Fuel Processing Technology 106 (2013) 9–20

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Fuel Processing Technology

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Review

A review on water in low rank coals: The existence, interaction with coal structure
and effects on coal utilization
Jianglong Yu a, b,⁎, Arash Tahmasebi a, b, Yanna Han a, Fengkui Yin a, Xianchun Li a
a
Key Laboratory of Liaoning Province for Advanced Coal and Coking Technology, School of Chemical Engineering, University of Science and Technology Liaoning,
No.185 Qianshan Zhong Road, Anshan (114051), China
b
Thermal Energy Research Centre, Shenyang Aerospace University, No. 37 Daoyi Nan Ave, Shenyang (110136), China

a r t i c l e i n f o a b s t r a c t

Article history: Low rank coals are generally featured with a high water content which exerts strong influences onto their uti-
Received 13 February 2012 lization including pyrolysis, gasification, liquefaction and combustion. Understanding of fundamental aspects
Received in revised form 11 September 2012 of coal moisture and its effects on physical and chemical characteristics of coal and coal–water interaction are
Accepted 16 September 2012
very important in order to develop technologies to remove coal water effectively. This paper provides a com-
Available online 22 October 2012
prehensive overview on the fundamental understanding of water in brown coal and lignite, including the
Keywords:
physical and chemical structure of coal, the forms of water present in low rank coals, migration of water dur-
Low rank coals ing drying, coal structure changes during moisture loss, moisture re-adsorption, and effects of water removal
Coal–water interaction on subsequent applications including combustion, gasification and liquefaction. Applications of techniques
Forms of water such as NMR, DSC and FTIR in determination and quantification of types of water and coal structures are
Drying also summarized.
Thermal treatment © 2012 Elsevier B.V. All rights reserved.
Coal structure

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2. Coal–water interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3. Forms of water in brown coal and lignite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4. Coal structure change during moisture loss and re-adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1. Physical structure changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2. Chemical structure changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5. Effects of moisture on utilization of low rank coals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6. Summary remark . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1. Introduction coals are playing an increasingly important role in supplying primary

Currently known recoverable coal deposit around the globe will
last over 150 years at the current consumption rate [1]. Low rank
coals including brown coal and lignite and sub-bituminous coals ac-
count for nearly half of the coal reserve worldwide [2]. Low rank
⁎ Corresponding author at: Key Laboratory of Liaoning Province for Advanced Coal
and Coking Technology, School of Chemical Engineering, University of Science and
Technology Liaoning, No. 185 Qianshan Zhong Road, Anshan (114051), China.
Tel.: + 86 18609808557; fax: + 86 412 5929627.
E-mail address: jianglongyu@163.com (J. Yu).
energy in developing countries such as China. Low rank coals are clas-
sified as low grade fuel, and are generally featured with low calorific
value, high water content (25–65%) and low sulfur content. Currently
low rank coals are used primarily for electricity generation, but their
use for other applications will increase in the future because they do
have certain advantages over black coal [3]. These advantages include
low mining cost, high reactivity, high amount of volatiles, and low
pollution-forming impurities such as sulfur, nitrogen, and heavy
metals [4].
Water in low rank coals exerts significant influences upon their uti-
lization processes, including combustion, gasification and liquefaction.

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.051
10 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
The high moisture content results in lower calorific value, higher fuel
consumption and higher stack flue gas flow rate, higher power con-
sumption and lower efficiency, risk of spontaneous combustion, and in-
creased transportation cost. At present the amount of carbon dioxide
produced per MWh by burning brown coal is one third higher than
burning black coals [5]. Relative reduction of 30% in CO2/MWh can be
achieved when using coal with moisture reduced from 60% to 40% [6].
In combustion process, 20–25% of the heat from combustion of brown
coal is wasted in removing the associated water [5,7,8]. New cost-
effective drying technologies are needed for low rank coals to remain
competitive. On the other hand, the extent of drying is very important
for low rank coal reactivity in downstream applications that depends
on their physical and chemical characteristics [9–13]. The ease of
water removal is dependent on the forms of water in low rank coals.
The change in pore structure characteristics of low rank coal during
water removal is significant and this affects the mass transport and
chemical reaction mechanism involved in combustion/conversion pro-
cesses. Coal mesopore structure is composed of pore channels that con-
trol the transport of gaseous reactants and products (e.g., oxygen and
carbon dioxide in the case of combustion and steam; hydrogen, carbon
oxides and methane in the case of gasification) [14]. The fundamental
understanding of water in low rank coal, its effects on physical and
chemical characteristics of coal and coal–water interaction has ad-
vanced in the past but is yet to be clarified in the literature. Such under-
standing is essential to the development of efficient drying technologies
for low rank coals.
2. Coal–water interactions
The coalification process is accompanied by the elimination of
water due both to chemical changes associated with coalification pro-
cess and the physical consolidation of the coal deposit. Low rank coals
contain a number of oxygen functional groups resulting in material
with hydrophilicity, and this is the primary reason for their water
content being as high as 30–65 wt.% on a wet basis [2,5,15]. The
water content in coal decreases along through the coalification pro-
cess most probably due to elimination of polar functional groups es-
pecially hydroxyl (− OH) groups. Besides the hydroxyl groups,
carboxyl (COOH), methoxyl (OCH3), and carbonyl (> C O) groups as
well as ring oxygen are decomposed and so the carbon content in-
creases [16–18]. Natural coal bed moisture content is correlated
with the moisture holding capacity of coal at 30 °C and 96% relative
humidity [19]. Low rank coal exhibits a gel-like behavior and swells
and shrinks significantly (~ 30 vol%) with the loss and gain of water
[20–22]. The finely divided coal substance is dispersed in a continu-
ous water medium to form a gel which is stabilized by the carboxyl
and hydroxyl groups in the coal. As these groups are removed, the
coal progressively loses its hydrophilicity and colloidal nature
[20,23]. In bed-moist brown coal the pores and intermicellar capil-
laries are saturated with water and each coal micelle is surrounded
by multimolecular water layer with a thickness of 4 to 5 water mole-
cules. The monolayer water, which in soft brown coals comprises only
about one twentieth of the total water present, is attached to the coal
by hydrogen bonding at suitable polar functional groups [23].
Gutierrez-Rodriguez et al. [24] suggested that coal structure consists
of three sites with respect to hydrophobicity, i.e. strongly hydropho-
bic, weakly hydrophobic, and hydrophilic sites, and indicated that
the hydrophobicity of coal decreases with decreasing the coal rank
and carbon content and with increasing the oxygen and hydroxyl
content until bituminous coal. This results from the interaction of
moisture with coal surface structure.
Behavior of water in coal depends on many factors such as
intermolecular hydrogen bonding [25], coordination of water mole-
cules to cations [26,27], having short range coherence in their struc-
ture [28], and whether they are in the form of small clusters
[29–31], etc. Arisoy and Akgun [32] classified the water–coal bonds
as the following: adsorbed water by physicochemical forces, free
water held by physicomechanical forces, and chemically bonded
water. Water molecules interact with the surface of coal by hydrogen
bonds with oxygen-containing functional groups [33–37]. The hydro-
gen bonds include the coal intramolecule hydrogen bonds and coal–
water hydrogen bonds formed by carboxyls and hydroxyls in coal
[37]. Kaji et al. [38] found a linear relationship between these hydro-
philic sites and the water-holding capacity of coal. The relationship
between equilibrium moisture content (moisture-holding capacity
of coal) and polar groups is due to the fact that the polar groups
(carboxyl, hydroxyl, and carbonyl) have greater affinity to chemi-
cally bind the moisture, making the surface more hydrophilic [39].
Nishino [35] showed that highly acidic carboxyl groups are the preferen-
tial site of adsorption when compared with other functional groups and
the adsorption of water vapor and carbon dioxide was noted to increase
in proportion to the square root of the carboxyl group concentration,
regardless of the partial pressure or gas.
Svabova et al. [40] observed that there is a linear dependence of
the sum of the hydroxylic and carboxylic groups and the water up-
take of coal, with a high correlation coefficient (R 2 > 0.998). They
found that for low relative pressures, adsorption on primary sites
dominates, while with increasing pressure adsorption on secondary
sites gains in significance. The oxygen-containing functional sites
were considered as primary sites. Secondary site adsorption occurred
when there was binding between a water molecule and a primary site
already occupied by water or water adsorption on previously formed
secondary sites [15]. The percentage of secondary site adsorption de-
pends on the concentration of oxygen-containing functional groups,
because a higher concentration of functional groups supports bridg-
ing of the water molecules. For high oxygen content of coals, the ox-
ygen functional groups are in close proximity to one another,
enabling the formation of water clusters more easily [15]. Main pro-
cesses of water adsorption related to water diffusion on coals are
summarized in Fig. 1. The first process corresponds to sorption of pri-
mary sites, at a low relative pressure. The highest diffusion coefficient
was observed at the beginning of the second process, that is, the for-
mation of water clusters around the functional groups. Afterwards,
increasing relative pressure and decreasing diffusion coefficient, the
water clusters may fill the micropores of coal slowly. Finally, with ad-
ditional adsorption as a result of increased water vapor pressure,
these water clusters grow and finally condense to fill the capillary
pore structure of the coal particles [15,38].
Fig. 1. Adsorption processes of water vapor in coals with increase in relative pressure.
