Recent progress in coal structure research*

Matthias W. Haenel
Max-Planck-lnstitut fiir Kohlenforschung, Kaiser- Wilhelm-Platz 7, D-4330 Nliilheim a.d.
Ruhr, Federal Republic of Germany
(Received 27 January 7992)

Coal is physically and chemically a heterogeneous rock which mainly consists of organic material. It is
generally agreed that the organic coal material has been formed from plant debris. In a first. mainly
biochemical stage, peat was laid down which in a later geochemical stage underwent coalification over a
period of up to several hundred million years under the influence of pressure and temperature caused by
overlying sediments. The organic sedimentary rock thus formed is composed of fossilized plant remains
called macerals, and mineralized inclusions. The macerals are microscopically distinct areas which are
differentiated into three major classes: vitrinite, exinite (or liptinite) and inertinite. Vitrinite occurs most
frequently and is believed to be derived from woody plant material (mainly lignin). and the exinite from
lipids and waxy plant substances. The origin of inertinite is possibly charcoal formed by prehistoric pyrolysis
processes.
As the result of its origin, coal is an almost non-volatile, insoluble, non-crystalline, extremely complex
mixture of organic molecules varying considerably in size and structure. Detailed structural characterization
has been found to be extremely difficult, so that coal structure research is still a challenging task and
continues to be pursued intensively. In principle, two approaches can be used for determining the chemical
structure. One attempts to degrade the coal macromolecules into representative fragments and to derive
the original structure from the structures of such fragments. The alternative approach attempts to
characterize coal directly by techniques which allow the non-destructive investigation of solid materials.
Such techniques are, for instance, i.r. and solid-state n.m.r. spectroscopy, X-ray diffraction and small angle
scattering, electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS). X-ray absorption
spectroscopy (XAS. XANES. EXAFS). or Miissbauer spectroscopy. While for some of these techniques
the application to coal is severely hindered owing to the lack of necessary transmittance or crystallinity,
others have been developed recently in material science as important tools for the investigation of solids.
In recent years further important insights into structural features of different coal varieties have been
gained using new physical and chemical methods and known techniques that have been further developed.
Some of these methods are reviewed and the results obtained from application to coals are discussed in
the context of coal structure.

(Keywords: coal; chemical structure; chemical degradation)

Only a little more than 10 years ago the International the end of the classical period a rather comprehensive
Coal Conference 1981 at Diisseldorf restarted, after a 13 insight into the chemical and physical structure of coals
years’ interval, this series of important coal conferences’. has been obtained’. This quotation gives the impression
In the opening lecture and formal address Professor van that at that time everything that could be done on
Krevelen gave an overview of the development of coal structural research on coals had actually been done. The
research2. Van Krevelen structured his lecture in three slump in activities in coal research during the 1960s
chapters. After the first 80 years’ phase from 1831 until however, was followed, towards the late 197Os, by a
1913 there followed the classical period of coal research revival which, after the Diisseldorf conference, led to a
between 1913 and 1963 which, for him, included the new series of successful coal conferences held every two
‘golden period’ of the 1950s when he himself and his years. The need for and significance of research on the
well-known friends and colleagues were in the heyday of structure of coal is not least reflected in the fact that in
their activities and substantially contributed to coal 1990 there took place the first new international confer-
science. Let me quote van Krevelen on the subject: ‘At ence on ‘Coal Structure and Reactivity’ in Cambridge,
UK3. In his inaugural speech Mr Jim S. Harrison,
Director of the Coal Research Establishment and Chair-
man of IEA Coal Research, compared van Krevelen’s
*A lecture presented at the Third Symposium on Biotechnology of
Coal and Coal-derived Substances. Essen, 23-24 September 1991. and
view with the situation physics was in at the turn of the
dedicated to Professor Dr Werner Peters. whose 70th birthday (23 last century when the theoretical structure of that
September 1991) was celebrated on this occasion. The symposium was discipline was considered to be complete, except for a
jointly organized by Deutsche Montan Technologie fiir Rohstoff. few gaps, and Max Planck, who was then a young man,
Energie, Umwelt e.V. (DMT), Essen, and Deutsche Wissenschaftliche
was dissuaded from studying physics. The present lecture
Gesellschaft fiir Erdiil. Erdgas und Kohle e.V. (DGMK). Hamburg,
and sponsored by the Federal Ministry for Research and Technology. tries to summarize our knowledge on coal structure and,
Bonn, and the Ministry of Economics, Small Business and Technology in particular, to outline some of the progress made since
of the State of Northrhine-Westphalia. Diisseldorf. van Krevelen’s ‘golden period’.

00162361/92,‘11121 l-13
i(’ 1992 ButtcrworkHeinemann Ltd FUEL, 1992, Vol 71, November 1211
Recent progress in coal structure research: M. W. Haenel

ORIGIN AND COMPOSITION OF COALS

Nowadays it is generally agreed that coal is pre-
dominantly of vegetal origin4p6. Figure I shows a
very simplified representation of coal genesis. At first
the debris of sinking swampy forests formed, under the
action of bacteria, large peat deposits (biochemical
phase). In the later geochemical phase which extended
for several hundred million years, the peat underwent
coalification under the influence of pressure and tempera-
ture caused by overlying sediments, forming lignite and
thereafter, with increasing coalification, bituminous coal
and anthracite. Coal has therefore to be regarded an
organic sediment.
The elementary composition changes with increasing
coal rank (Figure 3). The carbon content, amounting to
roughly 55 wt% in peat, increases up to more than Figure 3 Microscopic view of a bituminous coal (from ref. 7; source:
M.-T. Mackowsky, Bergbauforschung GmbH, Essen)
92 wt% in anthracite, whereas hydrogen, initially at
10 wt%, drops to below 3 wt%, and oxygen, initially
35 wt%, to finally 2 wt%. Sulphur and nitrogen are
present in only a few per cent and the change in their
concentration
proportion
with coalification
of aromatic
is less significant.
carbon atoms, 0.5 in lignite,
The
I Lignin: The Main Vegetational Precursor of Coal?

