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Review on chemical upgrading of coal: Production processes, potential


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DOI: 10.1016/j.fuproc.2016.12.010

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Fuel Processing Technology 158 (2017) 35–56

Contents lists available at ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Review

Review on chemical upgrading of coal: Production processes, potential


applications and recent developments
Moshfiqur Rahman, Deepak Pudasainee, Rajender Gupta ⁎
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4, Canada

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

Article history: Coal is a major source of energy. In order to overcome the operational problems and environmental issues related
Received 7 October 2016 to direct utilization of coal, coal upgrading research and development works are in progress in terms of moisture
Received in revised form 9 December 2016 removal, demineralization, removal of harmful constituents such as sulfur, mercury etc. There have been two
Accepted 11 December 2016
major approaches to achieve this: dissolving minerals out of coal – the product is termed as ultra clean coal
Available online xxxx
(UCC) and solvent extraction of coaly matter – the product termed as ash-free coal (AFC). In this paper, current
Keywords:
knowledge regarding chemical upgrading of coal has been reviewed. In particular, production process and effects
Chemical upgrading of coal of various parameters on yield and product quality have been discussed. The potential applications of the
Ultra-clean coal demineralized coals and the economic assessment with respect to commercialization of this process have also
Ash-free coal been presented.
Applications of UCC/AFC Chemical treatment processes have been demonstrated as the most effective techniques for removal of ash
Clean energy forming minerals from coal to produce coal with minimal or almost no ash. In general, the ash content of UCC
is reported within the range of 0.15 to 0.6% either by treating bituminous coal with HF followed by HCl or
HNO3. Most effective treatment available in literature is HF followed by HNO3, achieving ash content as low as
0.15%. Organic solvents like polar, non-polar and mixed solvent have been used to extract the organic matters
from coal to produce AFC. In general, extraction yield has been found higher at high treatment temperature
with polar solvents.
The advantages of using UCC and AFC are that they emit lesser pollutants and cause less or no abrasion/erosion
and fouling/slagging in the boilers. However, the literature on economic evaluation of AFC applications is scarce
and needs to be carried out in future.
© 2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2. Physical separation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Chemical demineralization for ultra clean coal (UCC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1. Acid and alkali digestion method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1.1. Alkali digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.1.2. Acid soaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.1.3. Caustic soda regeneration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1.4. Effect of the acid or alkali concentrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1.5. Effect of temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1.6. Effect of particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.1.7. Effect of coal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.2. Challenges in demineralization of coal to produce UCC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4. Extraction of organic matters to produce ash-free coal (AFC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.1. Effect of solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.1.1. Extraction of coal by polar solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.1.2. Extraction of coal by non-polar solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

⁎ Corresponding author.
E-mail address: rajender.gupta@ualberta.ca (R. Gupta).

http://dx.doi.org/10.1016/j.fuproc.2016.12.010
0378-3820/© 2016 Elsevier B.V. All rights reserved.
36 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

4.1.3. Mixed solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45


4.1.4. Effect of pre-treatment with alkalis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.2. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.3. Effect of initial pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4. Effect of particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.5. Effect of coal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.6. Challenges in demineralization of coal to produce AFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5. Potential applications of UCC and AFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.1. Application of UCC/AFC in chemical looping combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.2. Catalytic gasification of ash free coals to produce syngas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.3. Use of AFC as a blending agent in coke making . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.4. Production of anode coke . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.5. Application of AFC as a fuel in direct carbon fuel cell (DCFC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.6. Coal water slurry (CWS) or coal water slurry fuel (CWSF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
6. Economic study of AFC production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
7. Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
7.1. UCC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
7.2. AFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
8. Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

1. Introduction problems with direct utilization of coal, coal upgrading has been priori-
tized. History of coal chemical cleaning dates back to 1940s in Germany,
The wide abundance of coal reserves and lower cost is increasing its where a process was developed for removing ash-forming minerals
utilization to produce energy and fuels. The direct utilization of coal has from physically cleaned black coal concentrates, involving heating the
several problems, such as higher ash forming minerals and moisture coal as a paste with aqueous alkali solution, followed by solid/liquid sep-
contents; lower heating value and the environmental pollution. In con- aration, acid washing and water washing [4,5].
ventional combustion processes minerals in coal are mostly rejected as There has been a growing interest in upgrading of low-rank coals
ash from boiler or particulate control devices or emitted into the atmo- such as lignite and sub-bituminous, in term of drying and demineraliza-
sphere as particle matter. The combustion of coal causes various envi- tion, influenced by increasing demand of power and limited supply of
ronmental problems such as emission of particles, SOx, NOx, the premium coals. Upgrading of coal can be done for several aspects
greenhouse gases, toxic metals emission [1–3]. Due to these several such as moisture removal, de-mineralization, removal of harmful

Fig. 1. Conceptual diagram of producing A) clean coal, B) UCC and C) AFC, and their characteristics.
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 37

constituents such as sulfur and mercury. There are two basic approach Froth flotation technique has been used for the beneficiation of finer
of coal cleaning: physical and chemical cleaning. Physical cleaning pro- coal particles (b0.6 mm in size) for N50 years [8,15]. This method re-
cess in general is cleaning the coal with only physical processes, where- quires a surface active agent which stabilizes the froth formed during
as, chemical cleaning methods can be divided into two categories: use of the separation of minerals and works on the principal of gravity and
chemicals that dissolve minerals or solvents for dissolving the coaly wettability of the coal particles.
matters. The first approach produces UCC using acids or alkalis dissolv- Oil agglomeration process is a technique for cleaning finer coal par-
ing all the minerals leaving the organic coal matrix under hydrothermal ticles and works based on the principle that hydrophobic coal particles
conditions. Second approach is dissolving organic components of the undergo agglomeration and separated from the mineral matters by
coal in organic solvent (as discussed in Section 4). the addition of suitable oil that helps to wet and agglomerate the coal
Fig. 1 demonstrates three pathways for removing mineral matters in particles [16,17].
coal – one physical and two chemicals. The detail production process Air dense medium fluidized bed technique is a very simple and an
has been explained in Sections 3 and 4. The objective of this review is economic process for coal beneficiation of feed particle size of 1–5 cm.
to provide state of art knowledge of chemical cleaning process. Howev- Fluidized bed allows the lighter coal particles containing less minerals
er, a brief description of physical cleaning process is described in Section to float on the surface of the bed and high mineral containing heavier
2. Physical process is suitable for cleaning of high ash containing coal, material to sink down the bed and cleaner coal can be easily separated
whereas UCC and AFC (by chemical cleaning process) are suitable for [6,8].
cleaning low ash containing coal. In clean coal preparation by physical These methods have several disadvantages, such as, these require
cleaning process minerals are separated by density difference and the finer coal particles and not suitable for removing chemically bound min-
coal structure does not change at all. Similarly, in UCC production pro- erals. These techniques are only capable of reducing limited amount of
cess there is no change in coal structure; only the acid/alkali reacts mineral matters, the ash content by more than half of the original
with mineral matters. On the other hand, in AFC production organic amount [18,19]. Physical separation technique has been used for very
matters dissolve in solvent and mineral matters remains in the residual fine particles, typically 3–5 μm size, to separate organic components
part, ultimately resulting chemical changes in the coal structure. (macerals) and inorganic constituents (ash forming minerals) from
Physical cleaning of coal can be considered as a pre-cleaning step or each other utilizing density gradient separation method under very
the first step to go for chemical cleaning process and is not very effective high centrifugal forces [14,20–23].
in removing finely distributed minerals in coal matrix. Physical coal
cleaning techniques in broad are classified based on difference in specif- 3. Chemical demineralization for ultra clean coal (UCC)
ic gravity and surface properties (wettability). Some of the widely used
techniques are gravity separation, froth flotation, oil agglomeration, 3.1. Acid and alkali digestion method
magnetic separation, electrostatic separation, and air dense medium
fluidization [6,7]. The brief descriptions of these technologies are avail- UCC has limited ash content (0.1 to 1.0 wt%) and its combustion is
able in the recent review by Meshram et al. [8]. Physical coal cleaning environmental friendly (less pollutants emission compared with the
has several limitations such as gravity separation requires feed size larg- raw coal) and causes less attrition and fouling in the boilers. Fig. 1
er than 0.5 mm; very fine grinding (energy intensive process) is neces- shows the overall conceptual diagram of producing clean coal by phys-
sary to release pyrite, only pyritic sulfur can be removed. Because of ical cleaning (path A), UCC (path B) and AFC (path C) by chemical
these limitations, and in order to remove finely distributed minerals cleaning methods. Physical separation method is more effective for
and chemically bounded species from coal matrix chemical cleaning high minerals containing feed coal, whereas, chemical separation meth-
process has been utilized. od is more suited for low minerals containing feed coals.
Katalambula and Gupta [9] presented a comprehensive review on Chemical treatment processes is the most effective technique for re-
both physical and chemical cleaning needed for reducing mineral con- moval of ash forming minerals from coal to produce UCC and have been
tent as well as moisture content of coal. They reviewed some of the extensively used [11–13,24–27]. This method requires reagents for the
upgrading technologies for coal upgrading in terms of their moisture, selective leaching of inorganic constituents. The acid and alkali reagents
ash, and other pollutant emission, including technological development those are used in chemical demineralization processes are HF [11,26],
and commercialization status. They argued that despite the availability HCl [26], HNO3 [12], H2SO4 [28] and NaOH [24]. Beside these some oxi-
of various potential techniques the coal upgrading has not been realized dizing agents like H2O2 [29], FeCl3 [28] have also been employed. The
in depth. There are several reviews on physical beneficiation coals [8, two most common steps used in demineralization during UCC produc-
10]. Meshram et al. [8] briefly presented chemical beneficiation of coal tion are HF treatment followed by HNO3 washing.
including acid leaching, alkali leaching and leaching of coal with alkali Steel et al. [26] treated Australian bituminous coal with HCl (aq.),
followed by acid mainly for production of UCC. Even though, UCC and which essentially dissolved all the minerals associated with Ca, Ma
AFC production, their application in various purposes have been priori- and Fe as carbonates, sulfates and phosphates but very little aluminosil-
tized in the recent past, there is no comprehensive review work pre- icate compounds. It was also observed that HCl (aq.) extracted essen-
senting the state-of-the-art technology related to UCC and AFC. In tially all of the Na and some of the Al, K and Ti but not Si from mineral
order to fulfill this gap, in this paper, UCC and AFC production process, matters. HCl is unreactive towards pyrites; therefore, not all the Fe is ex-
effects of demineralizing reagents or solvents, effect of temperature, tracted from the coal. Consequently, HF dissolves all of the Al, Si and K in
time etc. has been carefully reviewed, correlated with the available liter- the mineral matter at 20 °C. Thus, HF was found to be particularly effec-
ature and conclusions have been drawn. The potential applications of tive to react with most of the minerals present in the coal. Only pyrites
the demineralized coals and their economic assessment with respect present in the coal does not significantly react with HF. Therefore, it has
to commercialization have also been discussed. been suggested pretreatment with HCl is necessary followed by HF
treatment for an effective removal of minerals from black coal [30].
2. Physical separation methods But, Steel et al. [27] did not consider pretreatment with HCl as a feasible
option for the complete removal of Ca and Mg, which uses HF for pro-
Physical beneficiation processes, such as washing, froth flotation and ducing UCC.
oil agglomeration have been applied to reduce mineral matter [11–14]. Steel et al. [27] also developed a model to determine the concentra-
Recent years, air dense medium fluidized bed techniques have been ap- tion of fluoride complex, Al and Si species, free fluoride and hydrogen
plied for removal of mineral matter. These methods are capable of re- ions and molecular HF in solution while aluminosilicate compounds
moving mineral matters those are not within the coal matrix [6,8]. were treated with aq. HF. This model describes the chemical
38 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

mechanisms of the dissolution behavior of the minerals in coal in aq. HF (Pb, As, Hg, Cd, Zn, Cu, Ni, Co, Ti, Sb, Na, K, Ga, and Ge) and pyrites in a
and unwanted precipitation of various fluoride compounds. They mild temperature and ambient pressure conditions. Utilizing this con-
claimed that their model is applicable for the development of chemical venient leaching process they demineralized a moderately high ash
strategies for dissolving almost all the minerals from coal for the pro- (17%) containing coal (Talcher coal), using water alone, aqueous alkali
duction of UCC containing b 0.1 (wt%) mineral matters and capable of (NaOH) alone, HCl alone, and aqueous NaOH in combination with HCl.
eliminating the unwanted precipitation of fluoride compounds. They manage to clean the coal to a reasonably good extent up to 75%
In another paper Steel and Patrick [11] reported successful elimina- (degree of demineralization) using 10% NaOH followed by 2% aq. HCl
tion of mineral matter in a high volatile coal of UK origin utilizing aque- treatment. Increasing NaOH concentration beyond 10% did not improve
ous HF followed by aq. HNO3 for 3 h at 65 °C in each case. HF reduces the the degree of demineralization. They also manage to recover the
ash content to about 2.6 (wt%) from 7.9 (wt%), which contains mainly chemicals used in the process, which makes the process cost-effective
the pyrites (FeS2), unreactive towards HF. During the process some fluo- and more feasible.
ride compounds are formed such as, AlF3, NaAlF4, CaF2 and MgF2. Suc- Nabeel et al. [34] produced UCC from low-grade Topa coal by alkali-
cessive treatment with HNO3 reduced the ash content further to 0.6%. acid leaching using 20% aq. NaOH and 10% H2SO4 utilizing stepwise
They also found that HNO3 reacts with FeS2 only when the concentra- leaching technique and around 75% degree of demineralization was
tion N 1 M, preferentially with the organic coal structure. achieved. Utilizing even lower concentration (5%) of alkali-acid (2 h of
Steel and Patrick [12] also found that fluoride content of the coal in- each) treatment, after three consecutive steps 80% degree of demineral-
creases tremendously after HF treatment and then drops down upon ization was achieved.
HNO3 leaching. Increment of N content of the coal was observed, due Recently, Jorjani et al. [35] introduced microwave irradiation tech-
to the attack of the nitronium ion (NO+2 ) to the carbonaceous coal struc- nique for pretreatment and sequential leaching with HF followed by
ture, the overall ash content of the UCC reduced to 0.2 (wt%) and major HNO3 treatment for producing UCC. They observed that 1.5 h treatment
element in ash was Fe from unreacted pyrites. In a two stage leaching of native and microwaved (900 W for 7 min) coal with HF (2 M) re-
process using HF followed by HNO3, HNO3 can oxidize Fe in pyrite duced ash content significantly by 35 and 43%, respectively. Extended
(from Fe2 + to Fe3 +) and oxidize S in pyrite (from S− to SO24 −), as treatment time to 2.5 h enhanced the removal efficiency by 53 and
shown in following reactions [12,31]. 56% respectively. Further, increment of the time (N 2.5 h) did not result
in any significant reduction of ash content.
FeS2 þ 5HNO3 →Fe3þ þ 2SO4 2− þ Hþ þ 5NO þ 2H2 O Wijaya et al. [36] produced UCC from two Victorian brown coals by
sequential and single leaching techniques utilizing weak acids like,
2HNO3 ⇌NO2 þ þ NO3 − þ H2 O pyroligneous acid (waste solution derived from wood carbonization)
and citric acid (biodegradable organic acid). A strong chelating agent,
HNO3 þ 2H2 SO4 ⇌NO2 þ þ H3 Oþ þ HSO4 − disodium ethylenediaminetetraacetic acid (Na-EDTA) was also
employed with the combination of dilute acid (1 M HNO3) for breaking
Steel & Patrick [12] reported that pyrite in coal can be dissolved off the metallic complexes in the coal matrix [37].
completely even with lower HNO3 concentration range of approximate- Demineralization of coal to produce UCC depends on the number of
ly 0.03 M. During HNO3 leaching, carbonaceous matrix is affected, lead- factors, such as, severity of the operating conditions, type of reagents or
ing to a loss of C and H content, loss of calorific value (CV), and increased chemicals used for digestion and their concentrations, properties of
N and O contents. They proposed that H2SO4, which is formed from the coals, particle sizes and type of bounding of mineral matters in the
reaction between HNO3 and pyrite, may react with HNO3 to form NO+ 2 . coal structure.
They stated that concentrations of HNO3 and H2SO4 at the site, where These technologies in large scale have not been commercialized as
pyrite is dissolving might be sufficient for NO+ 2 to form. Once a powerful yet. Fig. 2 shows the UCC production process diagram in Yancoal Austra-
nitrating agent (NO+ 2 ion) is formed, it reacts with the carbonaceous lia Ltd. UCC Energy Pty Limited, a privately held company in Cessnock,
coal matrix. NSW, Australia, founded in 1987 and producing UCC by NaOH treat-
The combustion behavior of UCC containing 0.3 (wt%) ash was in- ment followed by H2SO4 washing. The overall ash content of the extract
vestigated by Rubiera et al. [13] in drop tube furnace operating at is b0.2%. The production of UCC from bituminous coal in plant scale with
1000 °C. The char obtained from chemically treated coal showed in- regeneration of leaching chemicals has been developed in Australia [38,
creased reactivity compared with the original coal and increased the 39]. Yancoal Australia Ltd. was formed in 2004 with the intention of pro-
combustion efficiency, with decrease in SO2 and increase in NO emis- ducing UCC. The pilot plant is located on the outskirts of Cessnock in
sion, due to HNO3 treatment. These results are also supporting the find- New South Wales; nominal feed coal capacity is 350 kg/h, correspond-
ings of Steel et al. [12], where (NO+ 2 ion) was formed from HNO3 and ing to nominal UCC output in the range of 1–2 kt/year [40].
subsequently reacted with the carbonaceous coal structure. The major reactions involved in the UCC production process at
Steel and Patrick [32] also developed a process by which selectively Yancol Australia [41] are described briefly as follows:
Si(IV) and Al(III) can be separated from coal and this process may be ap-
plicable to other areas like mineral processing technology, besides UCC 3.1.1. Alkali digestion
production. Utilizing this technique, they were able to separate 65 During alkali digestion, the major reactions involve are the dissolu-
(wt%) of Si(IV) selectively from a bituminous coal. Kizgut et al. [20] in- tion of silica and formation of solid sodalite and small amounts of
vestigated the thermal behavior of demineralized bituminous coals other impurities such as Al, Fe, P and organic carbon may also dissolve
from Turkish, Australian and Polish origin. They successfully during digestion.
demineralized these coals by applying HF followed by HNO3 treatment
and obtained the coals with the ash content ranging from 0.15 to 0.41%. SiO2 ðsÞ þ 2NaOH→Na2 SiO3 ðlÞ þ H2 O
They observed that the N and O content of the coal increased 2.15 to
3.94% and 11.82 to 17.66%, respectively. These changes were resulted
3Al2 Si2 O5 ðOHÞ4 ðsÞ þ 8NaOH→2Na4 Si3 Al3 O12 ðOHÞ ðsÞ þ 9H2 O
from the oxidation and nitrification effect of HNO3. Consequently, C
and H content of the coals were decreased by 7.49 to 12.48% and 0.62
to 1.39%, respectively. As a result, the higher heating values (HHV) of
these coals were decreased. 3.1.2. Acid soaking
Sharma and Singh [33] developed an alkali-acid assisted leaching Caustic leached coal is treated with dil. H2SO4 in order to dissolve So-
technique for demineralization of coal to remove the toxic minerals dalite, which produces a mixture of sodium and aluminium sulfates and
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 39

