x10-4

0.96

2.16

50
60

9.61x10-4

0.97

2.10

1.26x10-3

0.97

2.16

20

2.96x10-4

1.06

30
40

5.82x10-4

0.98

2.13
2.14

7.53x10-4

0.96

2.18

50

1.13x10-3

0.97

2.09

60

1.70x10-3

0.96

1.98

20

3.57x10-4

1.10

2.10

30

5.15x10-4

0.99

2.15

40

8.84x10-4

0.95

2.10

50

1.34x10-3

0.96

60

2.25x10-3

1.06

2.09
2.04

20

1.02x10-4

1.15

1.76

30

2.46x10-4

1.14

1.76

40

2.70x10-4

1.12

1.77

50

2.56x10-4

1.20

1.81

1.09x10-3
DT for 50% swelling, D 2 for initial swelling.

1.20

1.76

Barnburgh

Hucknall

Wearmouth

Wentz

60

103

2.22

Tnhle 6:
Swelling ratios of coals carbonised to varying temperatures

about their plast ic range

Coal
Rawdon

Coal
Barnburgh

Coal
Wearmouth

Temperature of
carbonisation (C)
25
340
370
400
430
460
490
520
555
575

Swelling
Ratio (QV)
2.17
2.38
2.62
2.55
2.25
2.03
1.92
1.42
1.14
1.02

Temperature of
carbonisation (C)
25
370
390
410
435
455
480
500
530
555

Swelling
Ratio (QV)
2.26
2.40
2.60
2.20
1.78
1.75
1.60
1.40
1.12
1.04

Temperature of
carbonisation (C)
25
340
378
400
425
450
465
480
520
555

Swelling
Ratio (QV)
2.10
15
2 27
2 26
1 88
1 41
1 53
1 88
1 13
1 00

104

Table 6 continued...

Coal
Line Creek

Coal
Woodside

Coal
CC
,

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
370
390
415
440
465
490
515
540
560

1.30
1 35
1 42
1 71
1 69
1 54
1 50
1 21
1 07
1 02

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
375
405
435
460
485
515
535

1.04
1.86
1.51
1.5X
1.46
1.40
1.10
1.02

Temperature of
carbonisation (CC)

Swelling
Ratio (QV)

25
330
350
375
395
415
440
460
485
510
530
555

1.02
1.06
1.36
1.63
1.48
1.14
1.44
1.45
1.47
1.41
1.12
1.02

105

Table 6 continued...
Coal
PD

Coal
Buchanan

Coal
Saraji

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
350
370
415
435
455
475
495
515
545

1.04
1.08
1.14
1.83
1.47
1.50
1.41
1.40
1.19
1.09

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
415
430
450
470
490
520

1.09
1.29
1.66
1.84
1.84
1.53
1.43

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
385
400
420
440
460
480
500
530
555

1.00
1.04
1.10
1.33
1.63
1.62
1.34
1.37
1.14
1.02

106

Table 6 continued...
Coal
Oakgrove

Coal
K

Coal
Pinnacle

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
400
420
445
470
490
515
540
565

1.01
1.05
1.13
1.34
1.20
1.32
1.30
1.32
1.03

Temperature of
carbonisation (C)

Swelling
Ratio (QV)

25
440
460
480
500
520
540
560

1.02
1.16
1.30
1.23
1.16
1.10
1.04
1.02

Temperatureof
carbonisation rC)

Swelling
Ratio (QV)

25
450
470
490
510
530
555
585

1.01
1.15
1.36
1.22
1.23
1.22
1.17
1.01

107

Table 6 continued...
Coal
Lady Windsor

Temperature of
carbonisation (C)
25
380
430
470
500
530
560
580
610

108

Swellir
Ratio (
1.02
1.03
1.06
1.08
1.12
1.07
1.05
1.03
1.02

Table.7
Surface Areas. Pyridine Extract Yields. Swelling Ratios. Activation
Energies and Pre-exponential Factors for Swelling

Coal

Surface
(m 2 g- 1 )

Extract
(wt%)

Qv range
20-60C

Ea
A
1
(kJ mol- ) (s" 1 )

Rawdon

129

17.3

2.06-2.22

31.6

2.3xl() 2

Barnburgh

105

19.0

2.09-2.26

33.9

2.48xl0 2

Hucknall

111

25.4

1.98-2.18

33.8

3.16xl() 2

Wearmouth

83

2.04-2.15

37.5

1.50x10?

Wentz

68

1.76-1.81

44.9

9.40x103

17.8

109

Table 8
Rate Constants and Swelling Ratios for Raw and Extracted Wearmouth Coal
in Pyridine. 2-chloropvridine and 2-fluoropvridine. Also Diffusional
Exponents for the Raw Coal in the Three Solvents

Temp / C

1Raw Coal
n

Kis- )

Extracted Coal
Qv

Kis1)

2.10

4.59xl()- 3

1.92

0.99

2.15

1.89

0.95

2.10

4.86xl05.5xl()- 3

6.12x107.5x10-3

1.93

Qv

'yridine
20
30
40

3.57xl0-4

1.10

5.15x10-
8.841(

50

1.34x10-

0.96

60

2.25x10-'

1.06

2.09
2.04

1.90
1.88
1.85

2-chloropyridine
20
30
40

7.67x10-

0.86

1.64

3.26x10-3
3.56x10-3

1.25xl()-

0.86

1.62

4.01x10-3

1.86

50

1.74x1 (H

0.88

5.09x10-3

1.79

60

2.45x1 (H

0.91

1.61
1.69

5.23x10-3

1.81

70

3.43x1 (H

0.93

1.70

2.59x10-3

1.82

1.86

2-fluoropyridine
20

30

3.36xl0-5

0.63

1.27

3.27x10-3

1.70

40

0.66

1.34

3.63x10-3

1.68

1.70
1.65

5.16xl0-

50

6.05xl(r

0.70

1.41

4.34xl0-

60

8.17xl()-5

0.76

1.41

4.90x10-3

70

0.71

1.38

1.07xl0-

110

Table 9; Basicities, molar volumes, and amounts of solvents absorbed at 3QC. also apparent
activation energies and pre-exponential factors for the swelling of the raw and extracted
Wearmouth coal in pyridine. 2-chloropvridine. and 2-nuoropvriiline

Solvent Properties
pKb

Molar volume
1

Raw Wearmouth Coal


Amount absorbed

Ea

Extracted Wearmouth Coal


QV

Amount absorbed

Ea

(cm'mol )

(mmol g i)

/kJ mol '

(s >)

al 3()'C

mmol g '

/kJ m o l

A
1

QV

(s )

at 3 0 X

Pyridine

8.6

80.9

10.93

37.4

1494

2.15

8.46

9.7

0.97

1.89

2-chloropyridine

13.5

94.6

5.20

31.7

21

1.64

7.00

10.5

1.04

1.86

2-fluoropyridine

14.4

86.

2.41

24.