increases to beyond 0.95 in anthracite. The changing

elementary composition is also reflected in the hydrogen!
carbon ratio, which, approximately 1 for lignite, de-
creases to less than 0.5 for anthracite.
Its genesis alone suggests that coal is a non-homo-
geneous material. Coal, being an organic sedimentary
rock, is composed of fossilized plant remains which, in
analogy to minerals, are called macerals, and of mineral
occlusions. Macerals are distinctive areas under the Wood: ca 40% Cell”lose
20 - 35% LlgnIn
ULI to 30% Hemlcelluloses

I Swamp Decomposition
Figure 4 Composition of wood and structure of lignin

microscope and are differentiated into three major

groups. Vitrinite is the most prevalent group, accounting
for 80%, and is believed to be derived from woody plant
material (mainly lignin). Exinite (alternatively called
liptinite) is said to have developed from lipids and waxy
plant substances. Char formed by prehistoric pyrolysis,
e.g. during wood fires, is suggested as a possible origin
15 Ill Peat 3 Ill Lignite 1.5 m Bitum.Coal Anthracite of inertinite, the third maceral group. Figure 3 shows a
Plant-c Peat -L Lignite-Bituminous Coal- Anthracite-?-Graphite microscopic view of a bituminous coa17.
- Coalification (rank) _

CHEMICAL STRUCTURE OF COAL

Figure 1 Genesis of coal (modified from ref. 6)
Lignin is, in terms of quantity, possibly the most
important vegetal precursor of vitrinite in coal (Figure
4)‘.‘.‘. The dry substance of wood consists of roughly
- Coalification ___+
40% cellulose, up to 35% lignin, and maximally 30%
hemicelluloses. Whilst the polysaccharides (cellulose and
Plant + Peat -b Lignite + Bituminous Coal + Anthracite .‘w Graphite hemicelluloses) are easily degradable by enzymatic
c % 55 70 80-90 92 hydrolysis of the glycosidic bond, lignin strongly resists
biochemical and chemical degradation. It was only
H % 10 8-5 6-4 3
recently that enzymatic degradation of lignin by means
0 % 35 25 1 o-5 2 of ligninase has been evidenced through fungi”.
Lignin is a polymeric, three-dimensionally cross-linked
caf%ot -0.5 0.60 - 0.95
oxidation product of coniferyl and sinapyl alcohol and
H/C 1 p 0.5 contains hydroxy-, methoxy-, and alkoxy-substituted
benzene units. When we examine the lignin structure
Figure 2 Elementary composition of peat and coals shown. it can easily be conceived that in the course of

1212 FUEL, 1992, Vol 71, November

 Recent progress in coal structure research: M. W. Haenel

coalihcation the initially monocyclic aromatic units could

be condensed with the aliphatic lignin structure to form
polycyclic aromatic units of naphthalene, anthracene, or Two-component system:
phenanthrene.
As a result of its origin, coal is an almost non-volatile, l Macromolecular three-dimensional cross-
insoluble, non-crystalline, highly complex mixture of linked network (immobile phase)
organic molecules of varying size and structure. The
detailed characterization of its structure has turned out
l Multitude of relatively small molecules with
to be extremely difficult, so that structural research on
coal is a persisting challenge and continues to be pursued varying structures embedded therein (mobile
intensively. For almost 30 years now, attempts have phase, lo-50 % share)
repeatedly been made to unite previously known concepts
with recent findings in structural models supposed to
represent a hypothetical average molecule characteristic
of coal of a specific rank ll.
One of the more recent coal models is shown in
Figure S12. It assumes that aromatic and hydroaromatic
structural units of, on average, three to five rings are
cross-linked through short aliphatic and ether bridges to
form macromolecular aggregates. Only the smaller
molecules embedded in cavities or in pores and the not
very strongly cross-linked coal constituents can be dis-
solved by solvents to give coal extracts. The proportion
of carbon atoms bound in aromatic units increases with
coalification, and simultaneously the oxygen and hydro-
gen contents decrease. Simultaneously the average size
of the aromatic units is believed to increase only slowly
until the region of low-volatile bituminous coals (steam Aromatics, Aliphatics, Small
coal, or Mayerkohle) and thereafter to increase rapidly hydroaromatics ether bridges molecules
within the range of anthracitic coals.
These coal models, however, have been criticized quite
recently. The critics say that an average molecule is Figure 6 Conceptual coal model: two-component system (modified
absolutely inappropriate to reflect the molecular and from ref. 14)
structural diversity of coals”‘13.14.
As an alternative for such hypothetical average
molecules of these coal models, a two-component system
has been suggested for the vitrinite of bituminous
coa1’s-‘7. This model largely abandons the concept of
individual structures (Figure 6). A macromolecular,
three-dimensional network of the coal substance forms
the immobile component or ‘phase’ in which is embedded
a multitude of relatively small molecules of varying
structures forming the mobile component or ‘phase’. The
sketch of this model shown in Figure 6, however, retains
some of the previous structural concepts, i.e. the
identification of aromatic/hydroaromatic structures and
aliphatic/ether bridges.
It is generally agreed that a major part of bituminous
coal consists of three-dimensionally cross-linked macro-
molecules. The viscoelastic and mechanical properties as
well as the swelling behaviour caused by specific solvents
are indicative of that. On the other hand, the extent of
the low-molecular proportion of the mobile component
is vehemently disputed. Experiments using nuclear
magnetic resonance reveal at least two types of hydrogen
atoms present in coal which, depending on the difference
in mobility, are associated with either the mobile or the
immobile component,. The low-molecular share of be-
tween 30 and 50% determined by this nuclear magnetic
resonance method is, however, considerably greater than
C661H561 N4°74s6 C100H64.9N0.6011.2S0.9 can usually be extracted by solvents. An attempt has
MG = 10 023 C,, / C,, = 0.69 been made to explain this fact by proposing non-
extractable compounds physically occluded in the net-
work as well as long side-chains and less strongly
Figure 5 Structural model of high-volatile bituminous coal (modified cross-linked segments in the macromolecular structure
from ref. 12) which still possess sufficient mobility.