Fig. 2. UCC production diagram in Yancoal Australia Ltd. Redrawn after [40].

acid-soluble silicic acid. of − 75 μm coal particles with HF concentration ranging from 0.5 to
3.5 M, ash removal increased significantly with the increase of concen-
2Na4 Si3 Al3 O12 ðOHÞ ðsÞ þ 13H2 SO4 →4Na2 SO4 þ 3Al2 ðSO4 Þ3 þ 6H2 SiO3 tration and achieved 57 to 71% ash removal from different coal samples
þ 8H2 O using 3.5 M HF solution. Further, increasing the concentration to 5 M,
the ash removal increased slightly but not that significant, i.e. the ash re-
Iron dissolution moval rate was slower. They also observed that by increasing the HF
concentration, there was no significant difference in the ash removal be-
Fe2 O3 þ 3H2 SO4 →Fe2 ðSO4 Þ3 þ 3H2 O tween the microwaved and non-microwaved coal samples.

Caustic soda neutralization 3.1.5. Effect of temperature


Based on the limited number of studies, it can be generalized that the
2NaOH þ H2 SO4 →Na2 SO4 þ 2H2 O
treatment temperature plays a major role on the effective chemical de-
mineralization of coal. Jorjani et al. [35] utilized microwave irradiation
technique for the subsequent demineralization of coal with HF and
3.1.3. Caustic soda regeneration
HNO3 leaching. They treated different coals with the particle size of
Liquor from the caustic digestion is treated with Ca(OH)2 in order to
− 75 μm with 3.5 M HF solution at different temperatures of 25, 35,
regenerate caustic soda and this precipitates the silica dissolved within
45, 55 and 65 °C, respectively. In those experiments, as the temperature
the digestion process as CaSiO3.
increased up to 55 °C the ash removal increased significantly, but ash re-
Na2 SiO3 þ CaðOHÞ2 ðsÞ→CaSiO3 ðsÞ þ 2NaOH duction at 65 °C was not substantial (Fig. 3).
Tables 1a–1c summarize the reaction conditions for UCC production
available in the literature utilizing different leaching reagents, coal types
Sodium sulfate generated from pyrite in the coal is also recovered in
and the mineral rejection or the ash content of the parent and upgraded
this step;

Na2 SO4 þ CaðOHÞ2 ðsÞ þ 2H2 O→2NaOH þ CaSO4  2H2 OðsÞ

Al2 ðSO4 Þ3 þ 3CaðOHÞ2 ðsÞ þ 3H2 O→2AlðOHÞ3 ðsÞ þ 3CaSO4  H2 O ðsÞ

H2 SiO3 þ CaðOHÞ2 ðsÞ→CaSiO3 ðsÞ þ 2H2 O

Na2 SO4 þ CaðOHÞ2 ðsÞ þ 2H2 O→2NaOH þ CaSO4  2H2 O ðsÞ

Fe2 ðSO4 Þ3 þ 3CaðOHÞ2 ðsÞ þ 6H2 O→2FeðOHÞ3 ðsÞ þ 3CaSO4  2H2 O ðsÞ

H2 SO4 þ CaðOHÞ2 ðsÞ→CaSO4  2H2 O ðsÞ

Fig. 3. Effect of leaching temperature on ash reduction for Tabas (T), Tabas-microwaved
3.1.4. Effect of the acid or alkali concentrations (Tm) at 900 W, 7 min, Zirab (Z), and Zirab-microwaved (Zm) at 900 W, 7 min coal
HF concentration, as reported by Jorjani et al. [35], plays an impor- samples (2.5 h, − 75 μm, 3.5 M HF) [35]. (Reprinted with permission from Copyright
tant role in the removal of ash content of coals. During the treatment (2011) Elsevier).
40 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

Table 1a
Reaction conditions for UCC production by alkali and acid treatments.

Reagent Mineral
Research used/process rejection
group used Conditions Coal type/mineral matter (wt%) Remarks

Sharma H2O, NaOH Coal + NaOH (2–20%), refluxed 24 h, Low grade Talcher coal 75% Development of alkali-acid assisted leaching technique for
and (2–20%) filtered, neutralized with 2% HCl, dried (ash 17%) demineralization of coal by removing the toxic minerals
Singh followed by 110 °C, 24 h (including pyrites) under mild temperature and ambient
[33] HCl (2%) pressure conditions. The chemicals used are recoverable.
Nabeel 20% NaOH Coal sample + dist. H2O + NaOH, refluxed, Topa coal (ash 33.60%) and 75–80% Concentration of NaOH and H2SO4 can be reduced to 1% by
et al. followed by 1–24 h, filtered, dried, 105 °C, 3 h, followed low-grade coals (ash 43%), utilizing step-wise alkali acid treatment.
[34] 10% H2SO4 by H2SO4 treatment, 100 °C, 1–24 h (−60 to +120 μm)

coals. Most of the research has been carried out with bituminous and with microwave irradiation can cause phase changes and expansion,
low grade coals. In general, the ash content of the upgraded coal within building internal pressures in coal matrix, weakening the structure
the range of 0.15 to 0.6% were achieved either by treating bituminous and creating fractures [43]. In Jorjani et al.'s [35] study as particle sizes
coal with HF followed by HCl or HNO3. But most effective treatment decreased to −75 μm, the effect of microwave irradiation decreased be-
was reported to be HF followed by HNO3 and achieved ash content as cause the leaching agent had sufficient accessibility to the mineral
low as 0.15%. Although, Wijaya et al. [36] used low grade coal treatment phases already. In another word, the weakening effect of microwave ir-
with mild acids like pyroligneous acid (1 M), citric acid (1 M) followed radiation is less dominant in fine particles.
by Na–EDTA (0.1 M) treatment resulted low ash content in the Table 1a, summarizes the reaction conditions for UCC production by
upgraded coal as 0.08%. Some researcher treated coal only with HF alkali and acid as leaching reagents. It is found that aqueous NaOH treat-
[42], others with NaOH followed by HCl [33], where the ash contents ment followed by dilute HCl or H2SO4 treatment of coal for digesting
in the upgraded coal was not reduced like those of HF treatment follow- mineral matter present in the coal is effective to a certain extent to pro-
ed by HNO3 and or HCl. Based on these available literatures, we can duce clean coal, but not suitable for producing UCC to be used in premi-
broadly generalize that coal treatment with HF followed by HNO3 is um purposes. Table 1b, summarizes the reaction conditions for UCC
one of the best process for producing UCC. production by inorganic acid treatments. As reveled by these literatures
aqueous HF treatment alone is capable of producing clean coal by re-
3.1.6. Effect of particle size moving ~ 95% of the minerals from finer (b 40 μm) and coursers
Coal particle size affects the degree of coal demineralization, which (b1000 μm) coal particles but does not meet the UCC criteria.
is also depending on the extent of the inherent mineral matter of the HF treatment followed by dilute HCl treatment resulted UCC with
parent coal. Wijaya et al. [37] studied the effect of coal particle size on very low ash content (b1.0%). Even better results were obtained upon
the degree of demineralization with the fine (−53, 106–153 μm), mod- HF treatment followed by dilute HNO3 treatment and obtained UCC
erate (153–300 μm) and coarse (300–600 μm) coal particles, utilizing with even lower ash content (0.2–0.69%). These results indicate that
recycled weak acids like citric acid, pyroligneous acid, and Na-EDTA. the later procedure is very effective for producing UCC. Table 1c, sum-
They observed the highest mineral matter removal were from 153 to marizes the reaction conditions for UCC production by organic acid
300 μm size particles, not from the fine (− 53 μm) coal particles. This treatment. It is evident from the results summarized in Table 1c, that
is possibly due the agglomeration of the fine particles and floating on weaker organic acids like pyroligneous and citric acid treatment follow-
the surface of the acids. As a result the leaching agent (acid) cannot ed by dilute EDTA treatment of Victorian brown coals produces UCC
come in proper contact with the fine coal matrix. On the other hand, with reasonably low ash content (0.08–3.4%). In general, Victorian
least minerals removal was observed from the coarse coal particle brown coals have very larger amount of clay and low ash forming con-
sizes (300–600 μm), indicating that the leaching agent has the diffusion stituents. Therefore, coal containing low ash forming constitutes are
resistance to the courser coal particles; thus, limiting the penetration of suitable for producing UCC by weaker organic acid treatment.
the leaching agent into coal particles for digestion. This result indicates
that both the fine and courser coal particles has the diffusion resistance 3.1.7. Effect of coal properties
and thus resulting negative demineralization effect, whereas the mod- Coal properties have an important role in removing minerals from
erate particle size (153–300 μm) showed positive demineralization coal matrix. These minerals are present on the surface or in the core of
effect. the coal and/or bonded with the coal molecule. It is necessary to know
Jorjani et al. [35] studied the effect of coal particle size during UCC the proximate, ultimate analysis and mineral composition of a particular
production by microwave irradiation as pretreatment and sequential coal to understand its properties. Most of the available literatures have
leaching with HF followed by HNO3. In their study, in order to evaluate presented only proximate and ultimate analysis of coal, which is provid-
the effect of particle size (from −1000, −500, −250 and −75 μm) on ing a general idea of the overall coal but not the composition of ash
ash reduction, two types of coal samples were grinded and microwaved forming mineral matter in coal and their fate during UCC production.
(900 W for 7 min), followed by leaching at 25 °C for 2.5 h with 2 M HF. It Based on the available literature data as shown in Tables 1a–1c, only
was found that the percentage of ash removal increase with decreasing few research groups utilized high ash (17–43%) containing low grade
coal particle size from −1000 to −75 μm (Fig. 4). This was due to an in- coal for demineralization and most of the studies are based on the bitu-
crease of external surface area per unit mass of coal, mass transfer is a minous coal, ash content ranging from 5 to 10.36%, and very effective
limiting factor in the process and HF does not have free access to the re- demineralization occurred during UCC production from these coals. Vic-
active sites within the particles (in coarse particles). Grinding to smaller torian brown coals usually contains NaCl and very low mineral matters
particle would provide this access and HF leaching was more effective (b4%). Effective demineralization of these coals with weaker acids [37]
for demineralization from smaller particles (− 75 μm). Thus, grinding produces UCC with very low ash. Therefore, it is very important to de-
coal to a smaller particle size enhances the degree of demineralization termine the nature of minerals and ash composition either by the com-
and achieved 54.6 to 62.0% ash removal utilizing −75 μm coal particles. bination of X-Ray fluorescence (XRF) and atomic absorption (AA)
They reported that microwave irradiation pretreatment has a posi- techniques or inductive couple plasma- mass spectrometers (ICP-MS)
tive effect on demineralization with HF, this was more remarked on analysis or petrographic analysis to find out the effect of coal properties
coarser size particles. It has been suggested that pretreatment of coal on demineralization.
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 41

Table 1b
Reaction conditions for UCC production only by inorganic acid treatment.

Reagent used/process UCC ash content


Research group used Conditions Coal type/mineral matter (wt%) Remarks

Steel et al. [26] HF (1–14 M) followed Low Temperature Asher (LTA) at Australian Black Coal (bituminous) b1% Mg and Ca present in the
by HCl (1–11.5 M) 320–370 °C, 5 days (b1 mm), ash (13.4–14.1%) clay compounds do not
HF, 65 °C, 3 h followed by HCl, 20, completely dissolve in HCl.
70 and 100 °C, 3 h Thus, this is not considered
a viable option for the
complete removal of Ca and
Mg for producing UCC.
Steel et al. [27] HF (aq. 50 wt%) 3 h stirring at 65 °C Australian Black Coal (bituminous) NAa HF reacted preferentially with
followed by HCl aluminosilicates in coal.
(36 wt%) The fluoride precipitates are
dependent on the free
fluoride ion concentration
and can be suppressed by
manipulating the ionic
equilibria in solution.
Steel et al. [11] HF (0–7 M) followed by 3 h stirring at 65 °C UK bituminous coal (b500 μm), ash 0.6% HF does not react with
HNO3 (0–1.6 M) 7.9% pyrites, whereas HNO3 alone
reacts with pyrites above 1 M
HNO3 concentration
Steel et al. [42] HF (1–1.75 M) 3 h stirring at 20 °C Australian bituminous coal (Fine: b40 Mineral Coal's carbonaceous matrix
and coarse: b1000 μm) rejection N95% has the most profound
effect on the dissolution of
Ti and only way to extract Ti
is to crush the coal to a finer
particle size.
Steel and Patrick [12] HF (1.17 M) followed by 3 h stirring at 65 °C UK bituminous coal (b62 μm), ash 5% 0.2% HNO3 reacts simultaneously
HNO3(0–1.58 M) with pyrite and
carbonaceous matrix of the
coal.
Rubiera et al. [13] 25% HF, 60 °C, 8 h HF, 60 °C, 8 h High volatile bituminous coal 0.3% Demineralized coal
followed by 25% HNO3, HNO3, 60 °C 16 h, (1–2 mm), ash 6% combustion showed
16 h, 60 °C decrease in SO2 emission
and HNO3 treated coal
increased NO emissions.
Steel and Patrick [32] HF (2.42 M) followed by HF, 3 h, 65 °C followed by Al(NO3)3 UK, high volatile bituminous coal Selective Selective separation
Al(NO3)3·9H2O(1.28 M) 24 h, 80 °C (b62 μm) separation of technique for Si(IV) and
65% Si(IV) Al(III) from aluminosilicates.
Hence, this technique is
suitable for mineral
processing. HF (N90%),
Al(NO3)3 and HNO3 (N95%)
are regenerated from the
process.
Kizgut et al. [20] HF (2 M) followed by Stirred @RT 3 h, HF, 70 °C, filtered, Turkish, Australian and Polish coals 0.15–0.41% Calorific value of the coal
HNO3 (2 M) treatment dried, 80 °C overnight, HNO3 (−74 μm), ash (5.97–8.27%) samples decreased possibly
treatment due to the oxidation and
nitrification effect of HNO3.
Jorjani et al. [35] HF (0.5–3.5 M) followed Microwave irradiation (900 W, Iran's Zirab (ash 8.31%) and Tabas Zirab (0.69%) HF leaching efficiency was
by HNO3(1.4 M), 65 °C 7 min) Coal (ash 10.36%), (b75, b250, b500 and Tabas influenced by the particle
& b1000 μm), Iran (0.39%) Coal size reduction but the
microwave irradiation was
more effective for courser
coal particles.
a
NA: data not available.