0.14

1.27

6.25

10.3

0.97

1.70

Table 10
Rate Constants. Diffusional Exponents and the Swelling Ratios for Swelling
of Wearmouth Coal in Butvlamine. Hexvlamine and Qctvlamine

Temp/. (' Q

Qv

(S" 1 )

-propylamine
30

1.89x10-3

0.67

1.77

20

0.69

1.92

30

7.34x10-4
1.14x10-3

0.69

1.84

40

1.68x10-3

0.61

1.89

50

2.5x10-3

0.62

1.77

60

3.24x10-3

0.52

1.77

30

1.98X1)-4
3.52x10-4

1.1
1.1

2.18
2.16

40

6.10x10-4

50

1.1
1.1

2.19

1.0

1.90

n-butylamine

n-hexylamine
20

60

8.04xl01.10x10-3

2.08

30

2.58x10 o

1.1

2.08

40

4.5 lx IO

0.97

2.10

50

6.01 10-s

1.10

2.17

1.1

1.97

n-octylamine

60

1.08x10

70

1.29.x 1(H

1.1

1.93

5.22xl0" 6

1.10

1.82

n-decylamine
30

112

Table
pKo and Molar Volumes of Amines. Swelling Ratios of Coal in each Amine and Molar
Quantity of Amine Absorbed at 30C. and the Activation Energy of the Swelling Process

Solvent

pKb

Molar Vol ume


(cm3inol- 1)

Swelling Riitio
Wearmoi ah coal

Molar c]iiantity of

Activation Energy

solvent absorbed

for the swelling process

at 30C

per gram of coal

Ea(kJmol-l)

(mmol g- 1)
n-propylamine

3.3

82.2

1.77

7.2

nd

n-butylamine

3.2

98.8

1.84

6.5

30.3

n-hexylamine

3.4

132.1

2.16

6.7

34.5

n-octylamine

3.6

165.3

2.08

5.0

35.2

n-decylamine

3.6

199.8

1.82

3.2

nd

n.d - not determined

Table 12
Rate Constants. Diffusional Exponents and Swelling Ratios in Pyridine
at 2()C for Various Particle Sizes of Raw Rawdon and Wearmouth Coals

Rawdon
Particle Size

K(s-i)

()

Weannouth
Swelling Ratio

K(s-l)

Swelling ratio

QV

Qv

355-600

4.83xl()"4

0.5

2.17

3.57xl()-4

1.10

250-355

8.98x10-

0.5

2.14

6.19xl0-4

.10

212-250

1.63xl()-3

0.51

2.08

7.4xl()-4

.02

150-212

1.72xl()-3

0.45

2.08

8.77xl0"4

1.1

2.10
2.02
2.06
2.02

Table 13
Oxygen Contents and Swelling Ratios in Pyridine at 20C for Raw
and Oxidised Rawdon. Wearmouth. Buchanan and Pinnacle Coals

Rawdon

Wearmouth

Buchanan

Pinnacle

Raw

Oxidised

Raw

Oxidised

Blank

Raw

Oxidised

Raw

Oxidised

13.9

21.28

8.23

16.71

9.08

3.72

9.20

4.25

5.58

2.17

2.37

2.10

2.33

2.12

1.09

1.87

1.01

1.81

U1

Oxygen content
wt% d.a.f.
Swelling Ratio in
Pyridine at 20C
Increase in
Swelling Ratio

0.20

0.23

0.78

0.80

Table 14
Rate Constants. Diffusional Exponents and Swelling Ratios for Swelling
of Oxidised Wearmouth Coal and its Blank in Pyridine

Rate Constant (ks-1)


1st Stase

Qv

2.33
5.92

0.96
0.76

2.33
2.34

2nd S tace

Oxidised Wearmouth (355 - 600 )


Oxidised at 2(X)C for 24 hours in an air oven
20

7.57 IO"6

30

40
50
60

1.65 I03.80 ) 5

1.28

0.77

2.26

0.65

2.38

0.56

2.32

6.27 IO1.60 )-

Heated Wearmouth (blank) (355 - 600 )


Heat-treated at 200C for 24 hours in vacuum
Raw Wearmouth coal
QV
20

1.32 HH

0.91

2.12

2.10

30

2.41 10-*

0.92

2.24

2.15

40

0.97

2.19

2.10

1.1

2.13

2.09

1.2

2.15

2.06

50
60

3.42 IO"

7.46 IO"
1.12 IO"

116

Table 15:Showtng the areas of the various absorption bands in the FTIR
spectra of raw and oxidised Wearmouth
and Buchanan coals
Wearmouth
Vibrational frequency

Buchanan

Raw

Oxidised

Raw

Oxidised

8.14

10.66

7.47

9.82

0.20

0.29

1.74

1.38

2830 cm-1

0.20

0.06

0.25

0.12

2853 cm" 1 v(CH 2)sym

0.22

0.07

1.10

0.25

2870 cm"1 v(CH 3)sym

1.38

0.50

0.64

0.13

2890 cm"1 v(CH )aliph (tertian')

Hydrogen bonded OH groups


3100-3600 cm" 1
Aromatic C- stretching
3050 cm-1
Aliphatic C- stretching

0.39

0.15

0.45

0.23

1.27

0.39

1.37

0.50

2960 cm" v(CH 3)asym

0.91

0.35

0.27

0.20

Total

4.37

4.08

1.43

Aliphatic / Aromatic (2923/3050)

6.35

1.52
1.34

0.78

0.36

2923 cm" v(CH 2)asym

Oxygen functional groups


1580 cm"1 carboxylate

0.17

1.59

0.32

0.47

0.32

0.81

0.22

0.40

0.06

0.50

0.01

0.07

0.11

1685 cm" conjugated ketones

0.12

1700 cm"1 carboxyl

0.15

1620 cm' hydroxy ketones


1635 c n r hydroxy ketones
1653 cm" quiones

0.01

0.48
0.04

0.02

0.03

1730 cm" esters

0.02

0.33

0.02

Total

0.65

3.88

0.55

1.19

1720 cm" esters or carboxyl

117

Tahle 16: Showing rate constants, oxygen contents, increase in oxviien contents and swelling ratios
lor various particle sizes of oxidised Rawdon and Wearmoiilh coals

Particle
Size Range
oo

Oxidised Rawdon
Oxygen
% Increase in Swelling ralio

ks"
1st stage

2nd stage

Content (wt%) oxygen content

355-60

7.41x10-6

2.94x10-5

21.28

250-355

8.01x10-6

1.72xl0"5

212-250

1.40x10-5

150-250

1.46x10-5

k(s"')

Wearmouth Coal
Oxygen

% Increase in
oxygen content

Swelling

Ratio

1st stage

2nd stage

content (wt%)

Ratio

53

2.37

7.56x10-6

2.33x10-5

16.71

103

2.33

23.95

72

2.27

1.61x10-5 6.01x10-5

17.74

115

2.30

1.66x10-5

24.04

73

2.25

2.27x10-5 6.18xl()-5

18.48

124

2.27

1.55x10-5

24.10

73

2.23

3.24x10-5 9.00x10-5

18.81

128

2.25

()

Table 17
Extents of Swelling at which the Second Stage begins and also
depth of Penetration of Solvent at the same point

Ox. Rawdon

Ox. Wearmouth

Particle
size range
/

change over
point (%)

Depth of
penetration

change over
point (%)

Depth of
penetration

355-600

69

77

55

56

250-355

86

72

81

64

212-250

89

59

90

62

150-212

89

45

93

53

119

Table 18
Percentage Pyridine Extraction Yields of Coals

Coal

Yield (%)
Raw coal

Rawdon

17.3

Barnburgh

19.0

Hucknall

25.4

Pitts 8

Yield (%)
Softening temp.