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Recent progress in coal structure research: M. W. Haenel

Chemical degradative reactions

The main methods of chemical degradative reaction
applied to bituminous coal are summarized in Figure 8.
Extreme conditions, i.e. high temperatures and high
hydrogen pressures as applied during pyrolysis, hydro-
Phytane C20H42 Pristane CISH, pyrolysis and technical hydrogenation of coal, will crack
the macromolecules of coal unselectively into a great
number of small molecules. Since secondary reactions,
e.g. rearrangements, cracking, hydrogenation and also
polymerization happen simultaneously, the constituents
of a tar or coal oil hardly allow any conclusions as to what
Fichtelite Retene their original structure may have been. It is attempted,
however, to just break up the most reactive chemical
bonds through short-time hydrogenation so that coal
molecules still exhibiting larger substructures are left
over. Ficgure 9 compares the different suggestions made
. for the structures of a heavy fuel fraction obtained by
-CH-ICH&-CH, coal liquefaction-in this case the so-called asphalt01
Cholestane Hopane n =o-5 fraction obtained from hydrogenation of Kentucky
bituminous coal-and of a petroleum residue”. Not-
withstanding their roughly identical molecular weights,
the structures derived are quite different. It should be
emphasized, however, that these are hypothetical average
molecules which, on the basis of averaged analytic data
and spectroscopic findings, an individual author has
suggested for a highly complex mixture of substances.
The oxidative reactions listed under the third heading
DPEP Etioporphyrine III in Figure 8 will also cause major destruction of coal
molecules. Nitric acid, potassium permanganate or
sodium dichromate preferentially oxidize the aliphatic
carbonaceous structures so that aromatic polycarbonic
Figure 7 Some geochemical fossils or biological ‘markers’ (modified
from ref. 14) acids are obtained13.“‘. Our knowledge of the main basic
structures of arenes and aromatic heterocycles in coal
originates basically from research on sodium dichromate
Many very different compounds contained in the oxidation in which the aromatic carbonic and poly-
‘mobile phase’ of coals have been identified by means carbonic acids obtained have been analysed, after
of ever more sophisticated analytical methods. Of the esterification, by mass spectrometry. In the case of Illinois
large variety let me just mention a few of the so-called No. 6, a high-volatile bituminous coal, it has for instance
geochemical fossils or biological ‘markers’i3.i8. All the been possible to identify 35 of those aromatic and
compounds depicted in Figure 7 are encountered, in heteroaromatic basic units, some of which can be seen
traces, in coal as well as in petroleum and betray their in Figure IO”. By the oxidative procedure, easily oxidized
biological origin from plants, algae or bacteria. In arenes such as anthracene and fluorene are obtained as
particular, in conjunction with petroleum these geo- anthraquinone and fluorenone derivatives. Figure II
chemical fossils have great relevance to the assignment of compares the relative abundances of some of these
petroleum fields to their source rocks and to the deter- aromatic units obtained by the sodium dichromate
mination of their degree of thermal maturation, since oxidation of lignite, bituminous coal, and anthracite.
both volume ratios and isomer distributions are subject
to continuous variation in the course of the catagenesis
and metagenesis of petroleumi8. Investigations of these
compounds are naturally of great interest, as they help
Chemical “Dissolving” of Bituminous Coal
in understanding the genesis and metamorphosis of coal
as a function of various geological conditions. Therefore,
in geochemical fossils huge potentials for the organic 1. Pyrolysis, hydropyrolysis
geochemistry of coals lie hidden’ 3.
2. Hydrogenation (hydrocracking) with hydrogen (BergiusIPier) or
hydrogen donor solvents (PoWBroche)
METHODS IN COAL STRUCTURE RESEARCH
3. Oxidation (HN03. KMnO,, Na2Cr207, H202/H+, NaJO,/RuCI,)
In order to investigate the chemical structure of coal.
there are in principle two strategies. The first attempts 4. Alkylation and acetylation in the presence of AK&
to degrade or to break down the coal macromolecules
into representative fragments and then to derive the initial 5. Acid-catalyzed “depolymerization” (Heredyn\leuworth)
Ar-(CH&-Ar’ + CsH50H 3 ArH + HOCsH.-(CH&Ar’
structure of the coal from the structures identified for
such fragments. The other strategy consists in character- 6. Reduction with alkali metals, reductive alkylation (Sternberg)
izing the coal directly by techniques which allow the
non-destructive examination of coal as it is, in the solid Figure 8 Methods of chemical degradative reactions applied to
state. bituminous coal

1214 FUEL, 1992, Vol 71, November

 Recent progress in coal structure research: M. W. Haenel

Figure 9 Hypothetical average molecules derived for a petroleum

Petroleum residuum residuum and for the asphalt01 fraction obtained from the hydro-
genation of Kentucky bituminous coal (modified from ref. 19)
wG2
Molecular weight 1000