3.2. Challenges in demineralization of coal to produce UCC treat the contaminated water and regeneration of chemicals used in
the process, which would make the overall process economic and cost
Coal contains alkali, alkaline earth and trace metals. Most of these effective. In addition, the mechanism of role of NaOH in coal cleaning
metals during combustion pose serious problems within the facility and its reactivity in the coal matrix is not properly understood, especial-
and in the environment once are released. So it is beneficial to remove ly with the inorganic minerals.
these metals from coal matrix during UCC and AFC production. Howev- Wijaya and Zhang [68] presented a review on mode of occurrences
er, removing these from the coal matrix is challenging. The main chal- of inorganic elements and organically bonded metals in coal matrix dur-
lenges of the direct use of coal are release of ash forming minerals and ing coal demineralization. Their paper addresses the fundamental as-
the related problems, like slagging, fouling in the combustion chamber pects and practical feasibilities related to removal of chemically
and emissions of toxic particulate matter, trace metals, NOx, SO2 etc. Re- bonded metals in coal matrix during coal upgrading process. They
moval of surface bound minerals or salts (like, NaCl, KCl or CaCl2 etc.) is have emphasized on the mode of occurrences of inorganic elements
possible by washing or rinsing with water but removal of organically and organically bonded metals in coal matrix and investigated the
bound metals are still a challenge. Since this process requires washing metals those are difficult to remove during UCC or HPC production pro-
of coal with fresh water and aqueous NaOH, it is very important to cess. The metals extracted by polar solvents during UCC production
42 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

possess complex structures, which are mostly acid-insoluble and are diagram of AFC/HPC process diagram, operating under the brand name
also difficult to remove through ion-exchange column. However, there KOBELCO, developed in 1999. This 0.1 t/day pilot plant is in operation at
have been studies in this area for low-rank Victorian coal having less Takasago, Japan and 10 t/day pilot plant is under construction [49]. Kobe
ash and high moisture content. Metals in low rank coal are mainly asso- Steel has been working on upgrading low rank coal with upgraded
ciated with organic matrix, in the form of organo-metal complex. Ethyl- brown coal (UBC) process to efficiently remove the water contained in
enediaminetetraacetic acid (EDTA), a chelating agent, has been used as low rank coal in heated light oil [50]. The project is subsidized by the
an efficient agent to remove metals including Fe bound with the organic Ministry of Economy, Trade and Industry (METI) and Japan Coal Energy
constituents in coal matrix. Center (JCOAL). A plant (production base capacity, 600 t/day) was con-
Grinding of coal is one of the ways to maximize the rate of removal structed in Indonesia and has been running to demonstrate a process
of mineral matter to a certain extent. However, this process is associated called the UBC process.
with high energy and cost and thus, it's been hard to realize. The dem- Even though, having a kind of demonstration plants, none of these
onstration of these results in a scale-up project is still among few chal- technologies are commercially available and many aspects of the tech-
lenges to meet. Therefore, the knowledge of these key aspects is nologies are still in research and developmental stage. A new cost-effec-
essential in order to understand the process involved and imply those tive and efficient approaches and technologies are therefore essential,
results for commercialization. especially to upgrade low-rank lignite and sub-bituminous coals. One
of such approaches could be the production of AFC.
4. Extraction of organic matters to produce ash-free coal (AFC)
4.1. Effect of solvents
Even though the UCC contains around 0.1–1.0% of ash it cannot be
directly fired in the gas turbines. Other concerns are associated with Solvents have the capability of relaxing the interactions among the
the corrosiveness and biodegradability of strong acids and alkali re- molecules constituting the organic portion of the coal. It also depends
agents used during UCC production and consequently the disposal of on the polarity of the solvents; low polar or non-polar will exhibit less
waste solutions. The second process uses organic solvents to dissolve or- and polar solvents have the high relaxing capability. As for example,
ganic matter and precipitating the AFC also known as hyper-coal (HPC) dimethylformamide (DMF) and N-methyl-2-pyrrolidinone (NMP) has
[44–46]. In this paper both of these are commonly termed as AFC. Fig. 1 the coal dissolving capability to a higher extent and thus results the
shows the schematic diagram of preparation of AFC by solvent extrac- higher extraction yields [51].
tion (path C). Solvent extraction of coal using organic solvents can pro- Extensive research is being carried out by several research groups
duce AFC that has significantly much lower ash content level (as low as (summarized in Tables 2a–2d) for the production of AFC suitable for
200 ppm) than UCC. In addition, this process helps to remove alkali and new power generation technologies. Solvent extraction have been car-
heavy metals and almost all inorganic sulfurs. ried out using different type of solvents such as polar, non-polar and
AFC research and process development have been carried out since mixed. Issues like recycling of the solvent, filtration condition, optimum
1999. Currently, the New Energy and Industrial Technology Develop- extraction conditions and universal solvent for coals of different origin
ment Organization (NEDO), Japan, is developing methods for using and good thermal stability need to be examined to minimize the cost
AFC in power generation system. Researchers have found that solvent of AFC production process.
extraction of raw coal utilizing suitable organic solvents can provide
AFC with the following major features [47]: 4.1.1. Extraction of coal by polar solvents
Polar solvents are one of the best solvents those have the capability
• Ash content decreases to ~200 ppm or less. of dissolving polar (O, N and S containing organic components) in the
• Alkali metals concentration (Na, K) decreases to ~0.5 ppm. coal matrix. Renganathan et al. [44] investigated N-methylpyrrolidone
• Calorific value increases by ~10–20% compared to raw coal. (NMP)'s ability to reduce the ash and pyritic sulfur content of coal.
• Inorganic sulfur is almost zero. They found that the ash content of various bituminous coals could be re-
• Heavy metals content significantly decreases to 1/100 or less. duced to as low as 0.1% by simple extraction with NMP using a mild op-
• Excellent gasification feedstock. erating condition at 202 °C and atmospheric pressure.
• It has excellent ignitability and combustion properties. Kim et al. [52] conducted a study for the purpose of producing low
• It exhibits good thermal plasticity. ash coal from low rank coals, such as lignite and sub-bituminous
through extraction using polar solvent, NMP and compared the extrac-
Several potential promising technologies for upgrading coals are at tion yield with bituminous coal. Extraction experiments were done in
different levels of development: experimental, demonstration and an the temperature range of 200–430 °C, initial applied pressure of 1–
industrial scale (KOBE Steel Ltd., Japan) [48]. Fig. 5 shows the schematic 20 bar and extraction time of 0.5–2 h using coal to solvent ratio of

Table 1c
Reaction conditions for UCC production by organic acid treatment.

Reagent UCC ash


Research used/process content
group used Conditions Coal type/mineral matter (wt%) Remarks

Wijaya Pyroligneous acid Coal + pyroligneous acid (1 M), Two Victorian Brown coals Coal A Cheap and weaker acids like pyroligneous acid
et al. (1 M), citric acid citric acid (1 M) + Na–EDTA (0.1 M), (106–150 μm), ash (1.65 and 2.35%) (0.08%) and citric acid has been successfully utilized for
[36] (1 M) and Na– stirred @RT 3 h, pure water washing, and Coal generation of UCC.
EDTA (0.1 M) dried @ 115 °C, 2 h B (1.5%) Substantial reduction of sulfur and chlorine
contents of UCC.
Wijaya Pyroligneous acid High temperature and high pressure Two Victorian Brown coals, Coal A, ash Coal A Potential use of waste weak acids for brown coal
et al. (1 M), citric acid leaching, autoclave reactor at 65, (1.9–2.37) and coal B, ash (2.22–3.4%), (0.12%) leaching to generate UCC. Both coarse and fine
[37] (1 M) and Na– 120, and 200 °C were conducted Four different particle sizes, b53, and Coal sizes negatively affect coal demineralization by
EDTA (0.1 M) with continuous stirring. 106–153, 153–300, and 300–600 B (1.07%) increasing the intra-particle diffusion resistance.
The degree of demineralization of brown coal
(rich in organically bound metals) was
independent of temperature.
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 43

The effect of addition of some polar compounds into non-polar ex-


traction solvent on the extraction yield was also investigated. The addi-
tion led to an increase in the extraction yield, while, the quantities of
solvent remained in the extract and residue increased. The extraction
yield did not reach the same level as the CMNO, even when the nitrogen
content in the mixture of solvent/additives was almost identical to that
in those solvents.
Recently, Mahat et al. [55] treated sub-bituminous and bituminous
coals with commonly used polar solvents like Chloroform, Dichloro-
methane (DCM) and Ethyl acetate (EA) under pressurized vessel system
utilizing microwave radiation heating. They also compared the perfor-
mance of the pressure-vessel techniques in terms of extraction efficien-
Fig. 4. Effect of coal particle size on ash reduction for Tabas (T), Tabas-microwaved (Tm) at
cy to that of Soxhlet extraction and found that overall 30–40% efficiency
900 W, 7 min, Zirab (Z), and Zirab-microwaved (Zm) at 900 W, 7 min coal samples (2.5 h,
25 °C, 2 M HF), [35]. (Reprinted with permission from Copyright (2011) Elsevier). enhancement. Although the extraction yield reported was very low
(b 8%) compared with the other high boiling solvents like LCO, CMNO
[46]. In addition to the enhancement of the efficiency in microwave ir-
1:10. The extraction yield increased with the increase of extraction tem- radiation method, it also allows substantial reduction of solvent and
perature, and the ash content of extracted coal decreased below 0.4% at sample used by a factor of 25 compared with the Soxhlet method.
400 °C from the raw coal samples that have the ash contents of 4–6%.
Experimental results showed increase in fixed carbon and calorific 4.1.2. Extraction of coal by non-polar solvents
value, and decrease in H/C and O/C ratio. Non-polar solvents have the capability of dissolving mainly non-
Although, NMP showed high [48] extraction rate (~70% daf), as one polar organic components of the coal. A team of Japanese researchers
of the strongest solvents to extract coals from various rank coals at [56], studied extraction of Argonne premium coals and an Australian
350 °C, a large amount of NMP was lost due to a strong linkage with brown coal in a flowing stream of non-polar solvents such as tetralin
coal molecules in every cases [53]. This is possibly due to the presence and 1-methylnaphthalene (1-MN) at 200–400 °C and 10 MPa pressure,
of the carbonyl functional groups at the C-2 in NMP, which reacts with where they observed that the bituminous coals has negligible decompo-
the coal particles. sition below 350 °C and thus obtained lower yields, whereas the extrac-
Ouchi et al. [54] studied thermal extraction of a Japanese bituminous tion yield reached 65–80% above 350 °C. Okuyama et al. [48] reported
coal (81.2%, 350 °C) in an autoclave under 1 MPa of nitrogen with pyri- that the use of non-polar two-ring aromatic solvent in some bituminous
dine and quinoline at 200–400 °C. They reported an extraction yield of coal can achieve an extraction yield of almost 70% (daf); however, the
50% at 400 °C with pyridine; whereas, quinoline produced similar ex- yield was below 60% in case of sub-bituminous coal. They also reported
traction yield at 300 °C. The maximum yield achieved was about a comprehensive techno economic analysis and estimated that the cal-
80 wt% with quinoline at 350 °C. This result was interpreted as being orie based cost of Hyper-coal would be competitive to a general coal
due to the intimate sealing of extractable material in the network mac- price including its ash disposal cost in Japan.
romolecular structure or in the larger molecules. It was confirmed that In order to obtain ash-less coal in a high yield, solvent extractions
the pyridine extracts are not thermal decomposition products, but the with various organic solvents such as tetralin, 1-MN,
true extracts. dimethylnaphthalene (DMN) and light cycle oil (LCO) at 200–380 °C
The extraction yield (for Illinois No. 6 coal) gradually increased over were carried out using batch type extractor by Yoshida et al. [45] for var-
200 °C, and a significant increase in extraction yield was observed from ious ranks of coals under nitrogen atmosphere. Subsequent solid/solu-
350 to 360 °C. In a separate investigation, same research group [46] per- tion separation was done at room temperature. They succeeded in
formed production of AFC with several organic solvents such as crude producing ash-less coal with b0.1% ash content for seven out of nine
methylnaphthalene oil (CMNO), LCO under hot filtration at 360 °C coals. Extraction yields with DMN at 360 °C were 24–54% regardless of
using a flow-type extractor. They got much higher extraction yield coal rank. LCO was found to be a useful solvent, since it gave similar ex-
(N80 wt%) using CMNO than LCO, which was previously reported as a traction yields (~40%) to three other solvents.
useful solvent for AFC production. It is interpreted that high extraction Okuyama et al. [48] investigated 20 different coals, mainly bitumi-
yield obtained was due to the solvent-induced relaxation of coal aggre- nous, belonging to Australian, Indonesian, United States and Chinese or-
gates by the nitrogen-containing compounds, in addition to the ther- igin and extracted with a non-hydrogen donor solvent, 1-MN at 360 °C.
mal-induced relaxation. The extraction yields were within the range 30–72% (shown in Fig. 6)

Fig. 5. Schematic diagram of AFC/HPC process in Kobe Steel Ltd. Redrawn after [49].
44 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

Table 2a
Reaction conditions for AFC production by polar solvents.

Research
group Solvent used Conditions Coal type Yield (%) Ash content (%) Remarks

Renganathan NMP (10:1 202 °C, 1 atm H.V. bituminous coals, 74% (maf) b0.1–0.7% Non-destructive isolation of organic materials from
et al. [44] solvent to coal) b74 μm, ash max bituminous coal and NMP. Recoveries were high (97%) and
(6.2–26.4%) yield did not contain any pyritic sulfur.
Ouchi et al. Quinoline, 200–400 °C, 1 MPa, Japanese bituminous 50–90% at NAa Pyridine extraction yields was ~50% at 400 °C, while
[54] pyridine N2 coal b149 μm, ash 350–400 °C quinolone extract was found ~90% even at lower
(7.6–9.7%) temperature (350 °C). Thermal decomposition and
polymerization played a role at higher temperature.
Miura et al. DMF 25 °C Argonne premium, ash 58–77% for 0.8% The highly polar solvent DMF has the capability of dissolving
[56] (4.8–19.8%) bituminous organic components from coal matrix or from the deposit
coals, 25 °C even at room temperature.
Kim et al. NMP (10:1 200–430 °C, Sub-bituminous coal, ~90% 0.4% The extraction yield increased with the increase of
[52] solvent to coal) 1-20 bar (0.5-2 h) b75 μm, ash (4–6%) temperature. The initial applied pressure showed slight
effect on the extraction yield without any significant ash
reduction.
Makgato et NMP, DMF RT, stirred South African 27.5–82% 0.7–1.6% Coal dissolves in DMF and NMP to a limited extent. Addition
al. [51] NaOH, tBuONa, (60 rpm), 24 h, N2, meta-bituminous of a strong base increased the degree of coal dissolution and
hydrated Na2S filtered, vacuum Tshikondeni coal, reached up to 90%. Addition of Na2S provided high purity
(60–62%) dried at 60 °C b150 μm, ash (9.4%) coal extract (ash content 0.7%), but with the cost of
additional reagent and lower coal recovery.
Kolak and DCM, CS2, SCCO2 DCM (40 °C) Bituminous coal, 40–60% NAa CS2 and DCM extraction yields were very similar, whereas,
Burruss CS2 (46 °C) 125–250 μm, ash SCCO2 produced lower extraction yield.
[73] CO2 (40 °C), (4.01–5.52%)
100 bar
Samanta and Tetrahydrofuran THF (66 °C), Indian coal, average NAa Ash rejection; THF has the better mineral matter reduction capability than
Mondal (THF), 1, 1,4-dioxane particles, 126 (A), 258 A (23.16%) that of 1, 4 dioxane and diethyl ether. Finer coal particles has
[74] 4-dioxane (101 °C), diethyl (B) and 403 (C) μm B (15.26%) a significant effect on reduction of mineral matters and
diethyl ether ether (35 °C) C (12.42%) yields more soluble compounds.
a
NA: data not available.

and these yields were largely depending on the characteristics of the temperatures ranging from 300 to 400 °C, and observed no significant
raw coals. In general, it was observed that lower moisture containing difference in extraction yields at lower temperatures (b320 °C) but ex-
(0.7%) Upper Freeport (UPF) coal produced higher extraction yield traction yields increased rapidly above 340 °C with the use of tetralin.
(~ 72%). Similar trend was also found in case of Guregory (GUR), This is possibly due to the release of transferable hydrogen in tetralin
Guregory-B (GUR-B), Oaky creek (OKC), Stratford (STF), Enshu at these temperatures (≥340 °C). This result indicates that transfer of
(Yanzhou) (EN), Pittsburgh (PIT) and Kestrel (KST) coals and yields hydrogen from solvent to coal increases the extraction yields. In other
were within the range of 52 to 68%. Only exception was Yakut 9 (YK9) word, by the use of tetralin, soluble coal molecules are not only extract-
coal, although it contains only 2.1% moisture, it produced low yield ed by the solvent from coal structures but also by thermal decomposi-
(30%). High moisture (17.2%) and high ash (24.9%) containing coal tion of the coal structure. As a result, small molecules are generating
Longkou (LK) produced moderate yield of ~38%. and stabilizing by accepting hydrogen, generated from the reaction sys-
Okuyama et al. [48] also investigated the effect of hydrogen donor tem or from the hydrogen donor solvents. Therefore, intermolecular hy-
solvent (tetralin) extraction yield capability comparing with 1-MN drogen transfer is playing an important role for enhancing the
(Fig. 7). They treated STF coal with 1-MN and tetralin at different extraction rate or the extraction yield.