(I) Adsorption on oxygen content sites; (II) H bond between water molecules; (III) formation
of water clusters; and (IV) micropore filling of water clusters and capillary condensation in
narrow pores (Charriere and Behra [15]).
 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20 11

3. Forms of water in brown coal and lignite

The nature of water in coals has been a course of study in the lit-
erature and there is still a need to clarify the terms and data. Water
is retained in low rank coals in several forms, and it is commonly ac-
cepted that water exists in a bound phase and a free phase [41,42]. It
has been found that water present in the coal matrix manifests itself
in different forms. Early research classifies the water in coal as
freezable and non-freezable [43,44]. Mraw and Naas-O'Rourke [43]
postulated that the non-freezable water is incapable of forming crys-
talline ice because it is either adsorbed on the internal surfaces or is in
the smaller pores. The freezable water is the fraction of the water in
larger pores in coal. The apparent freezing temperature of free bulk
water phase is slightly below 0 °C [42]. Fig. 2a shows the specific
heat capacity of coal samples (particle size, 1.2 to 2.5 mm), and the
apparent specific heat capacities of water in coal samples compared
to that of pure water are presented in Fig. 2b. The fusion peak of the
freezable water in coal is rounded which does not behave in the
same way as the pure bulk water does. It can be seen from Fig. 2a
that only a small fraction of the water in the coal resembles bulk
water. Samples containing the larger amounts of water show a
phase transition, and the peaks in these samples are largely rounded
and account only a fraction of the enthalpy change. Fig. 3. Heat of sorption of water on brown coal as a function of moisture content
Allardice and Evans [45] suggested that at least two classes of (Allardice [46]).
water exist in Yallourn brown coal at any particular temperature.
Firstly, water which can be removed by evacuation at that tempera-
ture and secondly chemisorbed water which can be released only water contents of 15 g per l00g dry coal, the heat of desorption in-
by raising the temperature to cause thermal decomposition of func- creases steeply. This increase in heat can be attributed to the desorp-
tional groups. Progressively more of the second type of water is tion of multilayer and then monolayer water which is progressively
released as the temperature is raised. Some but not all of the thermal- more strongly bound to the coal surface as the water content de-
ly released water can be re-adsorbed by exposure to water vapor at a creases [34]. Another classification of water in low rank coals was
lower temperature. This re-adsorbed water can only be desorbed by given by Deevi et el. [21]. Moisture may be held by coals in several
raising the temperature again. distinct forms: superficial free water; capillary condensed water;
Allardice [46] plotted the heat of sorption of water on brown coal sorbed water associated with polar groups and cations; and water re-
as a function of moisture content for both adsorption and desorption leased only by chemical decomposition of organic or inorganic
(Fig. 3). The isosteric heat of desorption is approximately equal to the matter.
heat of vaporization of bulk water [10] at water contents down to More detailed classification of water in coal involves [47,48]: (1) In-
about 60 g per l00g dry coal. This heat suggests that the water terior adsorption water is contained in micropores and microcapillaries
being desorbed in this region is not bound to the coal in any way, within each coal particle, deposited during coal formation; (2) Surface
but is water from the spaces between the coal particles or in large adsorption water forms a layer of water molecules adjacent to coal mol-
pores. In other words the isosteric heat of desorption from the satu- ecules but on the particle surface only; (3) Capillary water is contained
rated to capillary region of the isotherm, is identical to the latent in capillaries; (4) Interparticle water is contained in small crevices
heat of vaporization of pure water [34]. In the region between 60 found between two or more particles; and (5) Adhesion water forms a
and 15 g of water per l00g dry coal the heat of desorption increases layer or film around the surface of individual or agglomerated particles.
gradually. This increase in isosteric heat can be attributed to desorp- Water types (4) and (5) (i.e. surface moisture) can be removed by me-
tion of water from progressively smaller capillaries or pores. Below chanical dewatering methods. Water type (3) can be removed partially,

Fig. 2. (a) The specific heat capacity of samples of Wyodak coal containing the indicated amounts of naturally occurring water [percent defined as the grams of water per 100 g of
dried coal]. (b) The apparent specific heat capacity of the water in the Wyodak coal samples of (a) compared to that of pure water (Mraw and Naas-O'Rourke [43]).
12 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20

depending upon the size of the openings in the coal surface and the dry-
ing temperature. Water types (1) and (2) are inherent moisture and can
be removed by thermal drying processes [8,47]. A similar classification
is given by Dahlstrom et al. [49]. They classified water in coal as
chemisorbed, physisorbed, micro- and macropore water, inter-particle
and intra-particle held water. Overall, the classification method and
terms used in literature for coal moisture and water are not consistent
by different researchers. A coherent classification system and terms
are necessary in order to enhance the future study and technology de-
velopment. The classification system and terms should take into ac-
count the nature of the water as well as the interaction of water and
coal structure.
Two relatively new techniques that have been used to determine
the types of water in coal are proton nuclear magnetic resonance
(NMR) spectroscopy and differential scanning calorimetry (DSC).
The 1H NMR technique [50] determines the mobile and rigid hydro-
gen in coal. The non-freezable water refers to the part of water that
is still liquid at − 3 °C. The thermodynamic properties of this type
of water are modified due to its interaction with the coal structure [5].
DSC may quantify the amount of freezable water in coal from the en-
thalpy change on freezing and hence the amount of non-freezable
water can be calculated [43]. Using DSC, the non-freezable water is
defined as the water that does not freeze down to the lowest temper-
ature attained during analysis [5]. NMR is used by many researchers
to characterize water contained in coal [50–55]. Lynch et al. [50,55]
used 1H NMR technique to measure the relaxation characteristics of
water in coals at a temperature range of 220 K to 300 K. They found
that most of the water associated with brown coal is mobile above
0 °C and not bonded to the surface. They reported a Gaussian-
exponential transition for water at around 273 K. The apparent freez-
ing temperature of the bulk water in coal is a bit below 273 K and de-
creases with heat treatment of the coal [43,50,56,57]. Unsworth et al.
[56] used microwave attenuation, and both pulsed and continuous Fig. 4. DSC thermograms of the coal samples and pure water (Norinaga et al. [57]).
wave NMR techniques to examine the behavior of water in a range
of coals as a function of temperature and water content. Their results
suggested three types of water, i.e., tightly bound water exhibiting around 230 K was reported by Havidt and Borch [27] and Fei et al.
glass-like character at low temperatures (≈−80 °C), more loosely [59]. Apparently, there is a temperature variation by different re-
bound water exhibiting complex behavior between − 20 °C and searchers and not consistent in different reports. This needs to be
0 °C and essentially bulk-like water present in samples with high clarified in future research.
water content. The specific heat of small clusters exhibits a broadened peak cen-
Norinaga et al. [57] used DSC and proton NMR methods to quanti- tered at temperatures below the bulk melting point. When the molecu-
fy different types of water in various coals ranging from brown coal to lar cluster is too small (less than 10 molecules) the peak shifts towards
bituminous on the basis of congelation characteristics of sorbed lower temperatures and water becomes non-freezable. As the cluster
water. Two different types of freezable water were found in their size increases, the peak tends to sharpen and shift closer to bulk melting
DSC results, namely, free water and bound water, and these two point [30,31]. In such an environment on molecular scale, water con-
types of water were quantified from their experimental heat of con- denses in micropores and/or bounds to specific sites (acidic sites)
gelation. These two types of freezable water account for 35–78% of through hydrogen bonds. Each strong acid site has one very strongly
the total moisture content; the rest was defined as the non-freezable bound water molecule attached with another 10 or so molecules to
water. Fig. 4 shows the DSC curves for pure water and the coal sam- form water molecule–strong acid complex [30,57]. Hayashi et al. [58]
ples under cooling. The positive peaks appearing in the thermograms proposed a slit-like model for pores that are filled with pore water, as
were the result of exothermic congelation processes. Two exothermic can be seen in Fig. 5. They assumed that pores filled with the water
peaks are detectable in DSC thermograms for Yallourn (YL), Morwell are slit-like rather than cylindrical in shape. They detected and quanti-
(MW) and Loy Yang (LY) coals during cooling indicating two different fied the proton of free water, pore-condensed water and mobile coal
freezable waters in these coals. The larger peak centered at 258 K is proton based on their different relaxation times in 1H NMR to estimate
for pure water and accounts for free freezable water. The smaller the size of pores in moist coals on the basis of the nuclear magnetic res-
peaks centered at 226 K are indicative of water condensed in capil- onance relaxation characteristics. They measured the dimensions of
laries. Bound water and non-freezable water are present in pores pores for the raw Yallourn and Beulah Zap colas as about 3 and 2 nm,
with diameters smaller than 10 nm [58]. They measured the quantity respectively. The non-freezable water is non-separable from the
of heat, ΔH, as a function of water content and obtained values of bound water unless the latter type of water freezes. They found that
333 J/g water for the 258 K peak and 188 J/g water for 226 K peak. the pore dimension decreases with the content of pore water roughly
They reported that the amount of freezable water determined by in a linear manner [58]. This implies that pore structure of coal is strong-
NMR was in good agreement with DSC results. The congelation of ly correlated to water and its nature and will change as coal water is re-
freezable water in NMR was the conversion of slowly decaying com- moved progressively, as discussed in the following section.