Yield (%)
Max. contraction Temp

46.1

33.2

23.5

44.4

Wearmouth

23.3

23.7

45.1

Wentz

17.8

22.8

25.4

Ruhrkohle

8.5

16.9

Line Creek

6.6

Buchanan

2.1

19.9

19.0

Saraji

2.0

9.2

9.6

Oakgrove

1.5

7.2

22.3

Oakdale

2.0

Norwich

1.0

Pinnacle

1.4

Ladv Windsor

2.2

16.9
5.4

120

5.1

Table 19: Table showing the areas of the aromatic and aliphatic stretching frequencies
observed in the spectra of pyridine extracts of coals.
FHR band intensities / arbitrary units
% Refi.
Coal

Aromatic
3050 cm" I

Aliphatic
2830 cm"

V(C-H)arom

NJ

2853 cm-1

2870 c n r I

2890 c n r I

2923 cm" 1

2960 cm" 1

V(.CIb) S ym

V(CH3)sym

v(CH)

V(CH2)asyni

v(CH3) a s y m

Rawdon
Barnburgh

0.47
0.65

0.96

1.62(282'))

2.45(2852)

1.24(2870)

3.54(2895)

4.94(2923)

4.92(2963)

1.09

1.34(2824)

3.47(2855)

0.09(2867)

4.50(2893)

5.68(2924)

4.78(2955)

Hucknall

0.77

0.96

2.00(282'))

3.20(2856)

0.66(2873)

2.25(2829)

5.52(2924)

3.40(2958)

Weannouth

0.85

0.85

1.98(2830)

3.37(2854)

0.86(2870)

2.24(2893)

6.17(2922)

3.64(2954)

Wentz

0.92

0.85

1.38(2828)

2.07(2851)

1.43(2869)

2.63(2895)

5.57(2924)

3.42(2957)

Ruhrkholc

1.20

1.35

2.50(2831)

3.80(2853)

0.80(2868)

4.78(2894)

4.96(2923)

2.21(2954)

Line Creek

1.20

1.73

1.94(2832)

3.02(2856)

0.15(2866)

4.32(2893)

4.80(2922)

4.41(2953)

Buchanan

1.33

0.68

2.85(2832)

4.38(2853)

1.57(2869)

5.14(2892)

13.86(2924)

5.57(2958)

Saraji

1.42

0.60

2.81(2830)

4.53(2852)

1.51(2870)

5.42(2893)

14.43(2924)

5.92(2960)

Oakgrove

1.42

0.63

2.84(2836)

5.47(2854)

1.40(2870)

6.07(2893)

16.45(2924)

5.04(2957)

Oakdale

1.46

1.34

2.90(2832)

3.34(2853)

0.15(2868)

6.03(2893)

8.95(2923)

3.93(2953)

Norwich

1.49

1.37

2.58(2835)

3.68(2853)

1.26(2870)

3.72(2892)

9.90(2923)

4.32(2954)

Lady Windsor

1.82

0.95

2.96(2834)

3.20(2852)

1.70(2873)

3.12(2895)

9.93(2923)

3.27(2957)

Iahte 2Q; PvrcenlUK' contents of the various stretching modes of CIH and Cll groups
in the total aliphatic stretching modes in the FTIR spectra of pyridine extract of coals.

Coal

% Refi.

Total
aliphatic

2830 cm-1
unknown

2853 cm"1
viClbisym

2870 cm"1
v(CH3)sym

2890 cm"1
v(CII)

2923 cm"1
v(CH?)asym

2960 cm"1
V(CH3)asym

Rawdon

0.47

18.71

8.66

12.34

6.62

18.92

26.40

26.30

Barnburgh

0.65

19.86

6.75

17.47

0.00

22.66

33.35

24.07

Hucknall

0.77

17.03

11.74

18.79

3.88

13.21

32.41

19.96

Wearmouth

0.85

18.26

10.84

18.45

4.71

12.27

33.79

19.93

Wentz

0.92

16.50

8.36

12.55

8.67

15.94

33.76

20.73

Ruhrkohle

1.20

18.84

13.27

20.17

4.25

25.37

26.35

11.73

Line Creek

1.20

18.64

10.40

16.20

0.01

23.17

25.75

23.66

Buchanan

1.33

33.37

8.54

13.12

4.70

15.40

41.53

16.69

Saraji

1.42

34.62

8.12

13.08

4.36

15.65

41.68

17.10

Oakgrove

1.42

37.27

7.62

14.68

3.76

16.29

44.14

13.52

Oakdale

1.46

25.30

11.46

13.20

0.01

23.83

35.38

15.49

Norwich

1.49

25.46

10.13

14.45

4.95

14.61

38.88

16.97

Lady Windsor

1.82

24.18

12.24

13.23

7.03

12.90

41.07

13.52

Table 21: Table showing the areas of the aromatic out of plane deformation bands in the
FTIR spectra of the pyridine extracts of coal.
Infra red absorption peaks

rvj

Coal

% Rell

750 cnr 1

770cnr'

801cm"1

816 cm"1

860 cnr >

874 cm"1

888 cm"1

Total

Rawdon

0.45

0.70

0.94

1.12

0.19

0.23

0.85

4.03

Barnburgh

0.65

0.56

1.41

1.26

0.89

1.89

0.87

6.88

Hucknall

0.77

1.38

0.43

4.45

1.36

0.55

8.17

Wearmouth

0.85

0.59

1.48

0.7')

Ill

1.07

1.09

6.16

Wentz

0.92

0.72

1.04

0.17

0.79

0.71

0.77

4.20

Ruhrkhole

1.20

1.54

1.97

--

1.24

1.33

0.95

0.39

7.42

Line Creek

1.20

1.84

0.43

2.05

1.08

0.90

2.09

0.31

8.70

Buchanan

1.33

0.51

0.31

0.87

--

0.38

0.10

2.17

Saraji

1.42

0.72

0.64

0.72

--

0.27

0.03

2.38

Oakgrove

1.42

0.75

0.22

0.20

0.57

0.19

0.27

0.07

2.27

Oakdale

1.46

1.77

0.33

1.19

0.93

0.45

1.00

0.53

6.20

Norwich

1.49

1.71

0.69

1.04

0.75

0.32

0.84

0.40

5.75

Lady Windsor 1.82

1.44

0.37

2.91

0.35

0.23

0.23

5.53

Table 22: Table showing the areas of the bands for the oxygen functional groups in the FTIR
soectra of pyridine extract of coals after standardisation using the areas
of the 1600 cm-1 band as an internal standard.