Table 2b
Reaction conditions for AFC production by non-polar solvents.

Research Solvent
group used Conditions Coal type Yield (%) Ash (%) Remarks

Miura et al. Tetralin, 200–400 °C, Argonne premium and 65–80% for 0–0.3% The extraction yields of lower rank coals were not high compared to
[56] 1-MN 10 MPa Australian brown coal, ash bituminous coals at bituminous coals. This technique is useful to extract organic
(1.5–19.8%) 350 °C molecules without decomposition of coal.
Yoshida et Tetralin, 200–380 °C, 16 coal samples with wide DMN (21–54%), LCO b0.1% About 40% extraction yield was obtained from LCO and reported be a
al. [45] 1-MN, 0.4 MPa, 1 h variety of carbon content, (15.0–38.9%), tetralin cost-effective industrial solvent for coal extraction.
DMN, ash (3.8–19.6%) (24.5–26.1%)
LCO
Okuyama et 1-MN, 360–380 °C Bituminous coals 70% (daf) for 0.01–0.05% Development of a promising de-ashing technology for AFC
al. [48] Tetralin, 0.1 MPa, N2 b250 μm, ash (4.8–24.9%) bituminous coal production in a cost-effective manner.
1-MN is recyclable and has a good affinity to coal as well as good
thermal stability.
Takanohashi 1-MN 300–420 °C, Bituminous coal, 66.7% (daf) at 360 °C 0.03–1.0% The distribution of carbon type in HyperCoals obtained from
et al. [58] 1 MPa, 1 h b150 μm, ash (3.2–15.1%) extraction below 360 °C was similar to their parent coals.
HyperCoals showed high thermo plasticity during heating, at
temperature as low as 150 °C. NMR results revealed that the ratio of
aromatic carbon increased with increasing extraction temperature.
Lee et al. 1-MN 370 °C, Samhwa brown coal, NAa 0.19% Evaluated the performance of AFC, raw coal, active carbon, carbon
[75] 30 bar b74 μm, ash (2.4%) black and graphite as fuel for DCFC. The power density of AFC was
strongly temperature-dependent and in general decreased over
time.
a
NA: data not available.
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 45

Table 2c
Reaction conditions for AFC production by mixed solvents.

Research
group Solvent used Conditions Coal type Yield (%) Ash (%) Remarks

Iino et al. CS2/NMP (1:1) Room Bituminous coals 30–66% (daf) b0.5% ~60% yield was obtained from bituminous coal at room
[60] Temperature, b250 μm and Argonne temperature. Anthracite, sub-bituminous and lignite coals
1 atm coal b149 μm, ash did not give high yields.
(2.5–31.7%)
Sun et al. SCCO2/NMP (1:1) scCO2/NMP and 24 Chinese coals, lignite 3.30–27.96% NAa The scCO2/NMP mixed solvent extraction yields from low
[76] CS2/NMP, 5 °C, to anthracite, b180 μm, rank coals were higher than that of CS2/NMP and both of
18 h stirring at ash (4.89–36.52) these mixtures have much higher yield than that of pure
revs min−1 NMP extraction. Therefore, scCO2 can be considered as a
proper solvent to replace CS2.
Sonmez NMP, NMP/EDA Microwave Turkish coal (Cayırhan, Thermal 0.11–1.1% NMP/EDA and NMP/tetralin mixed solvents were found to
and (17:1), NMP/Tetralin irradiation, Soma and Tuncbilek), (13.0–33.8%) be promising for coal extraction by microwave irradiation,
Giray (9:1) 180–202 °C b250 μm, ash Microwave although, NMP/EDA mixed solvent produced slightly
[77] (22.1–27.2%) (12.2–31.2%) higher thermal extraction yield.
Kashimura Polar materials 360 °C and 1 MPa, Sub-bituminous coal, 73% (daf) NAa Polar materials were successfully concentrated from a
et al. fractionated from 1h b150 μm, ash 8.8% (Methanol-water cost-effective industrial solvent, CMNO, the extraction
[61] CMNO using HCl and soluble fraction of yields of which were 20–30% higher than that of original
CH3OH-water CMNO) CMNO. A small amount of methanol addition to
N-containing polar solvent significantly increased the
thermal extraction yield at 360 °C.
a
Sakimoto 1-MN, Indole (0, 10, 20 Semi-batch Argonne Premium and ~71% NA The extraction yield increased linearly with the increase
et al. mass% to 1-MN) reactor, Mulia coals, b150 μm, of Indole concentration. Higher extraction yield from
[63] N2(1 MPa), 360 °C ash (1.7–15.5%) low-rank coals were achieved with high oxygen content;
polar solvent is recommended for high oxygen (≥8.2%)
coal.
a
NA: data not available.

In case of non-hydrogen donor solvent 1-MN, the extraction yield in- It was observed that ash-less coal had many light components that
creased rapidly until 350 °C, and then decreased gradually with the in- volatize and decompose easily and has high thermal reactivity. All the
crease of temperature. This phenomenon can be explained by the fact ash-less coals showed high thermo plasticity during heating near
that 1-MN could not transfer hydrogen to increase the extraction rate. 150 °C. Nuclear magnetic resonance (NMR) measurements showed
On the other hand, at this temperature range (N350–500 °C), coal mol- that the ratio of aromatic carbon increased with increasing extraction
ecule may undergo rapid thermal decomposition and generates free temperature, indicating that some modification reactions occurred.
radicals, which may combine with each other or with large stable mol- Recently, Anon [59] has used liquid or supercritical CO2 (scCO2) to
ecules [57] via cross-linking to produce residual coal. They also observed produce AFC. They observed that AFC from liquid CO2 extraction has a
that the H/C atomic ratio of coal liquid extracted by 1-MN rapidly de- high calorific value and only negligible amounts of ash. Moreover, it
creased. This result indicates that there was gradual condensation of re- showed excellent thermal plasticity properties even though the raw
sidual coal; this phenomenon may inhibit the release of the solvent- coal did not show such behavior.
soluble coal molecules from the cross-linking coal matrix.
Takanohashi et al. [58] undertook the characterization (structural 4.1.3. Mixed solvents
and thermal analysis) of ash-less coal produced by thermal extraction To overcome the issues related with the use of NMP alone at higher
of various ranks coals with 1-MN at temperatures from 300 to 420 °C. temperatures (≥ 350 °C) (discussed in Section 4.1), researchers have

Table 2d
Reaction conditions for AFC production by miscellaneous solvents.

Research
group Solvent used Conditions Coal type Yield (%) Ash (%) Remarks

Yoshida 1-MN, DMN, LCO, 200–360 °C, 1 MPa Argonne Premium coals, CMNO CMNO High extraction yields of HyperCoal with several
et al. CMNO b150 μm, ash (4.4–15.0%) (74.6–80.7%), (0.20–0.3%), organic solvents under hot filtration at 360 °C using a
[46] LCO LCO (0–0.1%), flow-type reactor.
(44.0–55.8%), DMN The high extraction yield with CMNO might be due to
DMN (0.7–2.3%) the solvent-induced relaxation of coal matrix by
(62.3–74.0%) N-containing compounds.
Andrews Refinery oil and Solvent/coal (2:1), Bituminous coals, Blue 76–91% 0.18–0.5% A small micro-reactor based experimental set-up was
et al. anthracene oil sand bath, Gem, Davis, Springfield used in sand bath to assess the dissolution of coals in
[69] 450–550 °C, and Pittsburg, b75 μm process solvents to produce low ash containing coking
1.4 MPa (200 psi), ash (1.2–19%) coal with reasonably high conversion yield.
1h
Vostrikov Supercritical 30 MPa, 400– Brown coal, 20–25, 48–62.8% NAa Utilization of SCW in continuous coal conversion
et al. water (SCW) and 760 °C 40–50, 75–80, system would be more effective once coal water slurry
[78] O2 200–315 μm, ash (10.1%) (CWS) is supplied as fuel for energy production
without agglomeration of coal particles.
Rahman 1-MN, 200–450 °C, 10 psi, Lignite and 78.4% 0.0–0.08% Assessing the impact of coal quality on extraction yield
et al. hydrotreated and 1h sub-bituminous coals, was difficult due to involvement of several parameters
[62] non-hydrotreated b150 μm, ash such as temperature, solvent, coal type. However,
industrial solvent (10.58–21.64%) maceral content of coals played an important role in
coal extraction. Higher vitrinite-rich coal produced
higher extraction yield.
a
NA: data not available.
46 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

dissolve the constituents of coal. It has been observed that MW-S


contained more indole than AC-S. The results of additional tests sug-
gested that indole has a greater ability to extract coal constituents
than quinoline. They also observed that the addition of 5% methanol
to a mixture of 1-methylnaphthalene, indole, and quinoline (30/20/
50%) increased the extraction yield from 58 to 69%, which was close to
the yield of MW-S (73%). Therefore, it has been concluded that the
high extraction yield of MW-S can be explained by not only the compo-
sition of the nitrogen-containing polar materials in MW-S but also the
presence of methanol.
Rahman et al. [62], used hydrotreated coal tar distillate, also referred
as industrial solvent for the extraction of low grade Canadian coal for
the production AFC. GC–MS of industrial solvents confirms the presence
of mixed poly aromatic hydrocarbons (PAHs), mainly naphthalene and
anthracene derivatives, including some heterocyclic compounds. The
maximum yield of AFC utilizing the industrial solvent was 73% (daf,
based on the produced AFC) and 78.4% (daf, based on unconverted re-
sidual coal) at 400 °C.
Sakimoto et al. [63], investigated the effect of addition of polar com-
ponent (Indole) to nonpolar solvent (1-MN) and found that the extrac-
Fig. 6. Comparison of the coal extraction yields at 360 °C. Okuyama et al. [48]. Note: YK9 to tion yield increased linearly with the increase of Indole concentration
UPF are coal types used in the study. (Reprinted with permission from Copyright (2004) from 0 to 20% (mass of 1-MN). They also recommended that polar sol-
Elsevier).
vent is necessary for achieving the higher extraction yields from low-
rank coals with the high oxygen content (≥8.2%).
tried mixing solvents. Such as, Iino et al. [60] utilized NMP and CS2 (1:1 Painter et al. [64], observed that use of ionic liquid (1-butyl-3-
by volume) for extracting bituminous coals at room temperature and methylimidazolium chloride) as co-solvent with NMP and Pyridine, sig-
successively achieved extraction yield over 60%. The anthracite, sub-bi- nificantly enhances the extraction yields, although Upper Freeport coal
tuminous coals and lignite did not give high yields. They suggested that produced slightly lower yield (29.2%) than that of pyridine alone (35%).
solvent loosens the bonding of organic matters in coal. The synergistic Ionic liquids have the capability of solubilizing, disintegrating and dis-
effect, i.e. the large increase in yield and rate for the mixed solvent com- persing certain fine coal particles to a remarked extent. Coals possess in-
pared with those for CS2 and NMP alone has been explained by increas- consistent behavior and not most coals have densely cross-linked
ing solubility and diffusibility of the extracts and increasing swelling of networks, where a portion of soluble material remains trapped in coal
the coals, in the mixed solvent. Okuyama et al. [48,53] also found that matrix, even upon swelling in good solvents, which fracture and only
mixed solvents of CS2 with quinoline, pyridine and Tetrahydrofuran partially fragment coals at ambient temperatures and allowing dissolu-
(THF) gave lower extraction yields than the CS2-NMP mixed solvent. tion of trapped materials. It is also observed that the degree of swelling
Kashimura et al. [61] reported ash-free coal production from low- and the soluble materials recovery from low rank coals depends on the
rank coals, such as sub-bituminous coal by extraction with a polar sol- extent of covalent cross-linking, formation of salt bridges and π-cation
vent concentrated from a polar industrial solvent, CMNO at tempera- interactions in the coal matrix [65–67].
tures around 360 °C. The methanol-water soluble fraction of CMNO Tables 2a–2d summarize the reaction conditions, yield and ash con-
(MW-S) extracted 73% (daf) of Wyodak Anderson sub-bituminous tent in the upgraded AFC production by different research groups. Even
coal at 360 °C, while that obtained using aqueous HCl (AC-S) extracted though, the ash content of the upgraded coal should be b0.1% to be con-
63%. These extraction yields were much higher than those with CMNO sidered as AFC for application in IGCC power plant Wijaya and Zhang
(43%), indicating that fractionation concentrated the materials that [68], many researchers are producing AFC with higher ash content with-
in the range of 0 to 2.3%. Among the literatures cited in Tables 2a–2d
only three of them [45,48,62] are meeting the criteria for utilizing AFC
in IGCC.
As seen in Tables 2a–2d, most of the experiments have been done in
higher temperature N350 °C. In general extraction yield has been found
higher at high temperature. As for example, Andrews et al. [69] reported
extraction yield as high as 91% from bituminous coal with refinery oil
and anthracene oil at 450–550 °C, 1.4 MPa (200 psi). However, in
other study even at room temperature the extraction yield reached to
82% utilizing NMP, DMF NaOH, tBuONa, hydrated Na2S [51].
In Tables 2a–2d we have summarized the extraction yield and the
operating conditions that are available in the literature. It is difficult to
generalize and correlate the extraction yield to the operating conditions
of the process from those bulky data, considering that these need stud-
ies in controlled conditions. Nevertheless, in order to explain/explore
the effect of various parameters on the extraction yield we have de-
scribed the effect of each operating conditions in Sections 4.1 to 4.5.
It is evident from Table 2a that the polar solvent, NMP, is providing
N70% yield even at lower extraction temperature (202 °C), extraction
yield is reaching ~90% at higher temperature (N350 °C) with production
of AFC with very low ash content. Other polar solvents like Pyridine and
Fig. 7. Comparison of coal extraction performance between 1-MN and tetralin (STF coal) Quinoline are also reasonably good solvent for producing AFC with good
[48] (Reprinted with permission from Copyright (2004) Elsevier). yields at higher temperatures (N 350 °C). Polar solvents (DCM, CS2 and
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 47