ponents into a Gaussian one at 213 K to 273 K. The congelation heat Allardice et al. [5] used a range of techniques to characterize the
of capillary-condensed water is less than that of bulk water and this forms of water in Victorian brown coals and their hydrothermally
kind of water is referred as “bound water” [42,57]. Similar peaks dried (HTD) products. They found that non-freezing water was higher
 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
Fig. 5. Model of slit-like pores of moistened coal: The mobile coal protons are identical with those of hydroxylic groups. All of the hydroxylic groups are solvated by pore water at
pore surface (Hayashi et al. [58]).
for dark lithotypes than for the pale lithotypes and for the HTD prod-
ucts decreased with increasing drying severity. They observed that
the DSC results for nonfreezing water were on average 12% greater
than those measured through 1H NMR technique. This may be due
to the underestimation of freezing water by DSC, because DSC as-
sumes that the latent heat of fusion of all the water present in the
coal is equal to that of bulk water. A similar difference was also
reported by Baron and Lynch [55]. They also compared the
non-freezing water contents of the coals and HTD products with the
equilibrium moisture values. The value for non-freezing water was
the equilibrium moisture content at an almost constant relative hu-
midity of ca. 93% for coals and ≥ 96% for the HTD products. These
values are lower than 96–100% relative humidity for bituminous
coals [55]. The amount of water lost at relative humidities greater
than 93% (ca.) is similar to bulk water. The monolayer water (strongly
bound water) for Loy Yang (low ash) coal was estimated to be 6.5 g
per 100 g coal (d.b.), corresponding to the equilibrium moisture con-
tent at a relative humidity of 21% at 30 °C. The total amount of
non-freezing water is approximately a factor of 10 greater than the
amount of strongly bound (monolayer) water adsorbed at 15–20%
relative humidity [5]. The monolayer water content for Yallourn
coal corresponded to the equilibrium moisture content at a relative
humidity of 19% at 30 °C [34]. FTIR technique was also used by Mu
and Malhotra [60] coupled with desorption approach to study coal–
water interactions. They observed different desorption kinetics for
four O―H stretch vibrations, suggesting various desorption pathways
for various types of water. The absorbance loss of small water clusters
trapped between particles, liquid type water, hydrogen bonded water
to C O groups, and strongly hydrogen bonded water were associated
with 3618, 3395, 3210, and 3078 cm −1 wave lengths respectively.
Different types of water had different desorption kinetics.
4. Coal structure change during moisture loss and re-adsorption
4.1. Physical structure changes
Physical structure changes have been studied extensively in the lit-
erature and many researchers have reported that coals have gel-like
structures that shrink and swell in response to water loss and uptake
[21,22,43,54,61–68]. Evans [62] studied the drying behavior of Yallourn
brown coal containing 200 g of water per 100 g dry coal. It was ob-
served that the water in large pores was first removed by evaporation,
followed by those in the larger capillaries, but collapse of the coal struc-
ture is relatively small during this stage. By the time the moisture
13
content has dropped to about 40 g per l00g dry coal (water held in cap-
illaries of diameter 120 down to 5 nm) the shrinkage forces caused by
emptying such small capillaries cause their complete collapse. As the
multilayer sorbed water is removed, stronger hydrogen-bond bridges
between micelles cause the open gel structure to collapse, resulting in
more intensive shrinkage. The maximum shrinkage that occurs at a
moisture content of 16 g per l00g dry coal, corresponds to two water
molecular layers surrounding each micelle [20]. Mraw and O'Rourke
[42] suggested that amount of strongly held moisture in a lignite and
a subbituminous coal is not much affected by a drying cycle, and that
it may be the ‘medium-sized’ water clusters which are reduced in num-
ber, implying irreversibility of pore structures. During re-adsorption,
they observed that drying process has altered the original pore struc-
ture of the lignite, such that there were relatively few small- and
medium-size water clusters present in the reabsorbed water. This was
due to the “pore collapse” in the gel-like structure of the lignite
[20,62,69,70]. The reduction of the porosity of coal was induced by the
shrinkage in macropores [71]. Another aspect of coal pore structure is
the interconnection of pores. Kelemen et al. [68] defined a ratio (i.e. the
ratio of the surface area reflected by the quantity of equilibrated slow re-
versible pentane adsorption to the BET CO2 surface area) of 1.0 corre-
sponding to a completely unconnected pore network, and a ratio of 0.0
corresponding to a completely interconnected pore network. The range
of this ratio was 0.46–0.73 for coal dried under vacuum at room temper-
ature. This indicates that interconnection among pores is incomplete for
coals they have investigated [72,73]. They postulated that drying at
150 °C significantly alters the connectivity of the pore structure network
of coal. However, more detailed quantitative information is required to
confirm the change of the connectivity of pore structure caused purely
by drying.
The porous structure of low rank coals mainly comprises of meso-
and macropores, and these coals have higher mesopores than
macropores [74]. The surface area of the low rank coals is predominant-
ly controlled by the mesopores [71]. Androutsopoulos and Linaros [67]
investigated the effect of drying upon the macro- and partly mesopore
structure of Greek lignite. They observed considerable particle contrac-
tion (by ~1/3 of its original size), a minor decrease in the macro- and
partly mesopore volume and a marked increase in the relevant surface
area during lignite drying. They also found the formation of pores in the
size range 7.5–150 nm at the expense of pores in the range
150–1000 nm as coal moisture is progressively removed. Pore shrink-
age and pore emptying occurred due to the counteraction of particle
contraction and moisture removal. Salmas et al. [14] found that
mesopore structure evolves at temperatures ranging from ambient to
14 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
200 °C despite particle size shrinkage during thermal drying of Greek
lignite. However, thermal treatment of lignite at temperatures above
200 °C resulted in the decline of mesopore and surface area, even
though there was slight increase in weight loss.
Deevi and Suuberg [21] investigated the effect of different drying
severity, i.e. the extent of drying, on the physical properties of four
North Dakota lignites. They observed irreversible shrinkage of coal
during drying, even when drying was not complete. The shrinkage
of the samples was associated mainly with collapse of macroporosity
and so-called transitional porosity. Nitrogen adsorption revealed a
fairly clear trend of increased pore collapse and decreased surface
area with increasing the extent of drying in the range of transitional
porosity (2–18 nm range). CO2 adsorption showed an opposite
trend to that for N2 surface areas. This is because carbon dioxide re-
veals mainly microporosity (b2 nm) and it is likely that during drying
as larger pores empty and collapse, they add to the already existing
microporous volume, which existing volume also becomes more ac-
cessible to CO2 as it loses water. They concluded that irreversible
shrinkage of the samples is associated mainly with collapse of
macroporosity and transitional porosity [61]. Fig. 6a shows atypical
irreversible loss of moisture from bed moist state of Indonesian lig-
nite implying the collapse of pore structure during drying [70]. This
is attributed to shrinkage which alters the structure of a low rank
coal as a colloidal gel. Typical moisture re-adsorption curves for
dried coal samples are shown in Fig. 6b. In the atmosphere with a rel-
ative humidity 75% at 30 °C, the dried coal tends to equilibrate with
the atmosphere at the moisture content of approximately 13%, re-
gardless of its original moisture content. The raw coal tends to equil-
ibrate with the atmosphere at approximately 20% which is higher
than that of the dried coal samples. This also implies that irreversible
structure changes of the coal have taken place during drying.
Charriere and Behra [15] have constructed the adsorption/desorption
isotherms of water vapor for a high volatile bituminous B rank and a lig-
nite coal. Fig. 7 shows different adsorption capacities and isotherm
shapes for two coals. After the initial desorption the process seems to
be reversible. Hysteresis is seen in water adsorption/desorption iso-
therms for both coals. The hysteresis is caused by the limitation of
water access to the pore structure of the coal. Cross-linking reactions
may have sealed pores or limited the ability of collapsed pores to be ex-
panded on water re-adsorption [75]. Albert (high volatile bituminous)
coal and Grande Mine (lignite) coal had 10.7% and 25.1% oxygen content,
respectively. Taking into account that water cluster concentration is di-
rectly related to the density of oxygen-containing functional groups
[35], the greater extent of low pressure hysteresis for Grande Mine coal
than Albert coal was explained. Hysteresis for several coals of different
ranks has been reported by other researchers [33,76–79]. McCutcheon
et al. [77] postulated that there are two distinct types of water adsorp-
tion/desorption hysteresis, namely the low-pressure hysteresis that is
associated with coal swelling and the high-pressure hysteresis which is
Fig. 6. (a) Moisture desorption and re-adsorption isotherms, (b) re-adsorption behavior of the Indonesian low rank coal. Particle size b 1.0 mm, 30 °C, relative humidity (RH) 75%
(Li et al. [70]).
Fig. 7. Adsorption/desorption isotherms for water vapor on Albert (high vol. bit. B) and
Grande Mine (lignite) coals at 298 K. Closed and open symbols denote adsorption and
desorption, respectively (Charriere and Behra [15]).
attributed to “ink bottle” type pore structure. Low pressure hysteresis
has been attributed to the variation of coal structure in the presence of
water and it correlates substantially better with coal oxygen content
[15,77,78]. The “ink bottle” types of pores have restricted openings and
diminish as coal rank increases. The pressure exerted by water clusters
causes coal swelling at high relative pressure [76].