Whereas benzene units are the predominant aromatic

structural elements for lignite, with hardly any larger
arenes encountered, the proportions of polycyclic arenes
and heteroarenes increase strongly in the sequence from
bituminous coal to anthracite”.
On the other hand, hydrogen peroxide in the presence
of acids5,13 and ruthenium tetroxide prepared in siru
from sodium periodate and ruthenium(II1) chloride’j
preferentially oxidize the aromatic units so that aliphatic
carbonic and polycarbonic acids are also produced which
may provide some information on the aliphatic portion
of coal.
Coal fraction FriedelLCrafts alkylation24 and acylationZ5 of bitu-
minous coal (fourth heading in Figure 8) yield partly
C6,%W4 soluble products, but are suspected to cause numerous
Molecular weight 900
side reactions owing to the use of aluminium chloride.
In so-called ‘acid-catalysed depolymerization’, the coal
is allowed to react with phenol in the presence of either
boron trifluoride or strong acids (p-toluenesulphonic or
sulphuric acid)26. The reaction principle is a Friedel-
iHm
2
.IN:
Crafts transalkylation reaction of phenol by which the
bonds between aromatic and aliphatic carbon atoms of
the coal are cleaved. Numerous side-reactions, however,
H prevent the method from being applicable for more
advanced structural investigations. Reductive methods
using alkali metals, on the other hand, cause partial
Source: Malvina Farcasiu, Mobil Oil degradation of the macromolecular coal even under quite

Benzene Nophtholcnc Phenonthrenr

Fluoronthene Fluorenone

Dibenrofuron Benronophthofuron
Anthroqumone Benzonthroquinone ondlor
Nophthocenequinone

Xonthone Benrothlophcne
Benzoronthone Dibenro-p-dioxin

Dlbcnrothiophcne Pyridmc Ouloollne and/ Corborole Acridone

Or isoquinoline

Figure 10 Some aromatic units identified by oxidation of bituminous coal with sodium dichromate and mass spectrometric analysis (as methyl
esters) of the aromatic polycarbonic acids formed (modified from ref. 21)

FUEL, 1992, Vol 71, November 1215

Recent progress in coal structure research: M. W. Haenel

has shown that, during reduction with alkali metals,

ether bonds and some benzylic carbon-carbon bonds
fl LIGNITE
0 BITUMINOUS COAL
are cleaved. This means that from the molecular weight
I ANTHRACITE distribution of reductively alkylated soluble coal pro-
ducts no conclusion whatsoever can be drawn regarding
the molecular sizes in the original coal. In order to
find out if and to what extent larger coal molecules can
be dissolved without applying bond-breaking reactions,
we are trying to attach the dissolution-promoting alkane-
sulphonic acid groups to the coal molecules by means
of non-reductive methods. By using a mixture of
tetraphosphorus decaoxide and methanesulphonic acid
(Eaton’s reagent), methylsulphone substituents can be
attached to aromatic units of the bituminous coal (Figure
13)3’. Although the activated methyl group of the model

COAL-H.
n = 15-20/1ooc
50% soluble in pyridine

COAL $$& [COAL]“- COAL-(‘3CH&

DHE, -25Y ” = 5/lOOC

75% soluble in pyridine

COAL-((CH&-SO,H),
n=5/iOOC
PEGDME: CHJ-0.(CHI-CHz-0)“.CH1
90% soluble in water
Coal. Robed Westerholt
23.646 Y. m.
89 4 % C (dal)

Figure 12 Reduction and reductive alkylation of bituminous coal with

Figure 11 Relative abundances of aromatic and heteroaromatic units potassium (modified from ref. 14)
identilied by sodium dichromate oxidation of lignite. bituminous coal
and anthracite and mass spectrometric analysis (as methyl esters1 of
the aromatic polycarbonic acids formed (modified from ref. 12)
P4010 i H,CSO,H
,oal-(Ar-H), . Coal-(Ar-SO$?Hs),

,r = aromatlc unit n=6-7/100C

mild conditions, and products of remarkably good solu-
bility are obtained in particular by reductive alkylation”.

r. 0c
Figure 12 shows some examples of reduction and
SOa Lie
reductive alkylation of the kind we practise, in a modified SO?
Sternberg process, in our institute in Mi_ilheim28-31. It base

is possible to dissolve potassium, at temperatures below

0
0°C and by using oligomeric polyethylene glycol dimethyl a‘S 2 @02<so3Q Lic
ethers (PEGDME), into dark-blue solutions of solvated
electrons which are capable of reducing bituminous coal SOzQ Li’

to give a coal polyanion. Hydrolysis yields a hydro-

genated coal product, 50% pyridine-soluble2’. Conver- 0
sion by methyl iodide gives a reductively methylated coal oal-(Ar-H),
PPA I H,CCOCI
. Coal-(Ar-C -CH$,
product of 75% pyridine-solubility”. Labelling with the r = ammatlc unit n=6-7llOOC
carbon isotope 13C has been used as a spectroscopic
probe in 13C n.m.r. spectroscopy to provide structural
information3’. Furthermore, the coal polyanions react , >N;;.SOs’Na@w
Coal-Ar
with 1,3-propanesultone by nucleophilic opening of the )=N-
o- SOsQNa@

sultone ring and yield coal-propanesulphonic acids

which, surprisingly for a derivative of bituminous coal,
are up to 90% soluble in wate?‘. If one considers the :oal-Ar
5% of mineral matter which this coal contains, there k0
remains only about 5% of the coal which resists W

solubilization. The molecular weights of these coal-

propanesulphonic acids produced from a medium-
1 L’ -so3Q’(c4Hg)4 ) Coal-Ar -22 S038~(C4Hgj,
volatile bituminous coal (coking from the Ruhr area) are
in the range 500 to 50 000 daltons. This reaction provides 01 LI -S03Ph H&’ (SOsPh)
us with soluble coal derivatives which are attractive for
more advanced structural investigations. Figure 13 Attempts at developing non-reductive pathways to coal-
Comprehensive research on coal and model substances alkanesulphonic acids (ref. 32)