SCCO2) with low boiling point have also been used for the extraction of The coal particles are connected together by hydrogen bonding and
organic components from coal but the yield is comparatively low. Van der Waals attractive forces into the coal matrix. As described by
Polar solvent with high boiling point, DMF, is suitable for extracting Woskoboenko et al. [72], the inter-particle hydrogen bonding is attrib-
small molecular weight compounds from the deposit even at 25 °C, uted to the interaction of the carboxyl, hydroxyl and carbonyl functional
those could not be extracted by tetralin at 350 °C [56]. groups via the water in the micropores. The alkaline digestion mecha-
Table 2b, summarizes the reaction conditions of AFC with non-polar nism is pH dependent. At the natural pH range of 3.5 to 6.5, a portion
solvents like Tetralin, 1-MN, DMN and LCO. Among these solvents 2- of the acidic protons are dissociated and develops a negative charge
ring aromatic solvents Tetralin and 1-MN found to be better for produc- on the coal particles. As a result the mutual repulsion between the neg-
ing AFC with reasonably good yields at higher temperatures (N 350 °C), atively charged particles prevents the coalescence of particles. Once coal
while LCO and DMN is providing moderate yields (maximum ~ 50%). is treated with NaOH the ionic equilibrium of the system is interrupted
Table 2c, represents literature data obtained by the mixture of polar and the coal behaves like a polyprotic acid. In pH higher (range ~4–8),
and non-polar solvents with different ratios. NMP mixed with equal vol- carboxylic acids undergoes dissociation first then the less acidic phenols
ume of CS2 produced around 60% yield of AFC from bituminous coal at (pH 10–14). As the coal is gradually titrated with NaOH, the negative
room temperature, while the same solvent mixed with scCO2 and CS2 charges on the surface of the coal particle increase and the electrostatic
at 5 °C produced lower yields (~28%). Anthracite and lignite coal pro- repulsion between the surfaces increase too. This results migration of
duced even lower yields. Overall decrease in the extraction yield is produced hydrated Na+ ions into the pores of the coal particles and for-
probably due to the lowering the polarity of the solvent mixture and mation of an electrical double layer and maintains an electro-neutrality
lowering the extraction temperature from room temperature to 5 °C. within the pore. The electrostatic repulsion forces between the coal sur-
NMP found to be a good polar solvent for extraction of coal, but while faces and the swelling produced by the movement of hydrated Na+ and
mixing with EDA or Tetralin at different ratios and extraction was car- OH– ions into the micropores gradually pushes the surfaces apart
ried out under microwave irradiation at 180–202 °C, the yields were resulting breaking down of the chemical bonds.
reasonably low (~ 31%). Polar components extracted from CMNO by
HCl and methanol treatment was used to extract coal and found reason- 4.2. Effect of temperature
ably good yield (~ 73%) at 360 °C. Almost, a similar extraction yield
(~71%) was obtained under similar extraction conditions with the mix- Softening temperature of parent coal affects the extraction yields of
ture of non-polar solvent 1-MN and polar compound Indole. These re- AFC. Mochida et al. [57] has shown that the softening point of a coal has
sults indicate that polar additives and higher extraction temperature a significant effect on the extraction yield. The relation between coal
are essential to get the reasonably good extraction yields from lignite softening point and extraction yield is shown in Fig. 9. If the softening
or bituminous coals. point of coal is closer to the extraction temperature, the coal extraction
Table 2d, summarizes the use of miscellaneous solvents for the pro- rate becomes higher, which indicates that the softening point of coal af-
duction of AFC. Yoshida et al. [46] utilized 1-MN, DMN, and industrial fects dissolving rate of coal.
oils like light cycle oil (LCO) and crude methylnaphthalene oil Yoshida et al. [45] also found higher correlation between the soften-
(CMNO) for extraction of coal at 360 °C, and found that the CMNO pro- ing temperature of raw coal and the extraction yields with (a) DMN-W
vided the higher extraction yields (~80%). This is probably the effect of and (b) LCO (Fig. 10). As shown in the figures, the negative relationship
the polar components present in CMNO. Similarly, refinery oil, anthra- existed between the extraction rate and the coal softening temperature
cene oil and hydrotreated industrial oils produced excellent extraction i.e. coal with lower softening temperature tended to give higher extrac-
yields of AFC within the range of 76–91% with very low ash content in tion yield. As explained in their paper this might be due to thermal re-
the extracted coal. Supercritical water (SCW) and O2 have also been laxation of coal molecules. With lower softening temperature thermal
used and found around ~ 60% yield at very high temperature (400– relaxation of coal molecule would be more remarkable and extraction
760 °C). It is apparent from these results that industrial oils have the yield would be higher.
very good relaxation capability of coal matrix at higher temperature Rahman et al. [62] used Canadian coal for the production of AFC in a
(N350 °C) under pressure and thus dissolves most of the organic 0.5 L high pressure autoclave reactor in temperature ranging from 200
components. to 450 °C using 1-MN, with 1 h of holding time for CV coal (sub-bitumi-
nous) (Table 3). In those experiments, the extraction yield at 360 °C
with 1-MN and CV coal (sub-bituminous) was about 28.2%. Tempera-
4.1.4. Effect of pre-treatment with alkalis ture below 300 °C, AFC extraction yield was low, however, the yield in-
Sharma and Singh [70] extracted Assam coal with ethylenediamine creased with the increasing temperature (above 300 °C) and maximum
(EDA) using a Soxhlet apparatus for 24 h at 100 °C. This stepwise extrac- yield (30.4%) was observed at 400 °C. This might be due to the enhanced
tion of coal in EDA resulted in 44% extraction yield. Aqueous alkali treat- coal–solvent interaction at elevated temperature. The solvent induced
ment followed by solvent extraction enhanced the extractability of coal thermal relaxation of coal molecules occurs at high temperature releas-
in EDA and resulted in 50% extraction yield. Apart from EDA, they also ing mainly small molecules and free radicals from the cross-linking coal
tried various other organic solvents in the aqueous alkali treatment of structure to the solvent [48]. Increasing temperature beyond 400 °C did
coal, such as, tetralin, phenol, quinoline, ethanol and butanol. The ex- not increase the yield, such as at 450 °C yield decreased (13.5%), which
traction yields were low, within the range of 13 to 25%. They also uti- might be due to recombination of the free radicals [57].
lized weaker bases like Na2CO3 and Ca(OH)2 along with NaOH in the
alkali treatment to enhance the extraction yield, but did not improve 4.3. Effect of initial pressure
the extractability of the coal. Non-aqueous alkali treatment of coal
using solid NaOH in different organic solvents such as phenol, tetralin A very little information is available in the literature on the effect of
and pyridine also resulted an enhanced (14–20%) extraction yields. initial pressure on the extraction yield. Kim et al. [52] investigated the
These results indicate that alkaline degradation technique is a good effect of initial pressure on the extraction yield and they also tried to
method for producing clean coal by stepwise extraction of coal, even find a correlation between the initial applied pressure with the ash con-
with dilute NaOH (1.5%) at 100 °C under atmospheric pressure with a tent of extracted coal and residual coal. Fig. 11, shows the variation of
low to moderate extraction yield. Mechanism of such alkali treatment extraction yield Kideko and Roto South coal with initial applied pres-
methods for coal digestion was proposed by Camier and Siemon [71]. sure. They observed that once the initial pressure was 1, 5 and 10 bar,
They proposed the two step ionization mechanism for the alkaline di- the pressure developed inside the reactor vessel was 10–15, 30–50
gestion of brown coal (Fig. 8). and N50 bar, respectively. Although, with the increase of initial pressure,
48 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

O O O
NaOH NaOH
Hum C Hum C Na Hum C Na
OH O O
OH OH O Na
+ H2O + H2O
pH 4 pH 5-8 pH > 8

Fig. 8. Mechanism involved in coal digestion by NaOH. Redrawn after Woskoboenko et al. [72].

the reactor pressure increased substantially, but the extraction yield 4.4. Effect of particle size
was b60% in Kideko coal and ~ 70% in Roto South coal, indicating that
there was no significant change in the extraction yield. The extraction The effects of particle size on the coal liquefaction were studied and
yield was ~ 75% at initial applied pressure of 1 bar, while with the in- some inconsistent inferences exist in the available literature. Because of
creased pressure to 3 bar at 400 °C the extraction yield was up to 90%. the difference in the operating parameters, extraction solvents and con-
These results recommend that the initial applied pressure does not ditions, it is difficult to assess and make direct comparisons among the
have significant effect on the extraction yield. However, the extraction available literature to draw conclusion out of it. In order to investigate
yield can be improved by increasing extraction temperature rather the effect of particle size on the Elbistan lignite liquefaction, coal parti-
than initial applied pressure. This strategy was also supported by their cles of 0.25 and 1.5 mm were treated with Tetralin (solvent/coal ratio
observation, that at constant initial pressure of 1 bar and at 350 °C, the 3:1) at 400 °C for an hour, and observed that the reduction of particle
extraction yield was increased gradually; from 50 to 65% in case of size from 1.5 to 0.25 mm did not cause any significant changes in the
Kideko coal with the increase of reaction time from 0.5 to 2 h. total conversion, only changed from 72.57 to 72.79% [79]. Similar, trends
Figs. 12 and 13 show the variation of the ash content in extracted were also observed by Li et al., Curran et al. [80,81] with different coal
coal and residual coal with initial applied pressure for the Kideko and particle sizes ranging from 74 to 700 μm within the extraction temper-
Roto South coal samples. There was no significant change initiated by ature ranging from 350 to 450 °C. Some other studies have shown that
the increase of initial applied pressure with the extraction temperature the initial particle size has no effect on the extraction yields of coal liq-
(Fig. 12). Once the extraction temperature was increased to 400 °C, ash uefaction process [81–85]. Curran et al., studied the kinetics of coal ex-
content was b0.3%. This result also indicates that in order to achieve traction with pure hydrogen donor solvent (Tetralin) and reported
lower ash content in extracted coal, it is better to increase the extraction that their runs with two size fractions,74–149 μm and 297–700 μm,
temperature rather than increasing initial applied pressure. gave identical results and concluded the conversion and rate of reaction
Fig. 13 shows the variation of ash content in residual coal associated are independent of particle size [80].
with the change in the initial applied pressure. No significant effect of Giri and Sharma [86] investigated the mass transfer limitations on
initial applied pressure on the ash content in residual coal was observed, solvent extraction of coal with two ranges of particle sizes between
as long as extraction temperature remained the same. 841–2000 and 125–250 μm and found that the extraction yields of
The ash content in the residual coal samples increased slowly within coal were 13 and 33.6% respectively. Finer coal particles provided the
the temperature range of 250–350 °C. However, once the extraction higher extraction yields and this is believed to be due to the increasing
temperature rose to 400 °C during Roto south coal extraction, the ash of the surface area of the coal particles [86]. Samanta and Mondal [74],
content of the residual coal increased rapidly. This result indicates that investigated the effects of particle sizes on the reduction of mineral mat-
ash content of the residual coal at lower temperature (b 350 °C) was ter with three different average coal particle size 126, 250 and 403 μm
low; whereas, at higher temperature (400 °C) ash content was higher, using different polar solvents and observed that ash removal gradually
since the extraction yield was high (~90%). increases with the decrease of the finer coal particles and yields more
(Reprinted with permission from Copyright (2008) Elsevier). organic solvent soluble compounds.
Based on the literature survey summarized in Tables 2a–2d, we
attempted to find out the relationship of coal particle size and extraction
yield of AFC. It can be generalized that the higher extraction yields (74–
91%) were obtained from b75 μm coal particles, moderate (56–81%)
from b 150 μm and low to moderate (12–70%) from b250 μm. These re-
sults indicate that finer coal particles are providing higher extraction
yield. This is possibly due to diffusional resistance and more penetration
of the solvent into the coal matrix.

4.5. Effect of coal properties

Coal properties are important in assessing the quality of the coal and
its proper utilization in the industry. The extraction yield of coals by sol-
vent extraction is one of the most important aspects in AFC production
process, which depends on the number of factors, namely type of sol-
vent (polar, non-polar of mixed), softening temperature of coal, extrac-
tion temperature and properties of the feed coal. Koyano et al. [87]
investigated the coal properties (proximate and ultimate analysis) of
76 coals from different origin and found that the oxygen content of
the coal as an important parameter affecting the extraction yield of
Fig. 9. Relationship between coal softening temperature and coal extraction rate. AFC and they developed a correlation for the extraction yield of coal
Okuyama et al. [48]. (Reprinted with permission from Copyright (2004) Elsevier). with 1-MN at 360 °C. The influence of C/H became clear for 1-MN in
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 49

Fig. 10. Relationship between the softening temperature of raw coal and extraction yields with (a) DMN-W and (b) LCO [45]. (Reprinted with permission from Copyright (2002) Elsevier).

the case for coals with oxygen b8.2% and found that a non-polar (1-MN) coal is mixed with coal-derived solvent. The resultant mixture with H2 is
or slightly polar (LCO) is suitable for coal with b8.2% oxygen content. passed through a preheater and reactor. Hydrogen reacts with organic
However, coals with N 8.2% oxygen content requires polar solvent, like sulfur compounds forming the hydrogen sulfide. The clean coal product
CMNO to achieve higher extraction yield of HPC. can be recovered after separating and filtering H2S and mineral matters
The type of maceral and their contents in the coal matrix also have [96]. SRC contains mineral matter in the form of soluble organometallic
the influences on the conversion of coal and it's utilization. The direct compounds (cannot be removed by filtration), extraction with either
coal liquefaction performance has been evaluated using petrographic benzene or tetralin as a solvent in order to remove these from SRC.
methods to understand the maceral transition during solvent extraction Ashida et al. [97] presented a coal fractionation method to separate a
process and studied the reactivity of the inertinite and vitrinite-rich bituminous coal into several fractions without decomposing coal. They
coals with different organic solvents and observed that the extraction have shown the sequential solvent extraction at different temperatures
yield was lower for inertinite-rich coals [88–92]. Recently, Niekerk et lower than 350 °C and separated bituminous coals into several fractions
al. [89] studied South African coals of similar rank with the different having different molecular mass compounds, free from mineral matters.
maceral content and found a relationship between the extraction yields Morimoto et al. [98] studied on hydrothermal degradative extraction
and mean maximum reflectance (MMVR), indicating that the higher the method for converting low-rank coal into upgraded coal and thermo-
MMVR of the coal lower the extraction yield. Rahman et al. [62] also plastic extract in a flow of hot water at b 350 °C. The extraction yields
found a correlation of AFC extraction yields with vitrinite content and of low-rank coals ranged from 40 to 70 wt% depending upon the coal
MMVR of the feed coal. They observed that the vitrinite-rich Canadian rank.
lignite coal with a lower MMVR value resulted higher extraction yields.
In addition to the studies mentioned earlier, there are some studies in 4.6. Challenges in demineralization of coal to produce AFC
this area with different focus which will be described in following
paragraphs. Although, a small scale demonstration pilot plant (capacity
Cody et al. [93] measured the swelling of coals in chlorobenzene, 0.1 t/day) utilizing coal derived 2-ring aromatics was developed
THF, pyridine and found that the swelling of coals in these solvents (KOBE Steel, Japan) but not yet gone large scale production. In spite
was anisotropic, i.e. greater in perpendicular to the bedding plane many processes been demonstrated in small batch, operating them in
than parallel to it. Further, once swollen, coals from which most of the a continuous mode for longer period of time is another challenge. Coal
solvent (pyridine) has been removed do not return to their original tar distillate or coal derived oil's are producing AFC with high extraction
shape. Hall and Larsen [94] studied the coal structural change following yield, this may be a good supplement to maintain the solvent recycling
solvent extraction. For some coal they reported that the process of pyr- system; however, producing this industrial solvent in a cost effective
idine extraction does not change the chemical composition of coal manner is highly desirable. Since the detailed chemical reactions occur-
significantly. ring in solid–liquid–gas phases are not completely known and the oper-
Solvent-refined coal (SRC) process is similar to HyperCoal produc- ations have not been done in long term basis, which raises a huge
tion, with major difference in presence of H2 in SRC. SRC is derived concern about the reliability of the developed system possessing a
from the direct liquefaction of coal with highly polyaromatic character huge challenge in commercialization of AFC/HPC process. Realization
and relatively high in N, O and S content [95]. In SRC process, pulverized of the know-how and knowledge obtained so far to build a continuous

Table 3
Extraction yield of AFC at different temperatures from different coals. (Data from [62]).