Suuberg et al. [22] found that the volumetric shrinkage of coals
ranging from bituminous to lignite was excellently correlated with
the moisture loss of coal at 373 K, as can be seen in Fig. 8. Lower
rank coals collapse to a significant extent like ordinary colloidal gels.
They argued that the creation of open porosity during drying occurs
to a limited extent in lignites and open porosity already exists in
higher rank coals. The more severe lignite is dried, the more its poros-
ity would collapse and the lower the apparent surface area would be
[80]. Similar results have been reported for low rank coals dried by
non-evaporative methods. Favas and Jackson [81] used hydrothermal
dewatering (HTD) process to study the effect of process conditions on
drying of Loy Yang brown coal. The process temperature had a signif-
icant effect on the product intraparticle porosity, which decreased
with increasing temperature. Similar results were reported by Fei et
al. [82]. CO2 adsorption surface area decreased with increasing tem-
perature. However, the pore volume as determined by mercury
porosimetry was influenced by whether dewatering is done by Me-
chanical Thermal Expression (MTE). The mechanical pressure applied
in the MTE process resulted in a lower porosity. Hulston et al. [83] ob-
served the decrease in total pore volume with increasing MTE tem-
peratures and pressures. This was caused by the progressive
collapse of macropores, which was associated with a slight increase
in mesopore volume. Some of the macropores were converted into
mesopores probably through deformation of pore shape [83,84]. In
 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
Fig. 8. Volumetric shrinkage upon drying for coals of various ranks ranging from bitu-
minous to lignite. All drying experiments performed in a 373 K vacuum oven (Suuberg
et al. [22]).
contrast, the MTE process had little effect on the micropore volume
and surface area. Fig. 9 shows the effect of MTE pressure and temper-
ature on the macro-, meso- and micropore volumes of Loy Yang
brown coal. The moisture holding capacity of MTE treated coal de-
creased approximately linearly with increasing temperature, and de-
creased significantly with increasing pressure.
Gorbaty [85] investigated the effect of drying on metal ion ex-
change from aqueous solutions. Using an as-received and a dried sub-
bituminous coal, he found that drying is deleterious to ion exchange.
They used two hypotheses to describe this difference. One is that dur-
ing drying, the collapse of gel structure of coal caused the pores to
collapse [20,62,69]. The other is that when coal is dried, the drying
gas occupies the volume used to be occupied by water. The wetting
properties of the pore surfaces change after drying due to these ef-
fects and may prevent or considerably decrease wetting of dried
coal with water solution. Suuberg et al. [22] found that the presence
of moisture in coals significantly enhance the rate of uptake of sol-
vents by the coal. The process of drying or heat treatment of coal at
temperatures above 373 K can significantly decrease the solvent up-
take by the coal. Water acts as a plasticizing solvent for coal, enhanc-
ing transport of solvent by helping to pre-relax the surface structure
at lower temperatures.
Fig. 9. Effect of MTE temperature and pressure on the macro-, meso- and micropore
volumes of oven-dried LY brown coal MTE products (Hulston et al. [83]).
15
4.2. Chemical structure changes
The change in chemical nature of the coal surface is reported to be
predominantly in the formation and/or destruction of the oxygen-
containing polar functional groups (including carboxyl, hydroxyl,
and carbonyl). Decrease in the polar groups will cause a decrease in
the oxygen content and moisture-holding capacity of the coal
[38,71,86–88] which results in the decrease of coal tendency towards
spontaneous combustion. The destruction of oxygen containing func-
tional groups caused by heat treatment of low rank coals will increase
hydrophobicity of these types of coals [89]. Oxygen is removed in the
form of water and carbon dioxide generated by decomposition of ox-
ygen containing functional groups upon drying at elevated tempera-
ture [88]. Murray and Evans [23] thermally treated Yallourn and
Morwell brown coals in water under pressure to temperatures of
150 to 300 °C and measured the yields of organic functional groups
and inorganics in the product. Fig. 10 shows the yield of oxygen func-
tional groups as a function of drying temperature. Phenolic groups
start to break down at 150 °C. Above 200 °C this breakdown becomes
very significant. Alcoholic groups break down at temperatures above
200 °C (Fig. 10a). The main product of decomposition of both these
groups is mainly water. Free carboxylic acid groups are stable up to
150 °C and decompose thereafter (Fig. 10b). Fig. 10c shows a small
and steady breakdown of carboxylate groups from room temperature
to 200 °C, with more intense breakdown after 200 °C. The decompo-
sition of these groups mainly yields carbon dioxide [90,91]. Carbonyl
groups are stable up to 150 °C (Fig. 10d), but decompose thereafter,
leading to the formation of the carbon monoxide and probably
some carbon dioxide as well. Saikia et al. [92] observed the loss of
O―H and C O groups after thermal treatment in 250 °C in air. Shui
et al. [93] reported similar results suggesting the decreases in the
self-associated O―H hydrogen bonds and carbonyl bands of steam
treated Chinese subbituminous coals up to 250 °C. In more recent
work by the authors [94,95], the chemical structure changes accom-
panying drying of a Chinese lignite in superheated steam, hot air
and microwave were analyzed using the FTIR technique. It has been
Fig. 10. Effect of treatment temperature on yields of oxygen functional group: (a) hydroxyl;
(b) free carboxylic acid; (c) carboxylate; (d) carbonyl. ●Yallourn, ○Morwell No.1 cut,
■Morwell No.5 cut (Murray and Evans [23]).
16 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
observed that the absorption of carboxyl (COOH) and carbonyl (C= O)
groups decreased with increasing drying temperature, indicative the
progressive loss of oxygen functional groups with increasing drying in-
tensity during superheated steam drying (Fig. 11). Similar results were
reported by Sakaguchi et al. [86] and Mahidin et al. [71]. The progressive
decomposition of carboxyl groups has also been reported by Murakami
et al. [96]. Increasing microwave output level (increasing drying inten-
sity) gives similar results, as shown in Fig. 11. Aromatic ring stretch and
aromatic carbon remained relatively unchanged up to 250 °C and de-
creased significantly thereafter when coal was heated under steam.
Aromatic carbon remained relatively unchanged during microwave
drying even at maximum output power of 700 W. Under both super-
heated steam and microwave the loss of oxygen functional groups
resulted in progressive increase in aromaticity of coal. The absorption
of aliphatic hydrogen content decreased significantly when coal was
heated in air at 250 °C [94,95]. The aromatic carbon remained
unchanged during air drying, implying that oxygen in air reacts mainly
with aliphatic structure to produce oxygen functional groups. Progres-
sive decrease in CH3/CH2 ratio indicated that methylene structures
were the most active sites on coal structure to react with oxygen. Car-
boxyl and carbonyl groups increased significantly with increasing
drying temperature from 150 to 200 °C. The evolution of CO2 at temper-
atures near 100 °C in coal pyrolysis and drying is reported by other re-
searchers [97–99] while other studies observed the release of H2O and
CO2 at 110 °C [90,98,100]. These results suggest that alteration of chem-
ical structure in particular the oxygen-containing functional groups are
significant during drying of brown coal and lignite.
The removal of water has a profound influence on the concentration
and nature of the radicals present in brown coals upon drying. Wet coal
under nitrogen atmosphere showed typical free-radical concentration
increases of the order 10–20% over the time period of drying [91].
Their study suggested that vacuum drying at temperatures up to
150 °C may enhance the increase in free-radical content. Over the tem-
perature range studied, they found that the process of vacuum drying
appears to involve functional group breakdown, resulting in carbon di-
oxide evolution and free-radical formation [23,45,100,101]. Goldberg
et al. [102] reported similar results and indicated that the rates of evolu-
tion of these species were strongly dependent on the chemical nature of
the coal and the temperature history of sample. The changes in radical
Fig. 11. Evolution of carboxyl group (Left) and carbonyl groups (right) absorption as a function of drying temperature in superheated steam, microwave and air [94].
concentrations and species depend on decarboxylation and the removal
of moisture from heteroatomic sites within the coal macrostructure. Due
to the chemical changes, the removal of coal moisture has significant ef-
fects on coal oxidation [103–108]. Oxygen reactivity of the coal samples
is found to be directly related to the initial free radical concentration
[109]. Coal reacts with oxygen more rapidly when wet than when dry
[103,104]. This is because water could act as chain carrier to make
chain reactions possible by forming peroxide intermediates. Opposing
the view point that water enhances oxidation, it has also been suggested
that stripping moisture from coal would expose more fresh active sites
on the coal surface for contacting oxygen and therefore accelerate oxida-
tion [105]. Chen and Stott [106] and Berkowitz [110] argued that the
drying process exposed more active sites to promote oxidation until a
certain degree of drying. Oxidation rates decrease as the coal moisture
is removed further. This is attributed to the lesser amount of water avail-
able for the rapid formation of peroxide complexes.
5. Effects of moisture on utilization of low rank coals
Water in high-rank coal is less important because moisture con-
tent in black coals is very low and does not pose problems to their
use [111]. However, water in low rank coals exerts significant effects
in their utilization processes, including combustion, gasification and
liquefaction. The high moisture content results in lower efficiency, in-
creased transportation cost and higher carbon emission. On the other
hand low rank coals have the advantages of low mining cost, high re-
activity, high volatile matter content, and low content of pollution-
forming impurities such as sulfur, nitrogen and heavy metals [4,112].