4^

Coal

% Reflectane

1655 c n-1

1700 cm-1

Rawdon
Barnburgh

0.47
0.65

0.11(1 54)

0.26(1703)

0.12(1 54)

0.18(17.02)

Hucknall

0.77

0.17(1 50)

Wearmouth

0.85

0.22(1 53)

Wentz

0.92

Ruhrkhole

1720cnr'
-

Extract /%

01%

17.3
19.0

12.2
10.5

0.08(1722)

25.4

9.6

0.20(1698)

23.3

7.5

0.25(1 55)

0.40(1701)

17.8

7.3

1.20

0.35(1 56)

0.18(1698)

8.5

6.1

Line Creek

1.20

0.40(1 58)

0.07(1703)

0.01(1725)

6.6

5.1

Buchanan

1.33

0.63(1 54)

0.81(1700)

0.52(1722)

2.1

5.0

Saraji

1.42

0.74(1 52)

0.15(1697)

1.37(1721)

2.0

4.7

Oakgrove

1.42

0.48(1 54)

0.42(1703)

1.5

5.4

Oakdale

1.46

0.63(1 59)

0.09(1705)

0.08(1730)

2.0

5.4

Norwich

1.59

0.30(1 52)

0.24(1703)

0.06(1721)

1.0

6.7

Lady Windsor

1.82

0.48(1 56)

0.38(1703)

0.38(1721)

2.2

5.7

Table 23: Areas of Aromatic and Aliphatic Stretching frequencies in the FTIR spectra
of extracts of coals heated to their temperature of maximum contraction (arbitrary units)

3()50(cm1)

2830(cm)

2855(')

2875(cm ')

290()(cnrl)

2928(cm')

(C-ll)

2928(cm 1 )

2960(cm )

(aliph/arom)

296()(cm-')
(aliph/arom)

aromatic
Coal
tn

Rawdon
Wearmouth
Pittsburgh 8
Wentz
Woodside
Buchanan
CC
Saraji
Oakgrove
K
Pinnacle

0.54
0.72
0.77
0.76
1.16
0.70
1.13
0.79
0.60
1.17
1.05

2.68
1.50
3.35
1.50
1.21
0.58
1.23
1.69
0.77
2.25
2.25

4.07
0.75
0.89
0.75
I.I 1
1.25
0.69
0.96
0.32
0.53
0.79

0.18
2.4 3
1.12
2.43
1.79
0.30
0.94
3.62
2.35
1.41
4.17

5.52
1.44
2.36
1.44
1.57
0.81
-

1.21
0.44
-

0.64

7.77
2.30

14.39
3.19

--

2.30
2.01
1.44
1.99
5.09
1.8.3
2.90
4.49

3.02
1.73
2.06
1.76
6.44
3.05
2.48
4.43

4.55
2.20
1.99
2.20
2.38
1.04
1.51
2.54
1.17
1.88
2.58

8.43
3.06
2.58
2.89
2.05
1.49
1.34
3.22
1.95
1.60
2.46

Table 23 continued: Areas of the out of plane deformation deformation hands in the FTIR snectra
of extracts of coals heated to their temperature of maximum contraction (arbitrary units)

690(cm1)

72()(cm')

74()(cm ')

765(cm ')

780(cnri)

8(X)(cm>)

830(cm)

86()(cm>)

885(cm->)

0.28

0.20

--

0.72
--

--

0.25
0.62

--

1.43
1.75
0.76

0.12
0.30
1.56
0.42
0.41
0.30
1.71
0.78
1.30
1.18
0.19

1.16
1.26

0.72
0.42
1.68
0.17
0.01

1.47
1.50

0.10

0.56
1.28
0.55
0.5 1
1.02
1.02

Coal
Rawdon
an Weannouth
Pittsburgh 8
Wentz
Woodside
Buchanan
CC
Saraji
Oakgrove
K
Pinnacle

1.08

0.71

--

--

--

1.34
0.50

0.42

2.05
0.10
1.14
2.00

0.50

2.30

0.54

--

3.44
0.76
1.02
2.81

--

1.28
1.89
0.82
--

0.78
0.54
0.12
2.72

--

1.25
1.96
1.05
--

1.20
---

1.53

Table 24
Oxvgen Contents of Coal. Extracts, and Residues (wt% daH

Oxygen Content
of Coal

Oxygen Content
of Extract

Oxygen'
of Resid

Rawdon

13.9

12.2

13.7

Barnburgh

10.7

10.5

12.2

Hucknall

9.8

9.6

9.8

Wearmouth

8.2

7.5

8.9

Wentz

6.4

7.3

7.8

Ruhrkohle

6.3

6.1

6.8

Line Creek

5.1

5.1

5.6

Buchanan

3.7

5.0

3.7

Saraji

4.2

4.7

3.5

Oakgrove

4.4

5.4

4.1

Oakdale

5.1

5.4

4.0

Norwich

4.0

6.7

3.8

Pinnacle

4.2

4.5

3.5

Ladv Windsor

3.6

5.7

2.7

127

Table 25: Values of Oxvgen content of the coal residues and the
coal extracts for samples carbonised to T l and T2.

Coal

%Oxygen of coal
residue to Tl

%Oxygen of coal
extract to Tl

%Oxygen of coal
residue to T2

%Oxygen of coal
extract to T2

Rawdon

14.59

6.64

12.35

8.85

Pittsburgh 8

11.96

8.86

8.85

7.54

Wearmouth

8.70

8.15

8.46

6.30

Wentz

7.76

5.33

7.47

6.64

Ruhrkohl

5.73

Woodside

5.43

3.94

5.31

5.20

Buchanan

4.68

4.67

6.10

7.44

5.54

C. C.
Saraji

4.31

4.29

4.90

4.73

Oaksrrove

5.10

5.71

4.90

4.03

K.

4.99

Pinnacle

5.00

5.70

4.63

4.20

3.37

Ladv Windsor

3.94

128

Table. 26: Values of Retention volume and normalised Area under the curve of coal extracts of raw coal,
coal carbonised to T; and coal carbonised to T2 with tetrahydrofuran as the mobile phase.

Retention volume (cm3)


of raw coal extracts

Nonnalised area
of raw coal extracts

Retention volume (cm3)


of | extracts

Normalised area
ol"T| extracts
(mm2/mg)

Retention volume (cm3)


of '2 extracts

17.

122

15.1

500

15.2

71 I

14.2

929

15.4

613

14.6

671

17.7

219

15.0

980

15.8

607

15.3
16.5

314
493

15.6
16.2
15.9
15.9
15.9

578

1642

16.2

1549

16.4

1220

18.4

115

OlllTr/nig)

Rawdon
Barnburgh
Hucknall
Pittsburgh 8
-* Weannouth
10
Wentz
Ruhrkohl
Line Creek
Woodside
Buchanan
CC.
Saraji
Oakgrove
Oakdale
K.
Norwich
Pinnacle
Lady Windsor

15.9
15.5
16.1

765
515
456

--

15.3
15.5
15.0
16.1

1009
945
775
1168

--

16.4
15.3
18.4
16.9
16.3
15.6
16.5
16.4
16.9

791
46
662
504

16.5
17.1

1286
1588

Normalised area
of T2 extracts
(mtmVmg)

1119
1684
1782

619
241
172
442
1166

17.0

222

Table. 27: Values of Retention volume and normalised Area under the curve of coal extracts of raw coalcoal carbonised to T and coal carbonised to T 2 with chloroform as the mobile phase.