Coal Solvent Temperature (°C) Yield % (daf)a

CV 1-MN 400 30.4


SAb 400 57.5
SBc 400 62.0
GEN 1-MN 400 24.5
SA 400 62.5
SB 400 71.6
BD 1-MN 400 31.8
SA 400 74.3
SB 400 78.4
a Weight of dry AFC
Percentage yield based on residue produced (daf), Yield ðwt:%; dafÞ ¼ Weight of feed coal ðdafÞ
 100.
b
SA: non-hydrotreated industrial solvent.
c
SB: hydrotreated industrial solvent.
50 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

Fig. 11. Variation of extraction yield with initial applied pressure [52]. (Reprinted with
permission from Copyright (2008) Elsevier).
Fig. 13. Variation of ash content of residual coal with initial applied pressure [52].

operational commercial plant is a challenge. In addition, considering the thus formed can be easily recovered by condensing water vapor with
toxic nature of these solvents environmental impacts, residual coal uti- less energy involvement. The CO2 can be sequestrated with little or no
lization and waste management issues need to be addressed properly. energy penalty. In spite of several advantages, one of the major issues
with CLC of solid fuels is ash deposition and contamination of oxygen
5. Potential applications of UCC and AFC carrier with ash from coal during combustion. The problem related to
contamination can be solved using solid fuel with an insignificant or a
AFC or HPC here refers to a coal-derived solid fuel with overall ash lower amount of minerals. Thus, the ideal CLC with solid fuel would
content in the order of 0.1%, which has the potential to burn directly be with the fuel containing negligible or no mineral matter. In this con-
in gas turbine combined cycle (GTCC) systems with net power genera- text, AFC is the best candidate for CLC. In spite of these benefits, there
tion efficiency not b 48% and can also be potentially used in DCFC sys- are only few studies on CLC of AFC so far.
tems with N 60% power generation efficiency based on its HHV. Syn- Based on the research carried out recently in our group [62,101] we
gas production from these upgraded coal are more energy-intensive, have presented chemical looping combustion of AFC with CuO as an ox-
and can be used as a hydrogen source for high-efficiency electricity gen- ygen carrier. Thermogravimetric analysis was performed to evaluate
eration with zero emissions and as a feedstock for the synthesis of thermal reactivity behavior of CuO and AFC as solid fuel with different
value-added chemicals and liquid fuels [36]. Potential applications of ratios of CuO/AFC mixtures (10 to 50) at different temperatures (650–
these coals in the industrial sectors are described briefly as follows; 1000 °C) under nitrogen environment. CLC reaction mechanism were
also proposed and evaluated with the experimental results. Our group
5.1. Application of UCC/AFC in chemical looping combustion has recently performed multi-cycle tests with CuO/AFC ratio 30 and
found that there was no interference in the reaction due to deposited
Chemical looping combustion (CLC) is a novel technology for CO2 ash for the five consecutive cycles and the reactions remain almost the
capture with no or less energy penalty compared to conventional com- same for all the cycles [102].
bustion [99,100]. CLC uses metal oxide as an oxygen carrier. CLC process
consists of two interconnected fluidized bed reactors: an air reactor and 5.2. Catalytic gasification of ash free coals to produce syngas
a fuel reactor. The solid oxygen carrier is circulated between the air and
fuel reactors. In CLC process, the metal oxide supplies the stoichiometric Coal is gasified to produce syngas (H2 and CO). Steam gasification of
oxygen needed for fuel combustion, producing CO2 and H2O. The CO2 coal is widely used because of increase in H2 content in the off gas [103].
H2, CO, CO2 and CH4 are the principal products from the steam gasifica-
tion of coal. The distribution of these constituents in the product gas is
governed mainly by temperature, pressure and various chemical reac-
tions that may occur in the gasifier [104].

C þ H2 O→CO þ H2

CO þ 3H2 ⇌CH4 þ H2 O

2CO þ 2H⇌2CH4 þ CO2

CO þ H2 O⇌CO2 þ H2

In the absence of catalyst, steam gasification usually requires tem-


perature above 800 °C. However, kinetics of gasification process can
be significantly enhanced using catalysts and gasification can be
achieved at lower temperature [105]. Commonly used catalysts for
such application are alkali (e.g., potassium, sodium) and alkaline earth
Fig. 12. Variation of ash content of extracted coal with initial applied pressure [52]. (e.g., magnesium, calcium) metals [104]. One of the major problems
(Reprinted with permission from Copyright (2008) Elsevier). with catalytic coal gasification is the deactivation of the catalysts by
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 51

mineral matters in coal. Obviously, in order to address this problem the thermoplasticity of the coal blend more than GO caking coal. The ther-
best would be to remove the minerals from coal prior to gasification, as moplasticity of the blend with HPC was found to be higher than that
discussed in the earlier sections. Some of the studies [106–108] have of the standard blend but while comparing with 5–10% (mass) blending
shown that the better gasification performances of AFC with catalyst of HPC into a standard coal remarkably increased the thermoplasticity
rather than the catalyzed and non-catalyzed parent coals. Sharma et of the blend, in wide temperature range (250–450 °C). The study also
al. [109] has shown that the catalytic gasification of HyperCoal yielded investigated the effects of temperature on adding PaHPC to the standard
higher gasification rates at 700 °C, without catalyst deactivation. In an- coal blend. At an extraction temperature of 360 °C, thermoplasticity in-
other study Sharma et al. [110] have compared the catalytic steam gas- creased in the lower temperature range (250 to 450 °C). Addition of 10%
ification characteristics of HyperCoal and its parent raw coal. PaHPC, extracted at 400 °C, to the blend greatly increased the overall
Recently, Kopyscinski et al. [107] carried out steam gasification ex- thermoplasticity. The resolidification temperature range was found to
periments of AFC with and without catalyst (K2CO3) in a drop down re- similar to the standard blend. This shows the beneficial effects that
actor. They reported that catalyst in AFC increased the steam AFC/HPC can have by using it as a binding agent.
gasification rate by N10 times and decreased the activation energy by Another application is that AFC/HPC can also be added to increase
about 100 kJ/mol compared to the uncatalyzed one. In addition, the gas- the semicoke strength of the standard coal blends. The AFC/HPC has a
ification temperature was lower (600–700 °C).
Kim et al. [111] studied the reactivity of AFC in steam gasification for
H2 production. They found AFCs prepared from low rank coals were
generally less reactive than the parent raw coals. However, Kong et al.
[108] carried out the comparative study on the seam gasification of
AFCs (at 700–900 °C) and their parent raw coals ranging from lignite,
sub-bituminous, bituminous and coking coal. In their experiments, gas-
ification rate for AFCs were slower and they showed low H2/CO ratio,
AFCs behaved like a highly carbonized coal. The steam gasification and
CO to CO2 conversion of the AFCs were significantly enhanced by cata-
lyst (K2CO3), resulting in the higher H2/CO and CO2/CO molar ratio.
Sharma et al. [112] compared the steam gasification of raw coal and
HPC with gasification efficiency, gas yield with and without use of cata-
lyst (K2CO3) (Fig. 14). Gasification rates of coal and HPC were slow with-
out catalyst. Whereas, with the use of catalyst the gasification rate of
coal and HPC increased sharply. During gasification with HPC, the cata-
lysts were recycled for four times without and significant decrease in
gasification rate [109,110], this result demonstrates no catalyst deacti-
vation by HPC, since it does not contain mineral matters.
The gas yield and amount of CO, CO2, and H2 gas evolved were nearly
same for coal and HPC, without utilizing any catalyst, whereas, addition
of catalyst increased the gas yield significantly.
In addition, amount of H2 evolved during catalytic gasification was
several times higher than that of without a catalyst.

5.3. Use of AFC as a blending agent in coke making

Steel manufacturing process utilize high carbonious materials, com-


monly referred as coke. Good quality coke making process is time con-
suming and expensive, requires carbonization of inferior or low
quality coal. Carbonization of coal improves the bulk density of the
feed coal. The improvement of the bulk density leads to a closure con-
tact of the coal particles and thus results stronger bond between coke
cells [113]. United States Steel Corporation developed the clean coke
idea for producing metallurgical coke, chemical feedstocks and fuels
from non-metallurgical coals [114]. JSW steel manufacturing company
[115] have been successfully utilizing 35% of the inferior coals for pro-
ducing coke with a coke strength after reaction (CSR) in the range of
64–66%, a coke reactivity index (CRI) between 23 and 25% and M10 in
the range of 4–6%. AFC shows good thermal plasticity [47,59], this char-
acteristic is suitable for making coking coal. Therefore, AFC is a promis-
ing blending candidate as coke oven feedstock. It also makes the coke
stronger and reduces the consumption of high rank coking coal.
Since thermoplasticity of AFC/HPC is much higher than caking coal,
addition of AFC/HPC in standard coal blend enhances coke strength
and thermoplasticity of the blend. Takanohashi et al. [116] investigated
the effect of HPC addition on coke strength and thermoplasticity. Fig. 15
shows the effects of adding GrgHPC-360 to the standard coal blend KRS-
GO-K9 (35-35-30). In their experiment, equal amount of GO coking coal
was substituted by HPC. The thermoplasticity of GrgHPC blends was Fig. 14. Comparison of (a) gasification profiles, (b) cumulative gas yield, and (c) mole
higher than that of the standard blend, and it reached highest at 10% percent fraction of product gas, for coal and HPC at 700 °C with and without K2CO3
level. Their results suggested that GrgHPC enhances the [105]. (Reprinted with permission from Copyright (2009) American Chemical Society).
52 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

strong influence on the physical properties of the blend such as increas- use of any liquid. Cooper in 2005, for the first time, used AFC as the
ing the tensile strength as shown by Takanohashi et al. [116]. Fig. 16 fuel in a molten Carbonate DCFC. Use of raw coal as fuel in molten car-
shows the effects of HPCs (extracted at 360 °C) addition, on the bonate electrolyte & solid-oxide-electrolyte fuel has been presented
semicoke strength of standard coal blends. As shown in Fig. 16, the ten- earlier [119–121]. Use of coal in DCFC may cause problems due to inhi-
sile strength increased greatly in 5% GrgHPC and 5% WWHPC blends bition of cell operation by ash deposition after the cell reactions. Pro-
than the standard coal blend. However, decrease in tensile strength of cessing of coals to remove mineral matters can be an effective and
5% PaHPC than the standard blend in case of 5% PaHPC was related to economic ways to meet the fuels requirements of DCFCs [122]. The fea-
a higher percentage of lighter components in PaHPC, which might sibility of using AFC as fuel in DCFC has been studied by many re-
have volatilized easily as temperature was raised, resulting in a weak, searchers [75,117,122,123] as it does not leaves ash for inhibiting the
porous semicoke. mass transport after the cell reactions.
Kim et al. [122] used a solid-oxide-electrolyte for DCFC with contin-
5.4. Production of anode coke uous AFC feeding system. They found cell performance was affected by
operating temperature; performance increased with increase in tem-
Petroleum coke has been used in manufacturing carbon anodes for perature. The maximum power density was measured at 750 °C and in-
aluminium production. During manufacturing process, the blends of pe- crease in temperature beyond this did not increase power, in their
troleum coke with a small proportion of coal tar binder pitch are carbon- experiment.
ized. Large quantities of cokes are required for carbon anode Lee et al. [75] evaluated the performance of various carbon mate-
manufacturing to meet the need of aluminium industries. The quality rials: AFC, raw coal, active carbon, carbon black and graphite as fuel
and availability of petroleum coke for this process has been a growing for DCFC. They reported that the degree of carbonization determined
concern in the recent years. As an alternative, coal can be a viable carbon the electrochemical reactivity of fuels and the power density of AFC
resource for anode production, if it could meet the coke specifications. was strongly temperature-dependent and generally decreased over
As for example, Andrews et al. [69] at University of Kentucky Center the period of time (day by day). Dudek et al. [117] used ash-free
for Applied Energy Research (CAER) used Blue Gem coal to study the “hyper-coal” as a fuel in DCFC. They demonstrated stable operation
feasibility of producing anode grade coke by utilizing mild solvent ex- with reasonable current and power densities. In addition, they demon-
traction. In brief, coal was dissolved in solvent, the mineral matter and strated that the performance can be improved by the use of catalyst and
unreacted products were removed by filtration, and the clean coal liquid proper operating conditions.
was converted to coke. The properties of the calcined cokes were com- Rady et al. [124] used Victorian brown coals with minimal pre-treat-
pared with typical petroleum coke and their uses in production of car- ment and evaluated their performance in solid oxide electrolyte based
bon anodes were assessed. In their experiment, ash contents of the DCFC at 700 and 800 °C. They used commercial carbon black, chars pro-
cokes exceeded the anode coke specification by little which they believe duced from demineralized Morwell coal and the parent coal. The peak
might be due to contamination from the laboratory coker and may be power densities of raw and demineralized Morwell chars were similar
able to get rid of this problem in an industrial-scale process. at 700 °C. Whereas, at 800 °C the raw Morwell char showed much
higher power densities, compared to commercial carbon black. On the
5.5. Application of AFC as a fuel in direct carbon fuel cell (DCFC) other hand, raw Morwell char give rise to highest power densities.
The better performance of raw Morwell char is suggested due to a great-
Fuel cells generate electrical energy from fuels with higher efficien- er availability of CO at the anode. In addition, the performance might
cy. DCFC system directly converts the chemical energy stored in solid have enhanced due to presence of inorganic species in raw coal such
fuel into electricity. DCFCs are the only fuel cells that operate with as Fe, Ca and Mg which might have catalyzed the Boudouard gasification
solid fuels. According to the type of electrolyte used, DCFCs can be reaction (C(s) + CO2(g) → 2CO(g)). The performance of raw and AFC in
grouped into 3 types: molten hydroxides, molten carbonates and solid DCFC has been recently compared by Ju et al. [125]. They have studied
oxides [117]. Also many hybrid models do exist. Researches on the the influence of the physiochemical characteristics of raw coal, AFC
solid oxide electrolyte based DCFCs have been increasing due to a rela- and carbon black.
tively stable electrolyte and easy scale up [118]. DCFCs has advantages Fig. 17 shows the comparison of electrochemical performance of raw
of high efficiency, low cost fuel, highly concentrated CO2 in exhaust coal, AFC, carbon black in DCFC from 750 to 925 °C. The measured open-
gases, which can be sequestrated [117]. The concept of DCFC was pre- circuit voltage increased with an increase in operating temperature and
sented by W.W. Jacques in the 19th century. Ishida et al., in 1988 the cell resistance decreased linearly. Raw coal showed the highest
showed the feasibility of a DCFC with solid oxide electrolyte, without open-circuit voltage with highest electrochemical reactivity in all the

Fig. 15. Thermoplasticity as a function of temperature for the standard coal blend and Fig. 16. Tensile strengths of semicoke produced with HPCs extracted at 360 °C [116].
GrgHPC-360 blends [116]. (Reprinted with permission from Copyright (2008) Elsevier). (Reprinted with permission from Copyright (2008) Elsevier).
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 53

temperatures. Raw coal generated about twice fuel cell performances


compared to AFC due to the presence of volatile organic compounds
in it at temperature below 750 °C. Whereas, temperature over 900 °C,
both AFC and raw coals achieved similar power density. Their study
concluded that in the long-term operation of DCFC, power generated
from AFC would be more durable than from raw coal.

5.6. Coal water slurry (CWS) or coal water slurry fuel (CWSF)

Coal water slurry fuel (CWSF) is composed of fine coal particles


suspended in water and used as liquid fuel in place of oil, gas and coal
fired power plants. Wibberley [126] treated low rank coals hydrother-
mally to remove the moisture and as a result the treated coals become
hydrophobic in nature. Subsequent removal of the minerals and/or in-
organic components from treated coals by air/gas bubble flotation tech-
nique to produce ash-less or UCC coal, which has been utilized to
prepare coal water slurry fuel with higher solid loading for a particular
viscosity. This high solid loading slurry fuel can be utilized in combus-
tion boilers, diesel engines and kilns.