The use of pre-dried low rank coals is one possibility of increasing
the efficiencies of low rank coal fired utility boilers. As a mean value,
an increase of 2–4% in power plant efficiency can be achieved
[6,113–115]. Drying of LRC at mining sites can result in major savings
in transportation costs. Coal producers can save $0.19/GJ of energy on
storage, handling, and transportation costs if LRC is dried from 35% to
25% moisture content and the savings on logistics costs could be as
high as $7 million per year for a 600 MW power plant [116,117].
With reduced water content, the flame temperatures increase faster
and reach a higher absolute level which leads to modified pyrolysis
and char burnout characteristics [114]. Agraniotis et al. [118] reported
 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
a temperature increase of up to 200 K in the near burner zone and up
to 80 K in the furnace exit region by simulating dry coal firing. The
lower flame temperature may have a beneficial effect in reducing ni-
trogen oxide formation during combustion, meanwhile results in a
larger and more capital intensive plant compared with black coal
fired units of similar capacity [115,63]. Co-firing dry lignite in existing
power plants is feasible without exposing the boilers' operational be-
havior at risk [118].
Low rank coals are particularly suitable for gasification due to their
high gasification reactivity [119] even at lower temperatures. However,
in order to achieve high thermal efficiency for reducing greenhouse gas
emissions, water removal will have to be an integral part of
gasification-based technologies using low rank coals with high mois-
ture content. Zeng et al. [120] investigated the effects of MTE
dewatering on the pyrolysis and gasification reactivity of Victorian
brown coal. They found that dewatering at elevated temperatures
(>250 °C) partially degraded brown coal structure, leading to stronger
covalent bonds formed during pyrolysis (cross-linking) that require
higher temperature to break down [121]. They postulated that changes
in pore structure and chemical structure during dewatering have little
effect on char gasification reactivity [120]. The comparison of the pyrol-
ysis behavior of steam treated and helium treated Victorian brown coal
suggested that the pretreatment in steam at temperatures above 250 °C
resulted in lower tar yields during the subsequent pyrolysis at both fast
and slow heating rates. Hydrolysis of carboxylates and oxygen
containing functional groups played important roles in enhancing the
thermal decomposition of brown coal during steam treatment and in
promoting cross-linking reactions during the subsequent pyrolysis of
the steam-pretreated coal [122]. Both of these reactions led to decreases
in tar yields. Increasing the steam pretreatment temperature above
250 °C resulted in significant increases in the char yield. In that regard,
it is important to carefully select drying process and parameters for
brown coal drying before gasification. Meanwhile, it is left to discussion
whether low rank coals need to be dried if steam is used as the gasifica-
tion agent in the subsequent gasification process.
Drying low rank coals prior to liquefaction may eliminate the par-
tial pressure of steam and increases the partial pressures of hydrogen
and other gaseous components. Meanwhile, reaction at liquefaction
temperature between coal moisture with side chains in coal structure
may enhance the formation of oils and hydrocarbon gases [123,124].
Therefore, coal conversion during liquefaction is strongly dependent
on drying method. Miknis et al. [13] investigated the effect of differ-
ent drying methods (included thermal and microwave drying at ele-
vated temperatures and chemical drying at low temperature) on
reactivity of coals toward liquefaction. The conversion is consistent
with changes in the physical structure and cross-linking reactions be-
cause of drying methods. Coals that were dried thermally and with
microwaves had lower liquefaction conversions than coals containing
equilibrium moisture contents [11,13,124–126]. The reason being
that thermal and microwave drying caused a collapse in the pore
structure, thus preventing hydrogen donor solvents from contacting
reactive sites inside the coals, i.e. reducing the diffusion through
pore systems during liquefaction. Steam drying may promote the re-
activity of coal during liquefaction. Some studies [93] reported the en-
hancements of extraction yields after steam treatment at 200 °C and
suggested that the decrease in self-associated ―OH hydrogen bonds
in macromolecular network of coal due to removal of oxygen groups
enhanced the breakage of the coal macromolecules and allowing the
formation of much more hydrocarbon. Saini et al. [127] compared
the liquefaction residues of air-dried and vacuum-dried coal and
found that residues from the air-dried coal were more aliphatic and
carbonyl rich compared to the vacuum dried coal. The increase in
the carbonyls was due to the oxidation of the coal upon air-drying.
Oxidation of coal at 100 °C caused the retention of shorter chain ali-
phatics in the coal network as compared to the vacuum-dried coal.
They concluded that the enhanced conversion of the unoxidized
17
raw coal was due to the enhanced loss of carbonyls upon reacting
with water. Miknis et al. [128] investigated the effect of microwave dry-
ing of coal on its reactivity toward liquefaction. They observed that dry-
ing coal with microwaves beyond 75% moisture removals had a
detrimental effect on the reactivity toward liquefaction. Removal of
the remaining moisture caused a rapid temperatures rise during drying
[126,129]. Beyond 75% moisture removal, the additional moisture that
is removed is an integral part of the gel or pore structure of the coal.
These water molecules have a more difficult time aligning and
realigning with the radiation field, and thus would cause heating to
higher temperature, and possible disruption of part of the coal matrix
enabling some retrograde reactions to take place that diminish the reac-
tivity toward liquefaction [128,129]. However, chemically dried coals
had conversions greater than the pre-moisturized coals. During chemi-
cal drying processes, methanol was incorporated into coal pore struc-
tures to replace water, thus preventing formation of cross-links and
collapse of the pore structures during the dehydration reaction [130].
Therefore, chemical drying is more suitable from the view point of liq-
uefaction of low rank coals.
Another important effect of inherent moisture in low rank coals is
its role in low temperature oxidation of coal during storage, transpor-
tation, as well as in the waste dump from mining operations [131]. A
four stage coal oxidation process in proposed in literature which is
reviewed by Wang et al. [132], i.e., oxygen transport to the surfaces
of coal particles (convective mass transfer from the bulk to the film
surrounding a particle followed by the diffusive mass transfer in the
film) and within coal pores (pore diffusion); chemical interaction be-
tween coal and O2; and release of heat and emission of gaseous prod-
ucts. Both retarding and promoting roles of inherent water is
reported in literature [133–136]. Inherent water affects the oxygen
consumption at the active adsorption sites on coal structure and the
formation of intermediates (peroxides and hydroperoxides) at the
early stages of oxidation [132]. A minimum amount of water is re-
quired to act as the catalyst and reactant in interaction between
coal and oxygen [110,137]. There is a critical water content at which
the rate of oxygen uptake is at its maximum [134,106]. Wang et al.
[138] postulated that the values of critical water content correspond
to the monolayer capacities of coals of different ranks. The active
sites on coal structure become exposed to oxygen molecules when
the physically adsorbed (multilayer) water is removed. At this mois-
ture level, water encourages faster oxidation by preventing the for-
mation of stabilized radicals, although some of the extra heat may
be taken up by the residual moisture [134]. At moisture contents
above the critical moisture content loosely bound water condensed
in pores inhibits the oxygen diffusion towards the reaction sites in
coal pores and therefore retards the oxidation process [132,134]. On
the other hand, drying the coal to lower moisture content than the
critical moisture content will also slow down the oxidation process,
as water molecules are required in chemisorptions process of oxygen
on active sites to form peroxides and hydroperoxides. Further infor-
mation on low temperature oxidation of coal can refer to the litera-
ture [132,139,140].
6. Summary remark
Water–coal interactions are very complicated and water exists in
low rank coals in different forms. Terms such as freezable and
non-freezable, free water, surface water, bulk water, capillary water,
inherent, hygroscopic, combined or bound water have been used to
define the forms of water in coal. The different forms of water in
coal behave differently during thermal treatment or cooling, as ana-
lyzed by techniques such as NMR and DSC and coal–water interac-
tions are complicated. A coherent classification system and terms of
coal water are necessary in order to enhance the future research
and technology development and should take into account the nature
of the water as well as the interaction of water and coal structure.
18 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
Coals undergo chemical and physical changes upon drying. The
gel-like structure of brown coal shrinks in response to loss of mois-
ture. Considerable shrinkage takes place during drying of low rank
coals. Macropore and mesopore volume decreases due to pore col-
lapse when water is progressively removed and adds to micropore
volume of coal. The pore collapse is the main reason of irreversible
loss of moisture in low rank coals. The change in chemical nature of
the coal surface is due predominantly to the destruction of the
oxygen-containing polar functional groups upon drying. Decrease in
the polar groups cause a decrease in the moisture-holding capacity
of the coal.
Acknowledgments
This study was supported by the Natural Science Foundation of
China (21176109 and 20976106) and the authors wish to acknowl-
edge the financial support of the Australia–China Joint Coordination
Group on Clean Coal Technology Research and Development Grants.
References
[1] T. Nicholls, Coal: Explained, in: T. Nicholls (Ed.), How the Energy Industry
Works: An Insiders' Guide, Silverstone Communications Ltd., London, 2009,
pp. 111–112.
[2] D.J. Allardice, The Water in Brown Coal, in: R.A. Durie (Ed.), The Science of Vic-
torian Brown Coal, Butterworth-Heinemann, Oxford, 1991, pp. 102–150.
[3] S.V. Jangam, M. Karthikeyan, A.S. Mujumdar, A critical assessment of industrial
coal drying technologies: role of energy, emissions, risk and sustainability, Dry-
ing Technology 29 (2011) 395–407.