1216 FUEL, 1992, Vol 71, November

 Recent progress in coal structure research: M. W. Haenel

compound methylphenylsulphone could be substituted

by one or even two propanesulphonic acid groups,
experiments attempting the analogous transformations COALS
at the methylsulphone substituents of the coal product 2 sm 0
0.2 0.4 0.6 O-6 1.0
-7
failed. In a second approach, acyl chlorides in poly-
phosphoric acid (PPA) were used to gently acylate
aromatic units of bituminous coal, i.e. without applying GRAPHITE
the severe reagent aluminium chloride. In the attempt to 0.1 03 0.5 o-7 0.9 -

attach alkanesulphonic acid substituents on the acyl

groups via an oximether linkage, only one third of the
acyl groups underwent the reoximation reaction (see IN1
reaction scheme in Figure 13). Presently we are trying to
T
attain the attachment by taking advantage of the
reactivity of the acyl groups towards organometallic
reagents.

Spectroscopic methods
The direct non-destructive characterization of coal in
its original form in the solid state-mentioned above as
the second strategy of structural research-uses spectro-
scopic methods. Figure 14 summarizes, in the upper part,
the main methods of structural analysis and lists
developments which are especially relevant to coal
structure research.
Infrared spectroscopy has gained additional importance
by the introduction of the Fourier transform technique
and of measurement in reflection. Nuclear magnetic
resonance spectroscopy of the insoluble solid coal became
feasible only after solid-state 13C n.m.r. spectroscopy
Figure 15 X-ray powder diffraction spectra of coals (vitrinites) and
and special techniques for solid-state ‘H n.m.r. spectro- graphite (modified from ref. 4)
scopy had been developed33-35. Solid-state r3C n.m.r.
spectroscopy provided for the first time a direct method
to determine the proportions of aromatic and aliphatic
carbon atoms in coal. In the meantime specific measur- determination and possibly identification of extremely
ing techniques have become available for the further small amounts of individual compounds in complex
differentiation of particular aliphatic and aromatic mixtures such as coal extracts, tar, coal oil and
carbon atoms. In addition, the dynamic behaviour of volatile degradation products of coal. As has been
signal intensities in nuclear magnetic resonance is demonstrated by the examples of geochemical fossils,
increasingly used for structural information. An example these techniques have contributed enormously to our
has been mentioned above with the determination of the knowledge on low-molecular compounds extractable
mobility of hydrogen atoms in the mobile and immobile from coal. When pyrolysis mass spectrometry became
component’ 5-1 ‘. available, even compounds occluded in cavities of the
For mass spectrometry the object to be analysed has coal network as well as primary cracking and degradation
to be transferred into the gas phase so that, in principle, products of the macromolecular portion of coal became
this method is not appropriate for investigations of accessible for analysis by mass spectrometry’7,36.37.
non-volatile solid materials. Mass spectrometry, particu- Novel methods of electron spin resonance (FT-e.s.r.,
larly in conjunction with gas chromatography, allows the e.s.e.) are available for examining stable radicals in coals.
On the basis of relaxation times, apparently up to three
quite different types of radicals can be distinguished14.
X-ray diffraction of coals4.5,‘3*38 was investigated mostly
Method Development relevant for coal
during the 1950s but its application to non-crystalline
solids such as coals is severely limited. One further
IR FT-WI,measurement in reflexion development is small angle X-ray scattering (SAXS), used
NMR ‘3C-CP-MAS-NMFl (solid state) for determining the distribution of pore sizes39’40.
Relaxation experiments
Other physical methods, e.g. microprobe, electron
MS Pyrolysis-MS (Curie point MS)
microscopy, photoacoustic microscopy, Miissbauer
Pyrolysis-GC-MS, time resolution
spectroscopy and various kinds of X-ray and electron
ESR FT-ESR, ESE (electron spin echo)
Relaxation experiments spectroscopy (e.g. XPS, XAS, XANES, EXAFS), all of
uv / VIS - which have been developed in particular to examine
X-ray drtfraction Small angle X-ray scattering (SAXS)
surfaces and solids in materials science, are increasingly
also used for ‘non-destructive’ investigations on the
Microprobe, electron microscopy (TEM). photoacustic microscopy,
MoObauer spectroscopy, methods of electron/X-ray spectroscopy
structure of coals.
(XPS, XAS. XANES, EXAFS) Figure 1.5 compares the X-ray powder diffractograms
of various coals and graphite4*‘3.38. The 002 reflection
Figure 14 Spectroscopic methods relevant to coal structure research of graphite is essentially attributed to diffraction at the

FUEL, 1992, Vol 71, November 1217

Recent progress in coal structure research: M. W. Haenel

equidistant graphite layers. In the case of coals, anthracite

(96.5 wt% carbon content) shows a diffractogram in a
which the reflections of graphite can still be recognized. N=2/
W
With decreasing rank, however, from anthracite to lignite
(65.1 wt% carbon content), the diffraction pattern be-
comes more and more diffuse and the peak of the 002
l Hetero-
reflection is shifted slightly to smaller diffraction angles.
atom
The X-ray results have been interpreted in terms of a
graphite-like coal structure in which local aromatic stacks
are present in two or three layers (Figure 16). Coal rank
is considered to influence particularly the average
diameter of these aromatic layers. Coals containing less
than 75 wt% carbon are supposed to have an average
layer diameter of approximately 5 .& which corresponds
to 8 to 9 atoms within the aromatic layer. Between 78
and 92 wt% carbon, the average layer diameter is
believed to be relatively constant at roughly 7.5 A, which
corresponds to 15 to 18 atoms per layer; it is then thought
to increase rapidly in anthracitic coals, having carbon
contents above 92 wt%, to more than lOA, which
corresponds to more than 30 atoms within the aromatic
layer.
This interpretation of X-ray diffraction data achieved
at the end of the 1950s is strongly supported by more
recent investigations using transmission electron micro-
scopy (TEM)41,42. Special techniques have rendered Figure 17 Micrograph of a French coking coal (M&icourt, 88.6 wt’?‘o
visible structures of a French medium-volatile bituminous C. 73.4 wt% v.m. (daf)) obtained by transmission electron microscopy
coal (coking coal. 88.6 wt% C), with a resolution of less (TEM 1: 002 lattice image of fringes of parallel basic structural units in
a molecular orientation domain, and proposed model (modified from
ref. 42)