6. Economic study of AFC production

The literatures on economic evaluation of AFC are rarely available. To


the best of our knowledge, very few studies are available [48,68,127].
Okuyama et al. [48] established the material balance for HyperCoal
production plant with capacity of 6000 t/day that was constructed
near an Australian coal mining. The total cost was estimated to be
375 M$US including the manufacturing cost of the equipment
(11 M$US). The total construction cost (works and transportation etc.)
was estimated to be 250% of the equipment cost and 10.4 M$US for ni-
trogen circulation unit. 1.4 megatons/year of hypercoal is expected to be
produced from 2.3 megatons/year of Stratford coal. They have also pro-
posed the business model. Using average market price of the coal and
with some assumptions they have calculated the internal rate of returns
13% after 15 years of operations and concluded that it might be an eco-
nomically attractive business.
Fig. 18 shows the changing of calorie base price at the gate, free on
board (FOB), cost insurance and freight (CIF) for raw coal and hypercoal.
When the ash disposal cost is added to the general coal, the calorie
based price of HPC becomes almost the same as the general coal includ-
ing its ash disposal cost. This shows that HPC is economically competi-
tive with general coal in Japan. However, it is to be noted that there
are some typical characteristics of hypercoal-process and environmen-
tal tax in Japan such as higher transportation cost associated with the
raw coal (which is half of the total coal price), high cost for ash disposal
etc. these might have played the favorable role to make hyper coal more
economic. The economic study on the production of hyper coal applica-
ble for wider application is to be carried out in the future.
Wijaya and Zhang [68] in the review paper compared two coal de-
mineralization processes (i.e. acid/alkali leaching and solvent extrac-
tion) mainly in term of the removal efficiency of inorganic elements
and the economic aspect. They argue that both the methods are not Fig. 17. Comparison of the electrochemical performance of the DCFC for (a) raw coal, (b)
technically mature enough to generate ultraclean demineralized coal. ash-free coal, and (c) carbon black fuels at different temperatures [125]. (Reprinted with
Safety issues and economic feasibility, among others are identified as permission from Copyright (2014) Elsevier).
the barriers for commercialization of these technologies. They have pre-
sented the economic estimation based on a comparison to supercritical
pulverized-fuel coal boiler (SC pf) [68,127]. The capital cost ($M/MW)
based on AUD 2006 for chemical leaching and solvent extraction were limited domestic coal reserve, HPC is economical compared to the raw
estimated to be 0.932 to 0.949 and 0.882 to 0.942, respectively. Electric- coal when the cost for coal import, ash disposal and/or landfilling, ener-
ity cost breakdown ($/MWh) for chemical leaching process was pre- gy tax etc. are included. However, for countries having coal reserve and
sented as 106.2 to 106.5 (compared to 131.5 for SC pf) to be cheaper landfill disposal options the HPC production might not be eco-
competitive with LNG, HPC and UCC need to have a delivery cost nomic and relevant as shown in Japanese case. It has been proposed that
$2.50/GJ less than the cost of LNG. The cost for solvent extraction was to compete with liquid natural gas (LNG) for gas turbine combustion, ei-
estimated as 103.7 to 105.3 $/MWh. ther HPC or UCC has to further increase its process cost-effectiveness to
It is notable here that the economic estimation by Cottrell et al. cut the electricity delivery cost by $2.50/GJ less than the cost of LNG. The
[127], which is based on Japanese scenario. Since Japan has a very materialization of achievements obtained so far in HPC production area
54 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

into scale-up and industrial production involves many barriers includ- 7.2. AFC
ing safety, economic feasibility, increasing efficiency.
It is evident from literature review that the higher extraction yields
7. Summary of AFC depends on the following characteristics of coals: softening
point, extraction temperature, solvent polarity, feed particle size, feed
Upgrading of coal for removing ash forming minerals have been car- coals moisture content, maceral content etc. In general extraction
ried out for several decades in order to mitigate the plant operational is- yield has been found higher at high treatment temperature related to
sues and global environmental pollution. Chemical treatment processes both the solvent- and thermal-induced relaxation of the nitrogen and
has been demonstrated as the most efficient technique for removal of oxygen-containing compounds in the coal matrix. However, at certain
ash forming minerals from coal to produce UCC and AFC. UCC produc- temperature (N 350–500 °C) coal molecules tends to undergo thermal
tion by acid and alkali digestion or AFC production by solvent extraction condensation, as a result decreases the extraction yields. The parame-
of raw coals can be achieved with higher heating values and low mineral ters affecting the extraction yield of AFC are briefly summarized below;
contents, which can overcome the drawbacks of direct utilization of
coal. • Finer coal particles (b75 μm) provides higher extraction yield, possi-
bly due to the increasing diffusibility and penetration of the solvent
7.1. UCC into the coal matrix as well as the higher available surface area of
coal particles to come in contact with solvents.
The available literature show the ash content of the UCC is within the • Hydrogen donor solvent like tetralin produce higher extraction yield
range of 0.15 to 0.6% resulted either by treating bituminous coal with HF with higher extraction temperature (300–400 °C) whereas, for non-
followed by HCl or HNO3. The most effective treatment is HF followed hydrogen donor solvent, 1-MN, the extraction yield increase rapidly
by HNO3 which has achieved ash content as low as 0.15%. Some re- until 350 °C, and then decreases gradually with the increase in tem-
searcher treated coal only with HF, and others with NaOH followed by perature. Since, 1-MN could not transfer hydrogen to increase the ex-
HCl, demineralization in those cases were less than HF treatment traction rate, as well as coal molecules undergoes thermal
followed by HNO3 and or HCl. Followings are the summary of the condensation to produce residual coal via cross-linking at tempera-
major observations for demineralization of coal to produce UCC; ture range (350–500 °C) in coal matrix.
• The extraction yield increase linearly with the increase of polar con-
• HF does not react with pyrites whereas, HNO3 (concentration ≥ 1 M)
centration (Indole) in non-polar solvents from low-rank coals with
alone reacts with pyrites as well as with carbonaceous matrix of the
high oxygen content (≥8.2%) [63]. Maceral composition of coal plays
coal even at lower concentration (b1 M). HF concentration (up to
an important role for the coal extraction yield and higher vitrinite-
3.5 M) plays a significant role in removal of ash content of coals and
rich coal produce higher extraction yield [62].
its leaching efficiency is more effective with the finer coal particle
size (−75 μm). Fluoride content of the coal increases tremendously
due to the formation of fluoride compounds such as AlF3, NaAlF4, Upgraded coals have been applied in DCFC, chemical looping com-
CaF2 and MgF2 and drops upon HNO3 leaching. bustion, catalytic gasification to produce syngas, in coke oven process,
• HNO3 treatment increases the N and O content of the coal, due to the as a blending agent, production of anode coke. Studies on many issues
NO+ 2 attack to the carbonaceous coal structure, but the overall ash such as universal solvent or leaching reagent for UCC and AFC produc-
content of the UCC reduces. Therefore, two stage leaching process, tion, recycling the solvents and reagents used in the process, and
HF followed by HNO3 treatment was found to be more effective to socio-economic assessments are still in the developmental stage. How-
produce UCC with the ash content as low as 0.15%. The combustion ever, at this point we can foresee that in the long-term operation power
of UCC resulted reduction in SO2 emission levels but NOx emissions generated from UCC and AFC would be more environmental friendly
increased from UCC combustion obtained from treatment with HNO3. than that from raw coal. In spite of having these benefits, economic eval-
• Microwave irradiation leaching (up to 2.5 h) technique with HF uation of UCC and AFC are rarely available.
followed by HNO3 treatment was more effective for coarser coal par-
ticles (~1000 μm) with lower ash content. However, in case of weaker
8. Recommendations
acid treatment followed by Na-EDTA, both the fine and coarser coal
particles showed negative demineralization effect.
The ash content of the upgraded coal should be b0.1% to be consid-
ered as AFC for application in IGCC plant; however, many researchers
are producing AFC with higher ash content within the range of 0 to
2.3%. Among the bulky literatures available only few of them are meet-
ing the criteria for utilizing AFC in IGCC. Since the natural abundance of
low-grade coal is large, it is important to upgrade these coals and thus to
make it acceptable in terms of cleaner power generation as well as for
the environmental protection. It is recommended that;

• Research on regeneration of expensive and toxic reagents like HF and


HNO3 to be carried out to make the overall process cost-effective and
environmental friendly.
• Catalytic gasification of upgraded coal to produce syngas and applica-
tion in fuel cell and CLC would help in creating low emission technolo-
gy and greenhouse gases (mainly CO2) emission reduction. Thus, more
studies in this direction with performance evaluation are foreseen.
• Coal tar distillate or coal derived oil's are producing AFC with high ex-
traction yield and may be a good supplement to maintain the solvent
recycling system for producing AFC.
Fig. 18. Changing in the calorie base prices of general coal and Hyper-coal [48]. (Reprinted • The economic assessment and evaluation of AFC production process
with permission from Copyright (2004) Elsevier). are rarely available in the literature. Therefore, further fundamental
M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56 55

studies on economic assessment and it's feasibility of commercializa- [29] D.J. Boron, R.S. Taylor, Mild oxidations of coal: 1. Hydrogen peroxide oxidation, Fuel
64 (2) (1985) 209–211.
tion need to be carried out in the future. [30] H. Rottendorf, The recycling of fluoride in coal refining, Australian Patent 60, 6607,
1986.
[31] H.G.M. Edwards, V. Fawcett, Quantitative Raman spectroscopic studies of
Acknowledgement nitronium ion concentrations in mixtures of sulphuric and nitric acids, J. Mol.
Struct. 326 (1994) 131–143.
[32] K.M. Steel, J.W. Patrick, Re-generation of hydrofluoric acid and selective separation
The authors are grateful to Natural Sciences and Engineering Re- of Si(IV) in a process for producing ultra-clean coal, Fuel Process. Technol. 86 (2)
search Council of Canada under a Cooperative Research and Develop- (2004) 179–190.
[33] D.K. Sharma, S.K. Singh, Advanced process for the production of clean coal by
ment agreement (NSERC-CRD), Carbon Management Canada (Project
chemical leaching technique, Energy Sources 17 (1995) 485–493.
CMC-A02), and Canadian Centre for Clean Coal/Carbon and Mineral Pro- [34] A. Nabeel, T.A. Khan, D.K. Sharma, Studies on the production of ultra-clean coal by
cessing Technologies (C5MPT) and University of Alberta for providing alkali-acid leaching of low-grade coals, Energy Sources 31 (2009) 594–601.
funding for conducting this study. [35] E. Jorjani, G.H. Chapi, M.T. Khorami, Ultra clean coal production by microwave irra-
diation pretreatment and sequential leaching with HF followed by HNO3, Fuel Pro-
cess. Technol. 92 (2011) 1898–1904.
References [36] N. Wijaya, T.K. Choo, L. Zhang, Generation of ultra-clean coal from Victorian
brown coal — sequential and single leaching at room temperature to elucidate
[1] IPCC, in: Core Writing Team, R.K. Pachauri, A. Reisinger (Eds.), Climate Change the elution of individual inorganic elements, Fuel Process. Technol. 92 (2011)
2007: Synthesis Report, IPCC, Geneva, Switzerland, 2007. 2127–2137.
[2] IEA, 2013. IEA Clean Coal Centre Advances in Multi-pollutant Control. Anne M Car- [37] N. Wijaya, T.K. Choo, L. Zhang, Generation of ultra-clean coal from Victorian
penter. (CCC/227). Brown coal: effect of hydrothermal treatment and particle size on coal demin-
[3] D. Pudasainee, J.H. Kim, Y.S. Yoon, Y.C. Seo, Oxidation, reemission and mass distri- eralization and the extraction kinetic of individual metals, Energy Fuel 26
bution of mercury in bituminous coal fired power plants with SCR, CS-ESP and wet (2012) 5028–5035.
FGD, Fuel 93 (2012) 312–318. [38] K. Clark, J. Langley, The preparation of bulk ultra clean coal samples from the UCC
[4] A. Crawford, The de-ashing of coal by combined jig washing, froth-flotation, and Energy Pilot Plant for evaluation as a gas turbine fuel, Proceedings of the 2nd
extraction with caustic soda, Brit. Intell. Object. Subcomm.; Final Report No. 522, Japan–Australia Coal Research Workshop NEDO Yoko Kaikan, Tokyo, Japan 2002,
Item No. 30, 1946. pp. 47–53.
[5] A. Crawford, The preparation of ultra-clean coal in Germany, Trans. Inst. Min. Eng. [39] K. Clark, J. Langley, Developments in Ultra Clean Coal, North Sydney, 2005.
111 (1951) 204. [40] G.F. Yannolis, Ultra Clean Coal: An Option for Greenhouse Friendly Coal Fired
[6] P. Meshram, B.K. Purohit, M.K. Sinha, S.K. Sahu, B.D. Pandey, Demineralization of Power Generation, Presentation to APP CFE Taskforce Meeting, Montreal, Canada,
low grade coal – a review, Renew. Sust. Energ. Rev. 41 (2015) 745–761. Sept 2010 13–15.
[7] E. Azimi, S. Karimipour, M.M. Rahman, J.K. Szymanski, R. Gupta, Evaluation of the [41] G.F. Yannolis, Ultra clean coal: an option for greenhouse friendly coal fired power
performance of air dense medium fluidized bed (ADMFB) for low ash coal benefi- generation, ACPS Meeting Cessnock, NSW 20 August, 2008.
ciation, part I: effect of operating conditions, Energy Fuel 27 (2013) 5595–5606. [42] K.M. Steel, J. Besida, T.A. O'Donnell, D.G. Wood, Production of ultra clean coal: part
[8] E. Azimi, S. Karimipour, M.M. Rahman, J.K. Szymanski, R. Gupta, Evaluation of the III. Effect of coal's carbonaceous matrix on the dissolution of mineral matter using
performance of air dense medium fluidized bed (ADMFB) for low ash coal benefi- hydrofluoric acid, Fuel Process. Technol. 76 (2002) 51–59.
ciation, part II: characteristics of the beneficiated coal, Energy Fuel 27 (2013) [43] S. Marland, B. Han, A. Merchant, N. Rowson, The effect of microwave radiation on
5606–5616. coal grindability, Fuel 79 (2000) 1283–1288.
[9] H. Katalambula, R. Gupta, Low-grade coals: a review of some prospective [44] K. Renganathan, J.W. Zondlo, E.A. Mintz, P. Kneisl, A.H. Stiller, Preparation of an
upgrading technologies, Energy Fuel 23 (2009) 3392–3405. ultra-low ash coal extract under mild conditions, Fuel Process. Technol. 18
[10] R.K. Dwari, K.H. Rao, Tribo-electrostatic behavior of high ash non-coking Indian (1988) 273–278.
thermal coal, Int. J. Miner. Process. 81 (2) (2006) 93–104. [45] T. Yoshida, T. Takanohashi, K. Sakanishi, I. Saito, M. Fujita, K. Mashimo, The effect of
[11] K.M. Steel, J.W. Patrick, The production of ultra clean coal by chemical demineral- extraction condition on ‘HyperCoal’ production (1)—under room-temperature fil-
ization, Fuel 80 (2001) 2019. tration, Fuel 81 (2002) 1463–1469.
[12] K.M. Steel, J.W. Patrick, The production of ultra clean coal by sequential leaching [46] T. Yoshida, C. Li, T. Takanohashi, A. Matsumura, S. Sato, I. Saito, Effect of extraction
with HF followed by HNO3, Fuel 82 (2003) 1917. condition on “HyperCoal” production (2)—effect of polar solvents under hot filtra-
[13] F. Rubieira, A. Arenillas, C. Pevida, R. Garcia, J.J. Pis, K.M. Steel, J.W. Patrick, Coal tion, Fuel Process. Technol. 86 (2004) 61–72.
structure and reactivity changes induced by chemical demineralization, Fuel Pro- [47] New Energy and Industrial Technology Development Organization (NEDO), Japan
cess. Technol. 79 (2002) 273. Coal Energy Center (JCOAL), Clean Coal Technologies in Japan, 2006 1–116.
[14] R.H. Yoon, in: J.W. Leonard III, B.C. Hardinge (Eds.), Coal Preparation, SME-AIME, [48] N. Okuyama, N. Komatsu, T. Shigehisa, T. Kaneko, S. Tsuruya, Hyper-coal process to
Colorado 1991, p. 966. produce the ash-free coal, Fuel Process. Technol. 85 (2004) 947–967.
[15] G.R. Couch, Advanced Coal Cleaning Technology, IEA Coal Research, IEA Coal Re- [49] M. Tamura, International Symposium on Low Rank Coal, Innovation & Technolo-
search Publishers, 1991. gies for Sustainable Future, Melbourne, 2010.
[16] O. Trass, O. Bajor, Modified oil agglomeration process for coal beneficiation. Simul- [50] S. Kinmoshita, S. Yamamoto, T. Deuguchi, T. Shigehisa, Demonstration of upgraded
taneous grinding and oil agglomeration, Can. J. Chem. Eng. 66 (1988) 286–290. brown coal (UBC®) process by 600 tonnes/day plant, KOBELCO Technology Re-
[17] O. Trass, E.R. Vasquez, Modified oil agglomeration process for coal beneficiation. IV. view No. 29, Dec. 2010 (www.kobelco.co.jp/english/ktr/pdf/ktr_29/093-098.pdf
Pilot plant demonstration of the simultaneous grinding agglomeration process, (access Nov 2016)).
Can. J. Chem. Eng. 72 (1994) 113–118. [51] M.H. Makgato, L.J. Moitsheki, L. Shoko, B.L. Kgobane, D.L. Morgan, W.W. Focke, Al-
[18] Z.Y. Wang, Y. Ohtsuka, A. Tomita, Removal of mineral matter from coal by alkali kali-assisted coal extraction with polar aprotic solvents, Fuel Process. Technol. 90
treatment, Fuel Process. Technol. 13 (1986) 279–289. (2009) 591–598.
[19] H.G. Alam, A.Z. Moghaddam, M.R. Omidkhah, The influence of process parameters [52] S.D. Kim, K.J. Woo, S.K. Jeong, Y.J. Rhim, S.H. Lee, Production of low ash coal by ther-
on desulfurization of Mezino coal by HNO3/HCl leaching, Fuel Process. Technol. 90 mal extraction with N-methyl-2-pyrrolidinone, Korean J. Chem. Eng. 25 (4) (2008)
(1) (2009) 1–7. 758–763.
[20] S. Kizgut, K. Baris, S. Yilmaz, Effect of chemical demineralization on thermal behav- [53] N. Okuyama, T. Deguchi, K. Shimasaki, S. Shinozaki, Proceedings of International
ior of bituminous coals, J. Therm. Anal. Calorim. 86 (2) (2006) 483–488. Pittsburgh Coal Conference, University of Pittsburgh, USA, 2000.
[21] G.R. Drykacz, E.P. Horwitz, Separation of coal macerals, Fuel 61 (1982) 3–12. [54] K. Ouchi, S. Itoh, M. Makabe, H. Itoh, Pyridine extractable material from bituminous
[22] G.R. Drykacz, C.A.A. Bloomquist, Use of continuous flow centrifugation techniques coal, its donor properties and its effect on plastic properties, Fuel 68 (1989)
for coal maceral separation. 1. Fundamentals, Energy Fuel 6 (4) (1992) 357–374. 735–740.
[23] G.R. Drykacz, L. Rustic, J. Fredericks, An investigation into the process of centrifugal [55] R.K. Mahat, W. Rodgers, F. Basile, Microwave radiation heating in pressurized ves-
sink/float separations of micronized coals. 1. Some inferences for coal maceral sep- sels for the rapid extraction of coal samples for broad spectrum GCMS analysis, En-
arations, Energy Fuel 6 (6) (1992) 720–742. ergy Fuel 28 (2014) 6326–6335.
[24] S. Mukherjee, P.C. Borthakur, Chemical demineralization/desulphurization of high [56] K. Miura, M. Shimada, K. Mae, S.Y. Huan, Extraction of coal below 350 °C in flowing
sulphur coal using sodium hydroxide and acid solutions, Fuel 80 (14) (2001) non-polar solvent, Fuel 80 (2001) 1573–1582.
2037–2040. [57] I. Mochida, A. Takarabe, K. Taeshita, Solvolytic liquefaction of coals with a series of
[25] S. Mukherjee, P.C. Borthakur, Demineralization of subbituminous high sulphur coal solvents, Fuel 58 (1979) 17–23.
using mineral acids, Fuel Process. Technol. 85 (2003) 157–164. [58] T. Takanohashi, T. Shishido, I. Saito, Effects of HyperCoal addition on coke strength
[26] K.M. Steel, J. Besida, T.A. O'Donnell, D.G. Wood, Production of ultra clean coal - part and thermoplasticity of coal blends, Energy Fuel 22 (2008) 1779–1783.
I - dissolution behaviour of mineral matter in black coal toward hydrochloric and [59] Anon., Hyper-coal (ash-free coal) process with liquid CO2 as solvent, IP.com J. 9
hydrofluoric acids, Fuel Process. Technol. 70 (2001) 171–192. (4B) (2009) 27.
[27] K.M. Steel, J. Besida, T.A. O'Donnell, D.G. Wood, Production of ultra clean coal - part [60] M. Iino, T. Takanohashi, S. Obara, H. Tsueta, Y. Sanokawa, Extraction of coals with
II - ionic equilibria in solution when mineral matter from black coal is treated with CS2-N-methyl-2-pyrrolidinone mixed solvent at room temperature: effect of coal
aqueous hydrofluoric acid, Fuel Process. Technol. 70 (2001) 193–219. rank and synergism of the mixed solvent, Fuel 67 (1988) 1639–1647.
[28] N.P. Vasilakos, S.C. Clinton, Chemical beneficiation of coal with aqueous hydrogen [61] N. Kashimura, T. Takanohashi, I. Saito, Upgrading the solvent used for the thermal
peroxide/sulphuric acid solutions, Fuel 63 (11) (1984) 1561–1963. extraction of sub-bituminous coal, Energy Fuel 20 (2006) 2063–2066.
56 M. Rahman et al. / Fuel Processing Technology 158 (2017) 35–56