[4] W.G. Willson, D. Walsh, B.W. Irwin, Overview of low-rank coal (LRC) drying, In-
ternational Journal of Coal Preparation and Utilization 18 (1997) 1–15.
[5] D.J. Allardice, L.M. Clemow, G. Favas, W.R. Jackson, M. Marshall, R. Sakurovs, The
characterisation of different forms of water in low rank coals and some hydro-
thermally dried products, Fuel 82 (2003) 661–667.
[6] G. Domazetis, P. Barilla, B.D. James, R. Glaisher, Treatments of low rank coals for
improved power generation and reduction in greenhouse gas emissions, Fuel
Processing Technology 89 (2008) 68–76.
[7] M. Karthikeyan, J.V.M. Kuma, C.S. Hoe, D.L.Y. Ngo, Factors affecting quality of
dried low-rank coals, Drying Technology 25 (2007) 1601–1611.
[8] M. Karthikeyan, W. Zhonghua, A.S. Mujumdar, Low-rank coal drying technolo-
gies—current status and new developments, Drying Technology 27 (2009)
403–415.
[9] J.I. Ozaki, Y. Nishiyama, P.J. Guy, G.J. Perry, D.J. Allardice, Role of carboxyl groups
in the disintegration of brown coal briquettes by water sorption, Fuel Processing
Technology 50 (1997) 57–68.
[10] K.S. Vorres, D.L. Wertz, V. Malhotra, Y. Dang, J.T. Joseph, R. Fisher, Drying of Beu-
lah–Zap lignite, Fuel 71 (1992) 1047–1053.
[11] C. Song, A.K. Saini, H.H. Schobert, Effects of drying and oxidation of Wyodak sub-
bituminous coal on its thermal and catalytic liquefaction. spectroscopic charac-
terization and products distribution, Energy & Fuels 8 (1994) 301–312.
[12] T.K. Gale, T.H. Fletcher, C.H. Bartholomew, Effects of pyrolysis conditions on in-
ternal surface areas and densities of coal chars prepared at high heating rates in
reactive and nonreactive atmospheres, Energy & Fuels 9 (1995) 513–524.
[13] F.P. Miknis, D.A. Netzel, T.F. Turner, J.C. Wallace, C.H. Butcher, Effect of different
drying methods on coal structure and reactivity toward liquefaction, Energy &
Fuels 10 (1996) 631–640.
[14] C.E. Salmas, A.H. Tsetsekou, K.S. Hatzilyberis, G.P. Androutsopoulos, Evolution
lignite mesopore structure during drying. effect of temperature and heating
time, Drying Technology 19 (2001) 35–64.
[15] D. Charriere, P. Behra, Water sorption on coals, Journal of Colloid and Interface
Science 344 (2010) 460–467.
[16] S. Murata, M. Hosokawa, K. Kidena, M. Nomura, Analysis of oxygen-functional
groups in brown coals, Fuel Processing Technology 67 (2000) 231–243.
[17] E. Stach, M. Mackowski, M. Teichmuller, G.H. Taylor, D. Ghandra, R. Teichmuller,
Stach'e Textbook Of Coal Petrology, Gebruder Borntaeger, Berlin, 1982.
[18] O.I. Olayinka, Thermal upgrading effect on oxygen distribution in lignite, Fuel
Processing Technology 34 (1993) 73–81.
[19] B. Alpern, M.J.L.d. Sousa, D. Flores, A progress on the Alpen coal classification, In-
ternational Journal of Coal Geology 13 (1989) 1–19.
[20] D.G. Evans, Effects of colloidal structure on physical measurements on coals,
Fuel 52 (1973) 155–156.
[21] S.C. Deevi, E.M. Suuberg, Physical changes accompanying drying of western US
lignites, Fuel 66 (1987) 454–460.
[22] E.M. Suuberg, Y. Otake, Y. Yun, S.C. Deevi, Role of moisture in coal structure and
the effects of drying upon the accessibility of coal structure, Energy & Fuels 7
(1993) 384–392.
[23] J.B. Murray, D.G. Evans, The brown-coal/water system: part 3. thermal
dewatering of brown coal, Fuel 51 (1972) 290–296.
[24] J.A. Gutierrez-Rodriguez, R.J. Purcell Jr., F.F. Aplan, Estimating the hydrophobici-
ty of coal, Colloid and Surfaces 12 (1984) 1–25.
[25] A.C. Zettlemoyer, F.J. Micale, K. Klier, in: F. Franks (Ed.), Water A Comprehensive
Treatise: Water in Disperse Systems, Plenum, New York, 1975, pp. 249–291.
[26] V.P. Tayal, Librational modes of crystal water in hydrated solids, Applied Spec-
troscopy Reviews 16 (1980) 43–134.
[27] A. Hvidt, K. Borch, NaCl–H2O systems at temperatures below 273K, studied by
differential scanning calorimetry, Thermochimica Acta 175 (1991) 53–58.
[28] R. Mu, V.M. Malhotra, Y.P. Chugh, in: Y.P. Chugh, R.D. Caudle (Eds.), Processing
and Utilization of High Sulfur Coals, Elsevier, New York, 1987, pp. 94–106.
[29] H.R. Carlon, Do clusters attribute to the infrared absorption spectrum of water
vapor? Infrared Physics 19 (1979) 549–557.
[30] L.M. Clemow, W.R. Jackson, A.L. Chaffee, R. Sakurovs, D.J. Allardice, in: M. Marato–
Valer, S. Song (Eds.), Understanding Brown Coal–Water Interactions to Reduce
Carbon Dioxide Emissions, Kluwer Academic/ Plenum Publishers, New York, 2002,
pp. 203–250.
[31] P. Sheng, R.W. Cohen, J.R. Schrieffer, Melting transition of small molecular clus-
ters, Journal of Physics C: Solid State Physics 14 (1981) 565–569.
[32] A. Arisoy, F. Akgun, Modelling of spontaneous combustion of coal with moisture
content included, Fuel 73 (1994) 281–286.
[33] O.P. Mahajan, P.L. Walker, Water adsorption on coal, Fuel 50 (1971) 308–317.
[34] D.J. Allardice, D.G. Evans, The brown-coal/Water system. part 2. water sorption
isotherms on bed–moist Yallourn brown coal, Fuel 50 (1971) 236–253.
[35] J. Nishino, Adsorption of water vapor and carbon dioxide at carboxylic function-
al groups on the surface of coal, Fuel 80 (2001) 757–764.
[36] N. Qi, D. LeVan, Adsorption equilibrium modeling for water on activated car-
bons, Carbon 43 (2005) 2258–2263.
[37] K. Miura, K. Mae, W. Li, T. Kusakawa, F. Morozumi, A. Kumano, Estimation of hy-
drogen bond distribution in coal through the analysis of OH stretching bands in
diffuse reflectance infrared spectrum measured by in-situ technique, Energy &
Fuels 15 (2001) 599–610.
[38] R. Kaji, Y. Maranaka, K. Otsuka, Y. Hishinuma, Water absorption by coals: effect
of pore structure and surface oxygen, Fuel 65 (1986) 288–291.
[39] Y. Kadioglu, M. Varamaz, The effect of moisture content and air–drying on spon-
taneous combustion characteristics of two Turkish lignites, Fuel 82 (2003)
1685–1693.
[40] M. Svabova, Z. Weishauptova, O. Pribyl, Water vapour adsorption on coal, Fuel
90 (2011) 1892–1899.
[41] I.J. Lynch, D.S. Webster, Effect of thermal treatment on the interaction of brown
coal and water: a nuclear magnetic resonance study, Fuel 61 (1982) 271–275.
[42] S.C. Mraw, D.F. O'Rourke, Water in coal pores: the enthalpy of fusion reflects pore
size distribution, Journal of Colloid and Interface Science 89 (1982) 268–271.
[43] S.C. Mraw, D.F. Naas-O'Rourke, Water in coal pores: low-temperature heat ca-
pacity behavior of the moisture in Wyodak coal, Science 205 (1979) 901–902.
[44] K.S. Vorres, Effect of temperature, sample size, and gas flow rate on drying on
Beulah–Zap lignite and Wyodak subbituminous coal, Energy & Fuels 8 (1994)
320–323.
[45] D.J. Allardice, D.G. Evans, The brown–coal/water system. Part 1. The effect of
temperature on the evolution of water from brown coal, Fuel 50 (1971)
201–210.
[46] D.J. Allardice, The Water in Brown Coal, Ph.D. Thesis, University of Melbourne,
Melbourne, Australia, 1968.
[47] D.J. Allardice, D.G. Evans, in: C. Karr (Ed.), Analytical Methods for Coal and Coal
Products, Academic Press, NewYork, 1978.
[48] M. Le Roux, Q.P. Campbell, An investigation into an improved method of fine
coal dewatering, Journal of Minerals Engineering 16 (2003) 999–1003.
[49] D.A. Dahlstrom, R.P. Klepper, in: Y.A. Liu (Ed.), Physical Cleaning of Coal: Present
and Developing Methods, Marcel Dekker, New York, 1982, pp. 399–449.
[50] L.J. Lynch, D.S. Webster, An N.M.R. study of the water associated with brown
coal, Fuel 58 (1979) 429–432.