aromatic
-layer c than 10 A (Figure 17). As has been indicated in the
schematic model (upper part of Figure 17), the formation
of structures is attributed to the diffraction of electrons
at parallel aromatic planes, with sufficient contrast being
obtained only if two or three aromatic planes are
arranged absolutely parallel in a ‘basic structural unit’.
In conformity with the X-ray data just discussed, an
average layer
average diameter of the aromatic layers of less than 10 A
coals diameter atoms and a stack height of 2 to 3 aromatic layers have been
(%C) (A) (number) derived for these ‘basic structural units’ of a coking coal.
< 75 -5 8-9 Since solid-state 13C n.m.r. spectroscopy became
78-92 - 7.5 15-18 available some 15 years ago, it has developed into one
> 92 > 10 > 30 of the most important methods of coal structure
research33-35. In order to reduce the extremely broad
line-widths typical for solids, three techniques are usually
3 combined in solid-state 13C n .m.r. spectroscopy (Figzfvr
10.0 18. ‘High-power decoupling’ reduces the line-broadening
5
caused by dipolar interaction between carbon and
E
.m hydrogen nuclei. Second, ‘cross polarization’ avoids long
0
relaxation delays, enhances the sensitivity by a factor
7.5 $
of 4, and-important for quantitative interpretation-
4
enhances the relative sensitivity of the non-protonated
g carbon atoms. By ‘magic angle spinning’, finally, the
5.0 2
?
chemical shift anisotropy intrinsic to the solid state is
2.5 a reduced towards zero. The lower part of Figure 18
represents the 13C CP-MAS n.m.r. spectrum (75 MHz)
70 80 90 100
of an east German lignite. The aromatic and aliphatic
% Carbon
carbon atoms appear as separate signal groups at 180 to
90 and 80 to 8ppm and thus are easy to quantify.
Functional groups can be identified and quantified by
differentiating the signals further according to typical
Figure 16 Graphite-like coal structure as deduced from X-ray
diffraction data (after L. Cartz and P. B. Hirsch, 1960. modified from
ranges of the 13C chemical shift. Moreover, the technique
ref. 13) of ‘dipolar dephasing’ allows one to distinguish between

1218 FUEL, 1992, Vol 71, November

 Recent progress in coal structure research: M. W. Haenel

and bituminous coal. With increasing coalification both

3C CP/MAS NMR SPECTROSCOPY (SOLID STATE) the aromatic and the aliphatic oxygen functionalities
l High Power decoupling (HPD):
(hydroxy and ether groups) decrease drastically.
removal of ‘H_13C dipolar interactions
From the proportion of quaternary aromatic carbon
atoms bridging polycyclic arenes, one can derive an
0 Cross polarization (CP):
estimate of the average number of carbon atoms within
to avoid long relaxation delays
an aromatic unit, i.e. the average aromatic cluster size.
increase of sensitivity by factor 4
Using this approach, the average aromatic unit of lignite
. Magic angle spinning (MAS): > 2 kHz at 54’44’
would be formed by 9 atoms, which means that
removal of chemical shift anisotropy
the aromatic unit is somewhat smaller than naphthalene
l Dipolar dephasing:
with its 10 carbon atoms (Figure 20). In bituminous coals
separation of carbon atoms
the average aromatic unit contains between 14 and 20
carbon atoms corresponding to 3 to 5 condensed rings.
The average aromatic layer sizes derived from solid-state
13C n.m .r . data therefore fully agree with the results
obtained by X-ray diffraction, electron microscopy,
westelbian brown coal
and degradative reactions, e.g. by means of sodium
lithotype Schleenhain
dichromate oxidation, as discussed above.
The heteroatom nitrogen, which is present in coal in
the range 1 to 2 wt%, is bound more or less exclusively
Pv-
in aromatic heterocycles, that is, in the form of pyrrolic
nitrogen in five-membered rings and as pyridinic nitrogen
in six-membered rings5,5.‘3. X-ray photoelectron spectro-
scopy (XPS) allows direct determination of both of
the nitrogen functionalities in coal”4p57. The method
measures the bonding energy of the nitrogen 1s electron,
line deconvolution
of structural groups

ZiO 100 i wm

Figure 18 Techniques of solid-state 13C’ CP-MAS n.m.r. spectroscopy.

and 13C CP-MAS n.m.r. spectrum (75 MHz) of an east German lignite
(modified from ref. 33)

protonated and non-protonated aromatic carbon atoms

as well as between aliphatic methylene and methine
groups on the one hand and methyl groups and
b
quaternary aliphatic carbon atoms on the other hand.
% -
One of the most comprehensive investigations of
different coals by solid-state 13C n.m.r. spectroscopy
originates from the research groups of Grant and
Pugmire in Salt Lake City, USA43. Eight coals of the
Argonne Premium Coal Sample Program, ranging from
lignite to low-volatile bituminous coal, were intensively
investigated by all avenues of the present state of the
art in solid-state ’ 3C n.m.r. spectroscopy. The proportion
of aromatic carbon atoms increases with coal rank C
from roughly 54% in lignite to 86% for low-volatile % (L)
bituminous coal (Figure 19~). Further differentiation of 12 (SW
the aromatic carbon atoms by using the dipolar de- 10 6-W
phasing technique together with typical chemical shift 8 W’B)
I
ranges provides evidence that the quaternary carbon VW
atoms bridging polycyclic arenes increase most of all. 4 W’W
2
PW
Conversely, the proportion of aliphatic carbon atoms 0
calimy, c Arcmaw 0.0 Yiphm 0.0 (L’W
decreases with rising coal rank from 39% in lignite to L?xme4-m