Retention volume (cm.3)


of raw coal extracts

Rawdon
Barnburgh
Hucknall
Pittsburgh 8
_, Wearmouth
0
Wentz
Ruhrkohl
Line Creek
Woodside
Buchanan
CC.
Saraji
Oakgrove
Oakdale
K.
Norwich
Pinnacle
Lady Windsor

16.46
15.75
16.13

Normalised area
of raw coal extracts
(mm2/mg)

Retention volume (cm.3)


of | extracts

20
20
4X

16.27
16.58
16.35
16.77

25
68
102

Retention volume (cm3)


of T 2 extracts

5.90

30

15.54

90

16.01

48
25
50
74

15.66
15.69

53
56
9S

42

16.50

204

65

16.11

124

16.35

112

16.24
15.76
16.06

Normalised area
of T2 extracts
(mm 2 /mg)

15.86

96

16.46
16.95
16.73
16.91
16.43
16.80

Normalised area
of | extracts
(mm2/mg)

38

16.17
16.28

26
155

16.24

165

16.15

206

52

16.58

239

16.21

134

36

16.47

198

68

16.24

76
27

172

16.8
16.7

39

5.61

45

17.59

Table 28
Thermogravimetric Data on oals

Heating Rate
5C/mTn

Rawdon

Wearmouth

Buchanan

304
424
354
120
0.32

319
429
366
110
0.41

371
466
432
95
0.14

389
516
416
127
0.12

398
532
430
134
0.08

298
433
357
135
0.76

321
437
382
116
0.72

372
485
425
113
0.42

349
493
425
144
0.31

366
544
430
177
0.23

Heating Rate 15C


/min
304

T-,
438
368
;
134
T4
R(mg/min)
1.04

331
465
402
134
0.99

367
518
445
151
0.47

367
526
442
158
0.43

387
559
459
172
.27

308
451
379
143
1.51

329
481
405
152
1.37

372
538
447
166
0.70

363
535
447
172
0.54

388
554
465
166
0.37

Heating Rate 25C


/min
313

To
439
381
T3"
126
T4
T(mg/min)
1.85

337
474
418
137
1.78

369
577
451
208
0.97

361
554
461
193
0.77

391
594
469
203
0.50

Ti

T2
T3
T4
R(mg/min)

Oakdale

Lady Windsor

Heating Rate 10C


/min

,
To
3

T4
R(mg/min)

Heating Rate 20X


/min

To

R(mg/min)

Ti
To

T~,
T4
R

=
=
=

Temperature of commencement of volatile release


Temperature of end of volatile release
Temperature at the maximum rate of volatile release.
Temperature range of volatile loss.
Rate of volatile loss (mg/min).
131

Table 29
Comparison of Temperature of initial Weight Loss and Rate
of Weight Loss for Raw and Extracted Coals at at
Heating Rate of 5C min 1

Raw Coal

Extracted Coal

Temp, of initial

Soft.

weight loss
CO

Rate of Weight

Temp, of initial

Rate of weight

Temp. loss mg/min

weight loss

loss mg/min

CC)

CC)

Rawdon

304

339

0.32

334

0.70

Barnburgh

308

n.a*

0.58

343

0.62

Hucknall

312

n.a*

0.52

355

0.60

Wearmouth

319

345

0.52

355

0.60

Wentz

322

351

0.41

363

0.62

Ruhrkohle

367

375

0.35

368

0.50

Line Creek

365

n.a*

0.40

371

0.52

Buchanan

371

398

0.14

390

0.42

Saraji

390

410

0.22

383

0.36

Oakgrove

387

412

0.18

390

0.36

Oakdale

389

0.12

390

0.30

Norwich

390

426

0.18

389

0.29

Pinnacle

390

410

0.18

389

0.29

Lady Windsor

398

438

0.08

405

0.24

*n.a = not available

132

Table 30: Dilatometrie data of coals used in this studv

Rn

Wh

Wz

Rk

Bn

Si

Lw

Tl

339

345

351

375

398

410

438

T2

419

420

440

448

457

T3

525

450

458

470

490

489

%c

19

27

24

20

23

15

%d

46

88

45

71

40

14*

^Contraction measured at 500C

Table 31: Permeability data of coals used in this studv

Rn

Wh

Wz

Rk

Bn

Si

Lw

Ta

360

340

360

385

402

420

445

Tb

412

414

440

449

460

Tc

450

440

440

446

459

477

490

Td

480

485

545

530

530

490

133

Table 32: Thermoplastic data of coals carbonised


under varying gas pressure
Rawdon coal
Pressure (bar)

%C

0
15
25
40
60

24
26
34
33
32

%D

T1(Q

T2(C)

T3(C)

357

--

530

355

530

337
340
325

--

450
475
425

Wearmouth coal
Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C

0
5
10
15
20
30
40
50
60

13
8
13
13
16
16
19
22
25

51
87
89
101
87
79
76
63
55

375
375
365
362
362
350
330
325
320

424
419
415
417
416
420
425
418
420

537
537
525
550
540
550
550
550
550

Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C)

0
5
10
15
20
30
40
50
60

10
21
22
27
25
26
24
22
18

176
167
163
148
143
128
109
97
79

395
365
375
355
345
322
320
320
340

420
410
404
403
410
390
404
400
400

492
490
485
463
471
455
495
468
475

Pittsburgh 8 coal

134

Table 32: continued...


Wentz coal
Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C)

0
20
40
60

25
16
25
25

163
125
91

350
337
329
321

418
416
410
408

475
475
487
475

Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(CC)

0
10
25
45
60

13
12
13
14
14

1
2
5
8

385
389
375
360
358

470
462
462
460

500
500
500
505
500

Pressure (bar)

%C

T1(C)

T2(C)

T3(C)

0
10
20
30
45
60

25
26
28
25
25
24

206
157
126
109
55
48

352
349
342
325
325
310

418
417
411
403
402
399

476
482
490
475
502
500

Pressure (bar)

%C

<7cD

T1(C)

T2(C)

T3(C)

0
20
40
60

16
15
18
16

43
45
34
30

388
375
370
350

447
435
447
430

483
500
512
500

Line Creek coal

Woodside coal

PD coal

135

Table 32: continued...


Buchanan coal
Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C)

0
10
15
20
25
30
40
50
60

24
20
20
16
16
24
25
25
24

23
72
85
81
86
73
76
70
69

405
400
393
397
387
383
387
377
375

469
439
435
450
434
439
436
434
435

506
492
502
520
520
502
513
508
512

Pressure (bar)

%C

9rD

T1(C)

T2(C)

T3(C)

0
10
20
30
40
50
60

23
25
25
25
28
26
29

53
61
51
44
40
36
28

375
370
368
350
350
337
337

446
435
435
430
430
425
435

495
485
488
475
483
491
500

Pressure (bar)

%C

T1(C)

T2(C)

T3(C)

0
5
10
15
20
30
40
50
60

15
18
13
17
20
14
18
23
24

57
74
83
85
76
74
59
62
54

400
400
387
393
384
377
375
372
355

449
439
434
437
437
433
430
425
428

502
500
500
503
503
498
500
510
525

C C coal

Saraji coal

136

Table 32: continued...