[51] N.G. Cutmore, B.D. Sowerby, L.J. Lynch, D.S. Webster, Determination of moisture
in black coal using pulsed nuclear magnetic resonance spectrometry, Fuel 64
(1986) 34–39.
[52] R. Graebert, D. Michel, Determination of water in coals by means of proton spin
relaxation measurements, Fuel 69 (1990) 826–829.
[53] X. Yang, A.R. Garcia, J.W. Larsen, B.G. Silbernagel, Moisture determination and
structure investigation of native and dried Argonne premium coals. A 'H
solid-state NMR relaxation study, Energy & Fuels 6 (1992) 651–655.
[54] M.L. Gorbaty, S.C. Mraw, J.S. Gethner, D. Brenner, Coal physical structure: porous
rock and macromolecular network, Fuel Processing Technology 12 (1986)
31–49.
[55] W.A. Barton, L.J. Lynch, Coal inherent moisture—its definition and measurement,
in: Proceedings of the 6 th Australian Coal Science Conference, Newcastle, 17–19
October 1994, 1994.
[56] J.F. Unsworth, C.S. Fowler, N.A. Heard, V.L. Weldon, V.J. McBrierty, Moisture in
coal 1. Differentiation between forms of moisture by N.M.R. and microwave at-
tenuation techniques, Fuel 67 (1988) 1111–1119.
[57] K. Norinaga, H. Kumagai, J.-i. Hayashi, T. Chiba, Classification of water sorbed in
coal on the basis of congelation characteristics, Energy & Fuels 12 (1998)
574–579.
[58] J.I. Hayashi, K. Norinaga, N. Kudo, T. Chiba, Estimation of size and shape of pores
in moist coal utilizing sorbed water as a molecular probe, Energy & Fuels 15
(2001) 903–909.
[59] Y. Fei, A. Chaffee, M. Marshall, W. Jackson, Coal water determination by phase
transition—differential scanning calorimetry, in: Twelfth International Coal Sci-
ence Conference, Cairns, November, 2003, 2003.
 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
[60] R. Mu, V.M. Malhotra, A new approach to elucidate coal–water interactions by
an in situ transmission FT-i.r. technique, Fuel 70 (1991) 1233–1235.
[61] X. Li, Experimental Study on Lignite Upgrading and The Effects on Combustion
Characteristics, PhD Thesis, Dalian University of Technology, Dalian, China, 2010.
[62] D.G. Evans, The brown-coal/water system: Part 4. Shrinkage on drying, Fuel 52
(1973) 186–190.
[63] T.C. St Baker, L.A. Juniper, Combustion utilisation assessment of brown coals and
lignites, Australian Coal Geology 4 (1982) 187–191.
[64] D.J. Allardice, B.C. Young, Utilisation of low rank coals, in: 19th International
Pittsburgh Coal Conference, Australia, 2001.
[65] R. Fry, S. Day, R. Sakurovs, Moisture-induced swelling of coal, International Jour-
nal of Coal Preparation and Utilization 29 (2009) 298–316.
[66] E.M. Suuberg, Y. Otake, M.J. Langner, K.T. Leung, I. Milosavljevic, Coal macromo-
lecular network structure analysis: solvent swelling thermodynamics and its
implications, Energy & Fuels 8 (1994) 1247–1262.
[67] G.P. Androutsopoulos, T.J. Linardos, Effects of drying upon lignite macro-pore
structure, Powder Technology 47 (1986) 9–15.
[68] S.R. Kelemen, L.M. Kwiatek, M. Siskin, A.G.K. Lee, Structural response of coal to
drying and pentane sorption, Energy & Fuels 20 (2006) 205–213.
[69] H. Gan, S.P. Nandi, P.L. Walker Jr., Nature of porosity in American coals, Fuel 51
(1972) 272–277.
[70] X. Li, H. Song, Q. Wang, C. Meesri, T. Wall, J. Yu, Experimental study on drying
and moisture re-adsorption kinetics of an Indonesian low rank coal, Journal of
Environmental Sciences (2009) 127–130 (Supplement).
[71] Mahidin, Y. Ogaki, H. Usui, O. Okuma, The advantages of vacuum-treatment in
the thermal upgrading of low-rank coals on the improvement of dewatering
and devolatilization, Fuel Processing Technology 84 (2003) 147–160.
[72] J.W. Larsen, P. Hall, P.C. Wernett, Pore structure of the Argonne premium coals,
Energy & Fuels 9 (1995) 324–330.
[73] J.D. St. George, M.A. Barakat, The change in effective stress associated with
shrinkage from gas desorption in coal, International Journal of Coal Geology 45
(2001) 105–113.
[74] Y.S. Nugroho, A.C. McIntosh, B.M. Gibbs, Low-temperature oxidation of single
and blended coals, Fuel 79 (2000) 1951–1961.
[75] G.D. Bongers, W.R. Jackson, F. Woskoboenko, Pressurised steam drying of Aus-
tralian low-rank coals. Part 2. Shrinkage and physical properties of steam
dried coals, preparation of dried coals with very high porosity, Fuel Processing
Technology 64 (2000) 13–23.
[76] G. Ceglarska-Stefanska, A. Czaplinski, Correlation between sorption and dilato-
metric processes in hard coals, Fuel 72 (1993) 413–417.
[77] A.L. McCutcheon, W.A. Barton, M.A. Wilson, Characterization of water adsorbed
on bituminous coals, Energy & Fuels 17 (2003) 107–112.
[78] A.L. McCutcheon, W.A. Barton, M.A. Wilson, Kinetics of water adsorption/
desorption on bituminous coals, Energy & Fuels 15 (2001) 1387–1395.
[79] A.M. Youssef, Moisture sorption in relation to some characteristics of coal, Car-
bon 12 (1974) 433–438.
[80] G.G. Karsner, D.D. Perlmutter, Effects of drying and oxidation on coal pore struc-
ture, Industrial and Engineering Chemistry Process Design and Development 21
(1982) 348–350.
[81] G. Favas, W.R. Jackson, Hydrothermal dewatering of lower rank coals. 1. Effects
of process conditions on the properties of dried product, Fuel 82 (2003) 53–57.
[82] Y. Fei, Y. Artanto, L. Giroux, M. Marshall, W.R. Jackson, J.A. MacPhee, J.P. Charland,
A.L. Chaffee, D.J. Allardice, Comparison of some physico-chemical properties of
Victorian lignite dewatered under non-evaporative conditions, Fuel 85 (2006)
1987–1991.
[83] J. Hulston, G. Favas, A.L. Chaffee, Physico-chemical properties of Loy Yang lignite
dewatered by mechanical thermal expression, Fuel 84 (2005) 1940–1948.
[84] C. Bergins, J. Hulston, K. Strauss, A.L. Chaffee, Mechanical/thermal dewatering of
lignite. Part 3: physical properties and pore structure of MTE product coals, Fuel
86 (2007) 3–16.
[85] M.L. Gorbaty, Effect of drying on the adsorptive properties of subbituminous
coal, Fuel 57 (1978) 796–797.
[86] M. Sakaguchi, K. Laursen, H. Nakagawa, K. Miura, Hydrothermal upgrading of
Loy Yang Brown coal—effect of upgrading conditions on the characteristics of
the products, Fuel Processing Technology 89 (2008) 391–396.
[87] J. Chakrabarti, Analytical Methods for Coal and Coal Products, in: C. Karr Jr. (Ed.),
Academic Press, New York, 1978, pp. 323–350.
[88] Y. Sato, S. Kushiyama, K. Tatsumoto, H. Yamaguchi, Upgrading of low rank coal
with solvent, Fuel Processing Technology 85 (2004) 1551–1564.
[89] M. Cınar, Floatability and desulfurization of a lowvrank (Turkish) coal by low-
temperature heat treatment, Fuel Processing Technology 90 (2009) 1300–1304.
[90] S.W. Dack, M.D. Hobday, T.D. Smith, J.R. Pilbrow, Free radical involvement in the
oxidation of brown coal, Fuel 62 (1983) 1510–1512.
[91] S.W. Dack, M.D. Hobday, T.D. Smith, J.R. Pilbrow, Free-radical involvement in the
drying and oxidation of Victorian brown coal, Fuel 63 (1984) 39–42.
[92] B.K. Saikia, R.K. Boruah, P.K. Gogoi, B.P. Baruah, A thermal investigation on coals
from Assam (India), Fuel Processing Technology 90 (2009) 196–203.
[93] H. Shui, H. Li, H. Chang, Z. Wang, Z. Gao, Z. Lei, S. Ren, Modification of
sub-bituminous coal by steam treatment: caking and coking properties, Fuel
Processing Technology 92 (2011) 2299–2304.
[94] A. Tahmasebi, J. Yu, Y. Han, F. Yin, S. Bhattacharya, D. Stokie, Study of chemical
structure changes of Chinese lignite upon drying in superheated steam, micro-
wave and hot air, Energy & Fuels 26 (2012) 3651–3660.
[95] A. Tahmasebi, J. Yu, Y. Han, X. Li, A study of chemical structure changes of Chi-
nese lignite during fluidized-bed drying in nitrogen and air, Fuel Processing
Technology 101 (2012) 85–93.
19
[96] K. Murakami, H. Shirato, Y. Nishiyama, In situ infrared spectroscopic study of the
effects of exchanged cations on thermal decomposition of a brown coal, Fuel 76
(1997) 655–661.