14% in low-volatile bituminous coal (Figure 19b). This

decrease is mainly in methylene and/or methine groups.
whereas the portion of methyl groups and/or quaternary Figure 19 Structural parameters derived by solid-state 13C CP-MAS
aliphatic carbon atoms remains fairly constant. As can n.m.r. spectroscopy for eight different coals of the Argonne
be seen from the distribution of carbon atoms bound to Premium Coal Sample Program. L = lignite, SB = subbituminous coal,
HBV = high-volatile bituminous coal, MVB = medium-volatile bitu-
oxygen (Figure 19c), carbonyl carbon atoms are present
minous coal. LVB = low-volatile bituminous coal. Relative abundances
essentially only in lignite and in the typical subbituminous (a) of aromatic structures. (b) of aliphatic structures and (c) of oxygen
coals of N. America, which are of rank between lignite functionalities (modified from ref. 43)

FUEL, 1992, Vol 71, November 1219

Recent progress in coal structure research: M. W. Haenel

I X-ray absorption fine structure (XAFS) spectroscopy54,55

AROONNECOALS determines the electronic structure and atomic environ-
20
ment of an element by analysis of the fine structure
associated with an X-ray absorption edge of that
element. Distinction is made between two ranges: the
range of X-ray absorption near-edge structure (XANES)
extends up to 20-50eV above the absorption edge,
whereas the range of the extended X-ray absorption fine
structure (EXAFS) starts between 30 and 50eV above
the absorption edge and extends up to 500 and 1000eV.
The structure of the XANES range is caused by photo-
carbon atoms per aromatic unit I electron transitions to vacant levels and low-energy
scattering resonances. EXAFS oscillations originate in
Figure 20 Average number ofcarbon atoms per aromatic unit derived interferences between the outgoing and backscattered
from solid-state ‘T CP-MAS n.m.r. spectroscopy for eight coals of the wave functions of the photoelectrons and can be analysed
Argonne Premium Coal Sample Program ranging from lignite (North
by means of Fourier transformation methods in terms of
Dakota) to low-volatile bituminous coal (Pocahontas) imodified from
ref. 43) interatomic distances and coordination numbers to
atomic neighbour shells. For determining sulphur in coal,
XANES spectroscopy has very recently gained particular
significance51-5 3.55-5 ‘.
Figwe 23 summarizes recent results which the two
leading research teams have achieved by applying
XANES spectroscopy to coals of the Argonne Premium
Coal Sample Program. According to the results shown
in the upper diagram52, the aromatic (thiophenic)
sulphur rises with increasing coal rank from 30% of the
total organic sulphur in lignite to over 90% in low-

Figure 21 Direct determination of nitrogen functionalities in coal by

X-ray photoelectron spectroscopy (XPS). Left: nitrogen Is XPS
spectrum of a coal. Right: variation of nitrogen functionalitirs with
rank for some UK bituminous coals (modified from ref. 46)

which, owing to the difference in chemical environments,

is slightly different for pyrrolic and pyridinic nitrogen
atoms (Fiyzlre 21, left). The right-hand diagram in Fiylrre
21 shows the distribution of nitrogen functionalities as a
function of coal rank for some English coals.
*
The total and organically bound sulphur contents of 160.0 164.0 166.0 172.0
coals are variable and tend to depend on the source rather Binding Energy (eV)
than on the rank’3,48*49. Organic sulphur occurs in coal I
mainly in thiophenic heterocycles and aliphatic sulphides Oxidized
and it appears, in smaller quantities, in thiols, thiophenols
and diary1 sulphides. XPS is appropriate for the direct
non-destructive determination of the proportions of
thiophenic and aliphaticcsulphidic sulphur in coa1s0~53.
For example, in the XPS spectrum of RaSa coal (Fiyu~
22) it is possible by line shape analysis to separate the
sulphur 2p electron signal into two components corre-
sponding to 70% thiophenic sulphur and 26% aliphatic-
sulphidic sulphur5’. (The ideal sulphur 2p signal consists
of 2~,,, and 2~,,, contributions having a 2:l intensity -*__
ratio and separated in energy by about 1.2eV). After 5 I
days of air oxidation at 125”C, the signal component of 164.0 166.0 172.0

the thiophenic sulphur remains, whereas the aliphaticc Binding Energy (eV)
sulphidic signal component has largely disappeared and
a new signal group exhibiting higher bonding energies
for oxidized sulphur compounds has been formed instead. Figure 22 Direct determination of sulphur in coal by X-ray photo-
Another technique has recently been developed for the electron spectroscopy (XPS): spectra of RaSa coal (a) as received and (b)
direct non-destructive determination of sulphur in coal. o?tidiLed (modified from ref. 51)