Oakgrove coal
Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C)

0
10
20
30
40
50
60

20
19
24
21
27
21
24

112
115

75

399
383
383
383
375
373
365

435
434
430
425
420
422
420

495
510
505
505
510
512
522

Pressure (bar)

%C

%D

T1(C)

T2(C)

0
10
20
30
40
60

29
16
29
15
22
29

13
68
71
74
62
58

407
407
400
405
400
380

477
459
465
462
463
457

512
513
513
518
513
513

Pressure (bar)

%C

%D

T1(C)

T2(C)

T3(C)

0
5
10
15
20
30
40
50
60
75

20
17
25
19
25
17
22
21
23
25

10
50
48
80
58
65
64
68
67
57

430
430
425
410
403
406
403
400
390
385

487
485
462
455
458
456
453
448
447
440

525
524
525
525
524
525
525
525
525
525

105
95
86
85

K coal
T3(C

Pinnacle coal

137

Table 32: continued...


Lady Windsor coal
Pressure (bar)

%C

0
20
40
60

19
25
16
26

%D

T1(C)
442
420
410
410

138

T2(C)

T3(C)

Table 33
Surface Areas (C0 2 . 273 K) of Coals, and of their Semi-cokes
produced at 450. 500. 600 and 800C

Surface area/m2^-1

Coal
Raw coal

450C

500C

Rawdon

129

103

102

214

265

Barnburgh

110

120

140

212

247

Hucknall

111

87

141

182

239

Wearmouth

113

93

117

166

146

Wentz

68

80

81

160

132

Ruhrkohle

51

72

85

163

132

Line Creek

69

75

90

165

130

Buchanan

46

61

77

140

55

Saraji

42

58

79

130

57

Oakgrove

53

50

62

122

107

Oakdale

57

32

114

142

138

Norwich

66

64

67

138

110

Pinnacle

77

52

60

138

60

Ladv Windsor

75

64

61

143

83

139

600C

800C

Table 34
Oxygen Capacities of Semi-cokes (cc/g) produced at
450C. 500C. 600C and 800C

Coal

450'C

500*C

600C

800'C

Rawdon

1.01

1.61

2.73

6.19

Barnburgh

2.01

1.52

1.36

4.97

Hucknall

0.90

1.39

2.64

4.77

Wearmouth

0.39

1.28

2.53

2.27

Wentz

0.02

0.94

2.38

0.58

Ruhrkohle

0.34

1.75

0.23

Line Creek

0.34

1.35

0.28

Buchanan

0.16

1.01

0.15

0.28

1.09

0.26

Saraji
Oakgrove

0.02

1.07

1.03

Oakdale

0.79

1.26

1.08

Norwich

0.06

1.08

1.39

Pinnacle

0.95

Lady Windsor

0.06

1.36

1.22

All semi-cokes produced at 1000 C did not take up oxygen. Also semi-cokes
produced at 450C from Ruhrkohle to Lady Windsor did not take up oxygen.

140

Table 35
Nitrogen Capacities of Semi-cokes produced at 600C

Coal

Nitrogen Capacity (cc / g)

Rawdon

1.96

Barnburgh

1.13

Hucknall

1.40

Wearmouth

1.17

Wentz

0.68

Ruhrkohle

0.65

Line Creek

0.72

Buchanan

0.00

Saraji

0.26

Oakgrove

0.14

Oakdale

0.30

Norwich

0.12

Pinnacle

0.00

Ladv Windsor

0.95

Semi-cokes produced at 450. 500. 800 and 1000C did not


take up any nitrogen.

141

Table 36
Diffusional Parameters (xl(H) for Oxygen into Semi-cokes produced
from Coals at 450. 500. 600 and 80flC

Diffusional parameters (D/r2 10^) / s~l


Coal

450C

500C

600C

800C

Rawdon

2.34

0.98

9.15

3.32

Barnburgh

0.48

2.35

16.5

3.26

Hucknall

0.39

3.42

8.42

1.40

Wearmouth

0.19

1.88

7.00

0.34

Wentz

0.34

2.01

6.15

0.30

Ruhrkohle

1.69

6.42

1.03

Line Creek

1.35

5.42

1.80

Buchanan

0.91

4.53

0.42

Saraji

1.23

1.33

0.99

Oakgrove

1.28

3.18

0.99

Oakdale

1.39

4.75

3.47

Norwich

1.21

4.01

1.55

Pinnacle

3.84

Ladv Windsor

5.03

5.31

4.20

142

Table 37
Diffusional Parameters (xlQ-4) for Nitrogen into Semi-cokes
produced from Coals at 600C

Coal

Diffusional parameters ( IO-4) / s'

Rawdon

4.11

Barnburgh

8.44

Hucknall

4.76

Wearmouth

1.37

Wentz

1.22

Ruhrkohle

1.27

Line Creek

1.24

Buchanan

0.00

Saraji

0.86

Oakgrove

1.09

Oakdale

4.08

Norwich

1-05

Pinnacle

0.00

Ladv Windsor

1.11

143

TO TRANSDUCER AND COMPUTER

Thermometer

Water

Solvent

Sinter

Fig.l: Schematic diagram of the Dynamic Volumetric swelling Apparatus.

144

0.63
CJ

0.87
I

_ (30
"e
0.95

.0.98

0.00

0.10

0.20
2

Time, DIT t / a
Fl' "

0.30
2

Theoretical Fickian curve

0.63
o

0.87

_ CO

5
= 0.95

J- 0 . 9 8

0.00

0.20

0.40

0.60

Time, k o t / C 0 a

Fi.3: Theoretical Case 11 curve


145

Column

f
Solvent
V Reservoir J

^
SAMPLE
^

I H.P.L.C.
1 Pump

SJ*

UV
Detector

J>

Plotter -

Fig. 4: Schematic ((ingrani of the s.e.c


apparatus.

,
1 1 lUWIIILICI

s SAMPLE
1

OUT

Piiani Vacuum Gauge

Rotary Pump

j >

. 7 ; .
\ S N \ '

/ / / /

\ \ / \. ' \/ S-
/ S\ / \\ / \\ / \S /<'

( < (

Adsorption Tub es

Diffusion Pump

Mercury
Manometer

Fig. 5: McBatn spring b alance.

j^-y^

To now meters

Micro balance head

Helium
Puree flow

Gas to be adsorbed
or helium

Water outlet
Helium or gas
to be adsorbed
Heater

Sinter
Gas inlet

Fig.6: Apparatus for measuring gas


uptake by gravimetric method.

148

SO

0.30

0.26

40

60

'

80

Oxygen
Nitrofen

'

100

120

140

160

Weight of sample in helium


Fig.7: Buoyancy correction graphs f or oxygen and nitrogen in helium

149

a
u
zc
ti

'S!

100

200
time (mins)

400

Fig.8: Variation of swelling ratio with time for


the swelling of Rawdon coal in pyridine at 2()C.

150

.o

2.0

ti

1.5

1.0
0.0

0.5

Effia

1.0

2.0

1.5

Reflectance of coal (%)


Fig.9: Variation of swelling ratio w i t h coal rank
for swelling of coal in pyridine at 20 e C.

2.0

1.8
51

1.6

1.4
D

1.2

1.0
0.0

>

0.5

1 .0

Reflectance of coal

B
1

1 .5

2.0

(%)

Fig.lO: V a r i a t i o n of swelling ratio w i t h coal rank


for the swelling of coal in pyridine at 20 e C.