[97] J.H. Campbell, Pyrolysis of subbituminous coal in relation to in-situ coal gasifica-
tion, Fuel 57 (1978) 217–224.
[98] H.N.S. Schafer, Pyrolysis of brown coals. 1. Decomposition of acid groups in coals
containing carboxyl groups in the acid and cation forms, Fuel 58 (1979) 667–672.
[99] G.G. Karsner, D.D. Perlmutter, Kinetics of coal drying-decomposition, AICHE
Journal 28 (1982) 199–207.
[100] H.N.S. Schafer, Pyrolysis of brown coals. 2. Decomposition of acid groups on
heating in the range 100-900 °C, Fuel 58 (1979) 673–679.
[101] R.M. Carr, H. Kumagai, B.M. Peake, B.H. Robinson, A.H. Clemens, T.W. Matheson,
Formation of free radicals during drying and oxidation of a lignite and a bitumi-
nous coal, Fuel 74 (1995) 389–394.
[102] I.B. Goldberg, T.M. McKinney, K.E. Chung, R. Galli, Radical formation during vac-
uum drying of Wyoming subbituminous and Morwell brown coals, Fuel 65
(1986) 241–247.
[103] H.H. Lowry, Chemistry of Coal Utilization, John Wiley and Sons, New York, 1963.
[104] M. Itay, C.R. Hill, D. Glasser, A study of the low temperature oxidation of coal,
Fuel Processing Technology 21 (1989) 81–97.
[105] S.C. Banerjee, B.D. Banerjee, R.N. Chakravorty, Rate studies of aerial oxidation of
coal at low temperatures (30–170 °C), Fuel 49 (1970) 324–331.
[106] X.D. Chen, J.B. Stott, The effect of moisture content on the oxidation rate of coal
during near-equilibrium drying and wetting at 50 °C, Fuel 72 (1993) 787–792.
[107] K.K. Bhattacharyya, The role of desorption of moisture from coal in its spontane-
ous heating, Fuel 51 (1972) 214–220.
[108] D. Schmal, J.H. Duyzer, J.W. van Heuven, A model for the spontaneous heating of
coal, Fuel 64 (1985) 963–972.
[109] S. Unal, D.G. Wood, I.J. Harris, Effects of drying methods on the low temperature
reactivity of Victorian brown coal to oxygen, Fuel 71 (1992) 183–192.
[110] N. Berkowitz, An Introduction to Coal Technology, Academic Press, New York,
1979.
[111] K. Bratek, W. Bratek, I. Gerus-Piasecka, S. Jasienko, P. Wilk, Properties and struc-
ture of different rank anthracites, Fuel 81 (2002) 97–108.
[112] X. Li, R.K. Rathnam, J. Yu, Q. Wang, T. Wall, C. Meesri, Pyrolysis and combustion
characteristics of an Indonesian low-rank coal under O2/N2 and O2/CO2 condi-
tions, Energy & Fuels 24 (2010) 160–164.
[113] K. Weigl, G. Schuster, G.N. Stamatelopoulos, A. Friedl, Increasing power plant ef-
ficiency by fuel drying, Computers and Chemical Engineering Supplement
(1999) 919–922.
[114] K. Gorner, M. Liebetruth, Pre-drying of lignite to increase efficiency of brown
coal fired power plants, in: 6th Europian Conference on Industrial Furnaces
and Boilers, Estoril–Lisbon, Portugal, April 2002, 2002.
[115] E. Kakaras, P. Ahladas, S. Syrmopoulos, Computer simulation studies for the in-
tegration of an external dryer into a Greek lignite-fired power plant, Fuel 81
(2002) 583–593.
[116] B. Lucarelli, Benefits of Drying Indonesian Low Rank Coals, in: Cleaner Coal
Workshop, Ha Long City, Vietnam, August 19–21, 2008, 2008.
[117] H. Osman, S.V. Jangam, J.D. Lease, A.S. Mujumdar, Drying of low-rank coal (LRC) — a
review of recent patents and innovations, Drying Technology 29 (2011) 1763–1783.
[118] M. Agraniotis, P. Grammelis, C. Papapavlou, E. Kakaras, Experimental investiga-
tion on the combustion behaviour of pre-dried Greek lignite, Fuel Processing
Technology 90 (2009) 1071–1079.
[119] A. Tomita, Y. Ohtsuka, Gasification and Combustion of Brown Coal, in: C.-Z. Li
(Ed.), Advances in the Science of Victorian Brown Coal, Elsevier, Oxford, UK,
2004, pp. 223–236.
[120] C. Zeng, S. Clayton, H. Wu, J.-I. Hayashi, C.-Z. Li, Effects of dewatering on the py-
rolysis and gasification reactivity of Victorian brown coal, Energy & Fuels 21
(2007) 399–404.
[121] C. Zeng, G. Favas, H. Wu, A.L. Chaffee, J.-I. Hayashi, C.-Z. Li, Effects of
pretreatment in steam on the pyrolysis behavior of Loy Yang brown coal, Energy
& Fuels 20 (2006) 281–286.
[122] M. Siskin, A.R. Katritzky, Reactivity of organic compounds in hot water: geo-
chemical and technological implications, Science 254 (1991) 231–237.
[123] K. Murakami, J.-I. Ozaki, Y. Nishiyama, Effects of surface treatment on cation ex-
change properties of Australian brown coals, Fuel Processing Technology 43
(1995) 95–110.
[124] M.A. Serio, E. Kroo, H. Teng, P.R. Solomon, The effects of moisture and cations on
liquefaction of low rank coals, Preprint Papers - American Chemical Society, Di-
vision of Fuel Chemistry 38 (1993) 577–586.
[125] A.K. Saini, C. Song, H.H. Schobert, Influence of drying and oxidation of coal on its
catalytic and thermal liquefaction. 1. Coal conversion and products distribution,
Preprint Papers - American Chemical Society, Division of Fuel Chemistry 38
(1993) 593–600.
[126] H.F. Silver, W.S. Frazee, in: Integrated Two-Stage Coal Liquefaction Studies, Uni-
versity of Wyoming, Laramie, 1985, p. 460.
[127] A.K. Saini, C. Song, H.H. Schobert, Influence of drying and oxidation of coal on its
catalytic and thermal liquefaction. 2. Characterization of dried and oxidized coal
and residues, Preprint Papers - American Chemical Society, Division of Fuel
Chemistry 38 (1993) 601–608.
[128] F.P. Miknis, D.A. Netzel, T.F. Turner, An NMR investigation of the effects of differ-
ent drying methods on coal structure, Preprint Papers - American Chemical So-
ciety, Division of Fuel Chemistry 38 (1993) 609–617.
[129] A. Tahmasebi, J. Yu, X. Li, C. Meesri, Experimental study on microwave drying of
Chinese and Indonesian low-rank coals, Fuel Processing Technology 92 (2011)
1821–1829.
20 J. Yu et al. / Fuel Processing Technology 106 (2013) 9–20
[130] F.P. Miknis, D.A. Netzel, J.C. Wallace, C.H. Butcher, J.M. Mitzel, T.F. Turner, An in-
vestigation of the role of water on retrograde/condensation reactions and
enhanced liquefaction yields, in: Final Report, DOE Contract DE-AC22-
91PC91043, DOE, 1995.
[131] F.E. Huggins, G.P. Huffman, Coal Weathering and Oxidation: The Early Stages, in:
C.R. Nelson (Ed.), Chemistry of Coal Weathering, Elsevier, Amsterdam, 1989,
pp. 33–60.
[132] H. Wang, B.Z. Dlugogorski, E.M. Kennedy, Coal oxidation at low temperatures:
oxygen consumption, oxidation products, reaction mechanism and kinetic
modelling, Progress in Energy and Combustion Science 29 (2003) 487–513.
[133] O.P. Mahajan, M. Komatsu, P.L. Walker Jr., Low-temperature air oxidation of cak-
ing coals. 1. Effect on subsequent reactivity of chars produced, Fuel 59 (1980)
3–10.
[134] A.H. Clemens, T.W. Matheson, The role of moisture in the self-heating of
low-rank coals, Fuel 75 (1996) 891–895.
[135] J. Kudynska, H.A. Buckmaster, Low-temperature oxidation kinetics of
high-volatile bituminous coal studied by dynamic in situ 9 GHz c.w. e.p.r. spec-
troscopy, Fuel 75 (1996) 872–878.
[136] L.D. Schmidt, Changes in Coal During Storage, in: H.H. Lowry (Ed.), Chemistry of
Coal Utilization, Wiley, New York, 1945, pp. 627–676.
[137] J.C. Petit, A comprehensive study of the water vapour/coal system: application to
the role of water in the weathering of coal, Fuel 70 (1991) 1053–1058.
[138] H. Wang, B.Z. Dlugogorski, E.M. Kennedy, Role of inherent water in
low-temperature oxidation of coal, Combustion Science and Technology 175
(2003) 253–270.
[139] D. Schmal, Spontaneous Heating of Stored Coal, in: C.R. Nelson (Ed.), Chemistry
of Coal Weathering, Elsevier, Amsterdam, 1989, pp. 133–215.
[140] J.N. Carras, B.C. Young, Self–heating of coal and related materials: models, appli-
cation and test methods, Progress in Energy and Combustion Science 20 (1994)
1–15.