1220 FUEL, 1992, Vol 71, November

 Recent progress in coal structure research: M. W. Haenel

PHYSICAL STRUCTURE OF COAL

Coal has not only a chemical but also a physical
structure 65. In particular, the pore size and its distribu-
tion are highly relevant to chemical and biotechnological
5 90 reactions of coal (Figure 25). Professor Peters has made
4
essential contributions together with Professor Jiintgen
r$ 80
to the determination of the physical structure and
porosity of coal 66-70. Besides porosimetry using mercury
and gases, small-angle X-ray scattering (SAXS) is the
most recent method used to determine pore structures
and distributions39.40,65. Coals exhibit a quite large
distribution of pore sizes, from smaller than 5A to
40 1 I , I 1 1 I beyond 1OOOA. According to the results obtained by
70 75 80 85 90 95 100 SAXS4’, the maximum of pore size distribution is
% CARBON (dmmf) supposed to be roughly between 80 and 100 A. With
regard to biotechnology of coal”,71 79, however. the
pores are much too small to allow the penetration of
bacteria having a size of roughly between 1 and 5~tm
(10000 and 5OOOOA).
Another feature of the physical structure of coal is its
moisture content which, for lignite, may exceed 60 wt%.
Removal of moisture may lead to reversible but some-
times also irreversible alterations of the coal structure.
The latter aspect could be of relevance particularly to
biotechnological transformation.

FINAL REMARKS
If we look 10 years back on the Coal Conference in
73 73 75 78 81 83 83 86 91
% CARBON (dmmf)
Dusseldorf under the chairmanship of Professor Peters

Figure 23 Direct determination of organic sulphur in coals by XAFS . ionic bonds

(XANES) spectroscopy: relative change of aromatic (above) and
aliphatic (below) sulphur with rank for coals of the Argonne Premium R-COO- M2+ -OOC-R M = Ca. Mg. Fe, etc.
Coal Sample Program (modified from refs 52 and 58)
$
.z . hydrogen bonds
b
E \\
.-P
lN’. ..H - 0 - ;C = O...H - 0 -

volatile bituminous coal. The data are also in good Im l aromatic-aromatic interactions
agreement with results obtained by X-ray photoelectron
spectroscopy (XPS). Contrary to the aromatic (thio-
phenic) sulphur, the aliphaticcsulphidic sulphur de-
creases from about 40% in lignite to less than 10% in
low-volatile bituminous coal (data not included in the
upper diagram of Figure 23). The independent study of
Figure 24 Non-covalent interactions relevant to the solid-state
the other team (lower diagram of Figure 23)‘* is in full st&ture of coal
agreement by showing that the proportion of the
aliphaticcsulphidic sulphur decreases from almost 50%
in lignite towards zero in low-volatile bituminous coal. e
ro pore
Non-covalent interactions in coal
Besides covalent bonds, non-covalent interactions
must also be considered to contribute to the formation
of the solid structure of coal as an organic sedimentary
rock59p63. Among these are, in order of decreasing bond
Pore Size and Distribution Bacterium: I-5 pm
strength. ionic bonds, hydrogen bonding, and arenee
Methods: 10000
- 50000 A
arene interactions (Figure 24). Cross-linking through Mercury and gas poroslmetry
ionic bonds between carboxylic groups and di- and (W. Peters and H. JUntgen)
trivalent metals, e.g. calcium, magnesium, and iron ions, SAXS (IO - 1000 A) IUPAC (1972):

has to be considered particularly for lignite64. However, Macropores > 500 A

coats: < 5 - IOOO A Mesopores 20 - 500 A
it should be possible to destroy such an ionic bond by A
malnlv 80 - 100 A fSAXSI Micropores a - 20
trying to detach the metal ions, e.g. by means of strongly
complexing reagents.

FUEL, 1992, Vol 71, November 1221

Recent progress in coal structure research: M. W. Haenel

and on the inaugural speech Professor van Krevelen Schanne, L. Angew. Chem. 1980, 92, 653: Anger. Chem. Int.
delivered on that occasion, it appears to mc that since van Ed. Engl. 1980, 19, 636
31 Haenel. M. W., Richter, U.-B. and Hiller, H. Angew. Chem.
Krevelen’s ‘golden period’ some significant progress has 1985. 97, 340; Angew. Chem. Int. Ed. Engl. 1985.24. 342
been made in the research on coal structure. Science never 32 Rollwage. U. Dissertation. University of Dusseldorf. 1991 (also
stands still but rather forges ahead, and every novel and unpublished work by B. S. Bal. M. W. Haenel and U. Rollwage)
improved method allows new and more precise insights. 33 Meiler, W. and Meusinger, R. In ‘Annual Reports on NMR
Spectroscopy’ (ed. G. A. Webb), Academic Press, New York,
During the last few years especially, the fast advancing
Vol. 23, 1991, p. 375
field of materials science has provided innovative methods 34 Snape, C. E., Axelson, D. A., Botto. R. E., Delpuech. J. J..
which allow direct examination of coal in the solid state Tekely, P.. Gerstein. B.C.. Pruski, M.. Maciel. G. E. and Wilson,
and will thus gain increasing importance. I am sure, M. A. Fuel 1989, 68, 547
however, that also the biotechnology of coa1’“.71-79- 35 Maciel, G. E.. Bronnimann, C. E., Jurkiewicz, A., Wind. R. A.
and Pan. V. H. Fuel 1991, 70, 925
still quite a young science-will lead to new findings on 36 Meuzelaar. H. L. C., Haverkamp, J. and Hileman, F. D.
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enhance our knowledge on coal structure. By and large, 37 Yun. Y., Meuzelaar. H. L. C., Simmleit, N. and Schulten. H.-R.
Glrry~ Fuels 1991, 5. 22
coal is still an extremely complex system and will remain
38 Cartz. L. and Hirsch. P. B. Phil. Trans. Rev. Sac. Londorl 1960.
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39 Mahajan. 0. P. In ‘Coal Structure’ (ed. R. A. Meyers), Academic
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1222 FUEL, 1992, Vol 71, November

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FUEL, 1992, Vol 71, November 1223