151

0>

tn

Qi
C/}

time (mins)
Fig.11: Variation of ln((Se-St)/Se) with time for the swelling
of Rawdon coal in pyridine at 20C (Fickian process ).

tn
tn

Vt
Fig.l2: Variation of Se/St with square root of time for the swelling
of Rawdon coal in pyridine at 20 e C. ( A Fickian process)

152

tn
tn

ZJ

tn

10

20

time (mins)

Fig.l3: Variation of ln((Se-St)/Se) with time for the swelling


of Rawdon coal in pyridine at 50 e C.( Anomalous process)

j
C/2

-1 -

tn
I

tn

20

40

60

80

100

time (mins)
Fig.l4: Variation of ln((Se-St)/Se) with time for the swelling
of Wearmouth coal in pyridine at 30 e C (Case 11 process).

153

0.0029

0.0031

0.00 . 1 J

In k(R)

In k(B)

In k(H)

In k(We)

In k(Wn)

0.0035

/
Fig.15: Arrhenius plots for the swelling of Rawdon, Barnburgh,
Hucknall, Wearmouth and Wentz coals in pyridine.

154

100

200

pyridine

2-chloropyridine

2-fluoropyridine

300

time (mins)
Fig.16: Variation of swelling ratio with time for Wearmouth
coal in pyridine, 2-chloropyridine, and 2-fluoropvridine.

tn
en
I

tn

time (mins)
Fig.l7: Variation of In((Se-St)/Se) with time for the
swelling of Wearmouth coal in 2-chloropyridine at 70C.

155

-0.5-

tn
tn

tn

800
time (mins)
Fig.l8: Variation of ln((Se-St)/Se) with time for the
swelling of Wearmouth coal in 2-fluoropyrid ine at 40 C.

tn
tn

o
tn

time (mins)
Fig.19: Variation of ln((Se-St)/Se) with time for the swelling
of extracted Wearmouth coal in 2-fluoropyrid ine at 30C.

156

-C

0.0029

0.0030

0.0031

'

0.0032

0.0033

0.0034

0.0035

l/T
Fig.20: Arrhenius plots for the swelling of Wearmouth
coal in pyridine, 2-chloropyridine, and 2-fluoropyridine.

tn

tn
I

tn

time (mins)
Fig.21: Variation of ln((Se-St)/Se) with time for the
swelling of Wearmouth coal in n-hexylamine at 30 e C.

157

Pyridine

2-chloropyridine

2-fluoropyridine


tn

tn

tn

1000

2000

3000

time (mins)
Fig.22: Variation of ln((Se-St)/SE) with time for the
swelling of oxidised Wearmouth coal in pyridine at 20C.

tn
tn
I

SJ

tn

450

time (mins)
Fig.23: Variation of ln((Se-St)/Se) with time for the
swelling of oxidised Buchanan coal in pyridine at 20 C.

158

tn
tn

ZJ

tn

time (mins)
Fig.24: Variation of ln((Se-St)/Se) with time for the swelling of
Wearmouth coal heat-treated for 24hrs at 200eC in vacuum (blank).

159

.41

untici

0.390

MAUEMJnBEfiS

Fig.25:

FTIR spectra of Wearmouth coal

408.

.aim

snnPi

.340

0.320

0.300

S
o

a:

s!
0.200

0.240

0.220

0.1977
IlQU

20U0
MAUEinmBERS

Fig.26: F TIR spcclra of oxidised VVearmoulh coal

lOUQ

400.0

6HiPi

.e-

0.55-

a.S

lj

0.45

ISJ

0.40-

0.35-

0.30-

.gC
0.192

4000

3QU0

-j

euua

UAUEHUnBERS

Fig.27:

FTR spectra of liiiclinnnn coni

IOU0

400.


0.420-r

0.392

0.384

0.335-

0.307-

UU

0.279

0.250

0.222

0.194

.IBS
4000

3UUB

UAUEUUflflERS

Fig.28: F TR spectra of oxidised Buchanan coal

400.0

0.0727
0.070

HESIII

.BGO

0.050

0.040

4QQ

Fig.29: nifferenco spectra for oxidised nnd raw Wenrmouth coal

.0(131

IILitH
I

0.060

0.050

0.040

0.030

ui

0.020

0.010

UAUEHUriBERS

Fig.30:

Difference speclra for oxidised and raw Buchanan coal

400.0


tn
tn

tn

1000

2000

time

Fig.31: Variation of ln((Se-St)/Se) with time for the swelling of oxidised


Wearmouth coal of particle size range 212-250u.m in pyridine at 20C.

166

JU

20

G
D

Q
.

*9

01
0.0

0.5

2.0
1.0
1.5
% Reflectance of coal
Fig.32: Variation of percentage extraction with coal reflectance.

JU

20

10

o
1o

20

"I

30

40

Volatile matter ( % d.a.f).


Fig.33: Variation of extract yield with volatile matter.

167

*
u

log ddpm
Fi.34: Variation of extraction vield with coal fluiditv.

168

io

Norwich

Fitt.35:

I
lilt

i.la

Lady Windsor

FTIR spcclm (1700-3600 c m " 1 ) of pyridine evlrncls of coals.

VJ

Oakgrove
Oakdale
Norwich
I * '

(.

'

'

'

M a v .) IIS

.t o

Fig.36: F TIR speclra (10(1(120(10 c m ' 1

'

'

Lady Windsor

) of pyridine extracts of coals.

<
sn
3

s:

% CH2

%CH 3

CS

C/5
^

2.0

Reflectance of coal

(%)

Fig.37: Variation of (CH2)asym and (CH3)asym in


the aliphatic stretching bands of the F T I R spectra of
pyridine extract of coals with coal rank.

JU

20

<

0
0.0

CH 2/CH ar

CH 3/CH ar

10
C.

'

0.5

1.5

2.0

Reflectance of coal (%)


Fig.38: Variation of the ratios of CH2 and CH3 asymmetric
bands to the aromatic C H stretching band w i t h rank of parent coal.

171

Rawdon

Barnburgh
Hucknall
Wearmouth
Wentz
7a

aoo

sea

93

Ruhrkhole
Line Creek
72

SCO

900

B5Q

wavenum herstem

Fig.39:
The 700-900 cm-1 region of the
FTIR spectra of pyridine extracts of coals.
172

Buchanan
Saraji

Oakqrove
700

750

SCO

BSO

sea

Oakdale
Norwich
750

8C3

SSO

300

950

Lady Windsor
SOO

wavenumbers(cm -1 )
173

950

U.

CS

0.6

.2

0.4
IT)

0.2

TZ

0.0

'

1
0.5

El

1
1.0

1 .5

2.0

Reflectance of coal (%)


Fig.40: Variation of the area of the 1655 cm-1 band with
rank of parent coal.

174

<

14 '

12-

13
s

"
10 -

"
8-

sCU

c
o

ZI

"
6.
4-

2
0.0

0.5

1.0

1.5

2.0

Reflectance of coal (%)


Fig.41: Variation of oxygen content with reflectance of coal.

I4
14

12 -

!/5

il

10 -

X
Zi

8S

6-

>>

*+

0.0

0.5

1.0

QQ

1.5

2.0

Reflectance of coal (%)


Fig.42: Variation of oxygen content of extracts with reflectance of coal.

175

s
V3
CU

o
u

14-

1210-

8-

C
eu

c
o

scu

C
>->
X

6-

4-

B^B
B

2-

'

r-

'

0.5

o.o

2.0

Reflectance of coal (%)


Fig.43: Variation of oxygen content of residues with
reflectance of parent coal.

14-

12-

%i

tz

8cu

6-

4-

c
o
c

o
CX)

2-

>>

-"

r
2

'

'

10

Oxygen content of coal (wt

'

12

<

14

%).

Fig.44: Variation of oxygen contents of extracts with those of coals.

176

O
cu

CU
Zl

>->

1-

X
Zi

Zi

zi

0.0

> '

0.5

1.0

'

"

1.5

2.0

Reflectance of coal (%)

Fig.45: Variation of differences in oxygen contents of


extracts and coals with percentage reflectance of coals.

177

o cu

c
u

cu

CU C. s

eu
8 C

Og =
c j

4 S3 S3
SUO S
>> CJ C

C o o

0.0

0.5

1.0

Reflectance of coal (%)


Fig.46(b): Variation of oxygen contents of extracts of coals heated
to maximum contraction temperatues with rank of parent coal.
W3

es

3 o
ce .J

cu
c S

.g
'
=

cu C
" O

CU

Reflectance of coal (9c)


Fig.46(a): Variation of oxygen content of extracts of coal
heated to softening temperature with rank of parent coal.

178

.2 SX)
s

2*5

cu
XC

O
w

O
c *
C "

I
S

CU u

3= s
3
sx) o Q .

X . B
/. " cu
w

U)

12

14

16

Oxygen contents of raw coals


Fig.46(c): Variation of oxygen contents of extracts of coals heated
to softening temperatures with those of the raw coals.

5*
3
U
S
._
X
Zi S3

w
;
U
3

S = 2
O cu
c

s- E
c* c ej

s *"
C cu c
eu - = C

CU s : C5
C C > > CU

10

12

14

Oxygen contents of raw coals (wt %)


Fig.46(d): Variation of oxygen contents of extracts of coals heate d
to maximum contraction temperatures with rank of parent coal.

179

IV

co

1817-

16-

o
Q

QB

15 -

14 -1
0.0

.0

0.5

2.0

Reflectance of coal (%)


Fig.47: Variation of retention volume of extract in
tetrahydrofuran with rank of parent coal.

180

Fig. 48(a):

Permeability of Rawdon

coal

160

5
o
LL
en
(

200

400
Temp

Fig. 48(b)

600
(C)

Permeability

of Wearmouth

200

c
E
o

100 -

li
en
to

Temp

181

800

(C)

coal

Fig. 48(a):

Permeability

of

Rawdon

coal

160

o
LL

en
m
C

200

400
Temp

Fig. 48(b):

600

800

(C)

Permeability

of Wearmouth

200

E
u

100 o
LL

m
to

200

400
Temp (C)

182

600

800

coal

Fig. 48(c):

Permeability of Wentz

coal

200

e
|
u

100

5
o
ti

en
co

200

400
Temp

Fig. 48(d):

600

800

(C)

Permeability

of

Ruhrkohle

200

E
u

3
o

100 -

en
es

800

183

coal

Fig. 48(e):

Permeability

of Buchanan

coal

200

3
o

100 -

re

800

Fig. 48(f):

Permeability

of

Saraji

coal

200

E
u
o^
3
o

100-

LL
tn
o

200

400
Temp

184

600
(C)

800

Fig. 48(g):

Permeability of Lady Windsor

coal

160

o
u
3
o
en
CO

200

Fig.48(h):

Latter

400

600

Temp

(C)

half

of

800

permeability

curves

120

c
E
u
o
3
o
LL

Wearmouth

Wentz

Ruhrkohle

tn

re

185

Saraji

Buchanan

2O00

4000

6000

time (secs)
Fig.49: A typical graph showing the variation of fractional
uptake with time for the diffusion of oxygen into semicokes.

186

Region of dangerously
swelling coals

2.5B

ZI

E
cu

cu
cz
e.

1.5B

C5

CU

CX
X

0.50.0

'

0.5

1 .0

1.5

2.0

Reflectance of parent coal (%)


Fig.50: V a r i a t i o n of oxygen c a p a c i t y of s e m i c o k e
produced at 600C with r a n k of p a r e n t coal.

2.0

"03

.^:

Region of dangerously
swelling coals

1.5

1.0
B
B

5 0.5
sr
m*
QB

0.0
0.0

0.5

1.0

po-

r
1.5

2.0

Reflectance of parent coal (%)


Fig.51: Variation of nitrogen capacity of semicokes
produced at 600eC with rank of parent coal.

187

o.o-l

CI

-1.0 -

-2.0 -

^ E L ^

-3.0 -

- -

-f

time (sec.)
Fig.52: Typical graph of the variation of ln((Me-Mt)/Me)
with time for the diffusion of oxygen into semicokes.

4.0748 + 0.50443X

FT 2 = 0.987

-1 -

CU

-2DDE]
uin

B BB

mu-mi
3

In t
Fig.53: Variation of ln(Mt/Me) with In t for the diffusion
of oxygen into semicoke, a typical Fickian diffusion.

188

tt

'/3
.

ro

Region of dangerously
swelling coals

15 -

"

SJ

10

C3

'_

"

PI
Q

5 -

"325

n
BQ

0 0.0

0.5

1'

1 .0

1.5

Reflectance of parent coal

2.0

(%)

Fig.54: Variation of diffusional parameter with rank of parent


coal for the diffusion of oxygen into semicokes prepared at 600C.

10

TL

8 -

Region of dangerously
swell inu coals

u
cu

"55

0 -

0.5

11.0.0

[-Q- 1

1.5

2.0

Reflectance of parent coal (%)


Fig.55: Variation of diffusional parameter w i t h rank of parent
coal for the diffusion of nitrogen into semicokes prepared at 600C.

189

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European Commission
EUR 17150 Coal preparation
Identification of coal characteristics indicating problems
of swelling during carbonization
/. Edwards, K. Thomas, F. Nadji, I. Butterfield
Luxembourg: Office for Official Publications of the European Communities
1997 189 pp. 21.0 29.7 cm
Technical coal research series
ISBN 92-827-9227-7
Price (excluding VAT) in Luxembourg: ECU 31.50

During the carbonization of coals in the coke oven some coals generate a
very high internal pressure and swell so excessively that they damage coke
oven walls or cause coke pushing problems known as 'stickers'. Several
methods have been employed over the years in the assessment of coal for
its suitability in the production of metallurgical coke in the coke oven
process. These characterization methods include the assessment of
thermoplastic properties such as the free swelling index, the Gray-King
coke test, the dilatometry, plastometry and more recently high pressure
dilatometry and plastometry. Although these tests are adequate for
assessing the coking properties of coal they have failed to distinguish those
coals that swell excessively during carbonization and those that do not.
Hence the need to look at the problem of predicting dangerous swelling
characteristics of coal using a more fundamental approach. The aim of the
present project is to establish a fundamental understanding of the
relationship between the coal structural properties, the carbonization
mechanism and coke properties for coals which exhibit these properties.

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