[62] M. Rahman, A. Samanta, R. Gupta, Production and characterization of ash-free coal [96] R.G. Shaver, A solvent-refined coal process for clean utility fuel, Pollution Control
from low-rank Canadian coal by solvent extraction, Fuel Process. Technol. 115 and Energy Needs. Chapter 7 1974, pp. 80–90.
(2013) 88–98. [97] R. Ashida, K. Nakgawa, M. Oga, H. Nakagawa, K. Miura, Fractionation of coal by use
[63] N. Sakimoto, K. Koyano, T. Takanohashi, Relationship between extraction yield of of high temperature solvent extraction technique and characterization of the frac-
coal by polar solvent and oxygen functionalities in coals, Energy Fuel 27 (2013) tions, Fuel 87 (2008) 576–582.
6594–6597. [98] M. Morimoto, H. Nakagawa, K. Miura, Conversion of a wide range of low-rank coals
[64] P. Painter, N. Pulati, R. Cetiner, M. Sobkowiak, G. Mitchell, J. Mathews, Dissolution into upgraded coals and thermoplastic extracts having similar chemical and phys-
and dispersion of coal in ionic liquids, Energy Fuel 24 (2010) 1848–1853. ical properties using degradative hydrothermal extraction, Energy Fuel 24 (2010)
[65] P.C. Painter, P. Opaprakasit, A. Scaroni, Ionomers and the structure of coal, Energy 3060–3065.
Fuel 14 (2000) 1115–1118. [99] J. Adanez, A. Abad, F. Garcia-Labiano, P. Gayan, L.F. De Diego, Progress in chemical-
[66] P. Opaprakasit, P.C. Painter, M.M. Coleman, A.W. Scaroni, Ionomer-like structures looping combustion and reforming technologies, Prog. Energy Combust. Sci. 38 (2)
and their role in the pyridine-extractability of Argonne Premium coals, Am. (2012) 215–282.
Chem. Soc. Div. Fuel Chem. 46 (1) (2001) 331–333 (Preprints, San Diego, CA, [100] R. Siriwardane, H. Tian, G. Richards, T. Simonyi, J. Poston, Chemical-looping com-
April 1–5). bustion of coal with metal oxide oxygen carriers, Energy Fuel 23 (8) (2009)
[67] P. Opaprakasit, P.C. Painter, A.W. Scaroni, Ionomer-like structures and π-cation in- 3885–3892.
teractions in Argonne Premium coals, Energy Fuel 16 (3) (2002) 543–551. [101] A. Shabani, M. Rahman, D. Pudasainee, A.K. Samanta, P. Sarkar, R. Gupta, Chemical
[68] N. Wijaya, L. Zhang, A critical review of coal demineralization and its implication looping combustion of ash-free coal with CuO as an oxygen carrier - part I: ther-
on understanding the speciation of organically bound metals and submicrometer mogravimetric single cycle study and evaluation of the reaction mechanism, Can.
mineral grains in coal, Energy Fuel 25 (2011) 1–16. J. Chem. Eng. (2016), http://dx.doi.org/10.1002/cjce.22721.
[69] R.J. Andrews, T. Rantell, D. Jacques, J.C. Hower, J.S. Gardner, M. Amick, Mild coal ex- [102] A. Shabani, M. Rahman, D. Pudasainee, A.K. Samanta, P. Sarkar, R. Gupta, Chemical
traction for the production of anode coke from Blue Gem coal, Fuel 89 (2010) looping combustion of ash-free coal with CuO as an oxygen carrier - part II: ther-
2640–2647. mogravimetric multicycle performance evaluation, Can. J. Chem. Eng. (2016),
[70] D.K. Sharma, S.K. Singh, Extraction of coal through dilute alkaline hydrolytic treat- http://dx.doi.org/10.1002/cjce.22713.
ment at low temperature and atmospheric pressure, Fuel Process. Technol. 19 [103] T. Takarada, Y. Tamai, A. Tomita, Reactivities of 34 coals under steam gasification,
(1988) 73–94. Fuel 64 (1985) 1438–1442.
[71] R.J. Camier, S.R. Siemon, Colloidal structure of Victorian brown coals. 1 Alkaline di- [104] B.J. Wood, K.M. Sancier, The mechanism of the catalytic gasification of coal char: a
gestion of brown coal, Fuel 57 (1978) 85–88. critical review, Catal. Rev. Sci. Eng. 26 (1984) 233–279.
[72] F. Woskoboenko, W.O. Stacy, D. Raisb, Chapter 4: physical structure and properties [105] H. Junten, Application of catalysts to coal gasification processes. Incentives and per-
of brown coal, The Science of Victorian Brown Coal: Structure, Properties and Con- spectives, Fuel 62 (1983) 234–238.
sequences for Utilization, Elsevier 1991, pp. 151–246. [106] J. Kopyscinski, J. Lam, C.A. Mims, J.M. Hill, K2CO3 catalyzed steam gasification of
[73] J.J. Kolak, R.C. Burruss, The use of solvent extractions and solubility theory to dis- ash-free coal. Studying the effect of temperature on carbon conversion and gas
cern hydrocarbon associations in coal, with application to the coal–supercritical production rate using a drop-down reactor, Fuel 128 (2014) 210–219.
CO2 system, Org. Geochem. 73 (2014) 56–69. [107] J. Kopyscinski, M. Rahman, R. Gupta, C.A. Mims, J.M. Hill, K2CO3 catalyzed CO2 gas-
[74] R.S. Samanta, C. Mondal, Separation of mineral matter from Indian coal by using ification of ash-free coal. Interactions of the catalyst with carbon in N2 and CO2 at-
solvents, IJERT 3 (2014) 349–357. mosphere, Fuel 117 (2014) 1181–1189.
[75] I. Lee, J. Sunmi, C. Donghyuk, C. Hokyung, L. Sihyun, L. Kibong, Y. Jiho, Ash-free coal [108] Y. Kong, J. Kim, D. Chun, S. Lee, Y. Rhim, Lim, H. Choi, Kim, J. Yoo, Comparative stud-
as fuel for direct carbon fuel cell, Sci. China Chem. 57 (7) (2014) 1010–1018. ies on steam gasification of ash-free coals and their original raw coals, Int. J.
[76] Y. Sun, X. Wang, T. Feng, G. Yu, F. Wang, Evaluation of coal extraction with super- Hydrog. Energy 39 (2014) 9219–9220.
critical carbon dioxide/1-methyl-2-pyrrolidone mixed solvent, Energy Fuel 28 [109] A. Sharma, T. Takanohashi, I. Saito, Effect of catalyst addition on gasification reac-
(2014) 816–824. tivity of HyperCoal and coal with steam at 775–700 °C, Fuel 87 (2008) 2686–2690.
[77] O. Sonmez, E.S. Giray, Producing ashless coal extracts by microwave irradiation, [110] A. Sharma, I. Saito, T. Takanohashi, Catalytic steam gasification reactivity of
Fuel 90 (2011) 2125–2131. hypercoals produced from different rank of coals at 600–775 °C, Energy Fuel 22
[78] A.A. Vostrikov, O.N. Fedyaeva, D.Y. Dubov, S.A. Psarov, M.Y. Sokol, Conversion of (2008) 3561–3565.
brown coal in supercritical water without and with addition of oxygen at continu- [111] J. Kim, H. Choi, J. Lim, Y. Rhim, D. Chun, S. Kim, S. Lee, J. Yoo, Hydrogen production
ous supply of coal water slurry, Energy 36 (2011) 1948–1955. via steam gasification of ash free coals, Int. J. Hydrog. Energy 38 (2013) 6014–6020.
[79] H. Karaca, C. Koyunoglu, Co-liquefaction of Elbistan lignite and biomass. Part I: the [112] A. Sharma, I. Saito, T. Takanohashi, Effect of steam partial pressure on gasification
effect of the process parameters on the conversion of liquefaction products, Energy rate and gas composition of product gas from catalytic steam gasification of
Sources, Part A 32 (2010) 495–511. hyper coal, Energy Fuel 23 (2009) 4887–4892.
[80] X. Li, H. Hu, L. Jin, S. Hu, B. Wu, Approach for promoting liquid yield in direct lique- [113] P. Kumar, S. Barma, M. Ranjan, S. Ghosh, V.V.S. Raju, Maximization of non-coking
faction of Shenhua coal, Fuel Process. Technol. 89 (11) (2008) 1090–1095. coals in coke production from non-recovery coke ovens, Ironmak. Steelmak. 35
[81] G.P. Curran, R.T. Struck, E. Gorin, Mechanism of hydrogen-transfer process to coal (1) (2008) 33–37.
and coal extract, Ind. Eng. Chem. Process. Des. Dev. 6 (2) (1967) 166–173. [114] K.A. Schowalter, N.S. Boodman, The clean coke process for metallurgical coke,
[82] C. Figueroa, Modelling of Solvent Extraction of Coal(MSc thesis) University of Al- Chem. Eng. Process. 70 (6) (1974) 76.
berta, 2012. [115] S.S. Gupta, B.N. Singh, ‘Coke’, 55, JSW Steel Ltd., Jamshedpur, 2005.
[83] J.S. Abichandani, J.H. Wieland, Y.T. Shah, D.C. Cronauer, Kinetics of short contact [116] T. Takanohashi, T. Shishido, H. Kawashima, I. Saito, Characterisation of HyperCoals
time coal liquefaction. Part I: effect of operating variables, AICHE J. 30 (2) (1984) from coals of various ranks, Fuel 87 (2008) 592–598.
295–303. [117] M. Dudek, P. Tomczyk, R. Socha, M. Hamaguchi, Use of ash-free “Hyper-coal” as a
[84] M. Varol, A.T. Atimtay, B. Bay, H. Olgun, Investigation of co- combustion character- fuel for a direct carbon fuel cell with solid oxide electrolyte, Int. J. Hydrog. Energy
istics of low quality lignite coals and biomass with thermogravimetric analysis, 39 (2014) 12386–12394.
Thermochim. Acta 510 (2010) 195–201. [118] A.C. Chien, S.S.C. Chuang, Effect of gas flow rates and Boudouard reactions on the
[85] S. Vyazovkin, Model-free kinetics, J. Therm. Anal. Calorim. 83 (2006) 45–51. performance of Ni/YSZ anode supported solid oxide fuel cells with solid carbon
[86] C.C. Giri, D.K. Sharma, Mass-transfer studies of solvent extraction of coals in N- fuels, J. Power Sources 196 (2011) 4719–4723.
methyl-2-pyrrolidone, Fuel 79 (5) (2000) 577–585. [119] X.Y. Zhao, Q. Yao, S.Q. Li, N.S. Cai, Studies on the carbon reactions in the anode of
[87] K. Koyano, T. Takanohashi, I. Saito, Estimation of the extraction yield of coals by a deposited carbon fuel cells, J. Power Sources 185 (1) (2008) 104–111.
simple analysis, Energy Fuel 25 (2011) 2565–2571. [120] M. Chen, C. Wang, X. Niu, S. Zhao, J. Tang, B. Zhu, Carbon anode in direct carbon fuel
[88] R. Suárez, J.C. Crelling, Applied Coal Petrology: The Role of Petrology in Coal Utili- cell, Int. J. Hydrog. Energy 35 (7) (2010) 2732–2736.
zation, Elsevier, 2008. [121] H.K. Ju, S.H. Uhm, J.W. Kim, R.H. Song, H.K. Choi, S.H. Lee, et al., Enhanced anode in-
[89] D.V. Niekerk, G.D. Mitchell, J.P. Mathews, Petrographic and reflectance analysis of terface for electrochemical oxidation of solid fuel in direct carbon fuel cells: the
solvent-swelled and solvent-extracted South African vitrinite-rich and inertinite- role of liquid Sn in mixed state, J. Power Sources 198 (2012) 36–41.
rich coals, Int. J. Coal Geol. 81 (2010) 45–52. [122] J.P. Kim, H.K. Choi, Y.J. Chang, C.H. Jeon, Feasibility of using ash-free coal in a solid-
[90] J.A.R. van Veen, K. King, On the difference in reactivity between high- and low- oxide-electrolyte direct carbon fuel cell, Int. J. Hydrog. Energy 37 (2012)
inertinite coals, Fuel Process. Technol. 16 (1987) 3–17. 11401–11408.
[91] A. Davis, G.D. Mitchell, F. Derbyshire, R.F. Rathbone, R. Lin, Optical properties of [123] T. Gür, M. Homel, A. Virkar, High performance solid oxide fuel cell operating on dry
coals and liquefaction residues as indicators of reactivity, Fuel 70 (1991) 352–360. gasified coal, J. Power Sources 195 (2010) 1085–1090.
[92] R.A. Keogh, D. Taulbee, J.C. Hower, B. Chawla, B.H. Davis, Liquefaction characteris- [124] A.C. Rady, S. Giddey, A. Kulkarni, S.P.S. Badwal, S. Bhattacharya, B.P. Ladewig, Direct
tics of the three major maceral groups separated from a single coal, Energy Fuel carbon fuel cell operation on brown coal, Appl. Energy 120 (2014) 56–64.
6 (1992) 614–618. [125] H.K. Ju, J. Eoma, J.K. Lee, H. Choi, T.H. Lim, R.H. Song, J. Lee, Durable power perfor-
[93] G.D. Cody, J.W. Larsen, M. Siskin, Anisotropic solvent swelling of coals, Energy Fuel mance of a direct ash-free coal fuel cell, Electrochim. Acta 115 (2014) 511–517.
2 (1988) 340–344. [126] Wibberley Louis; Treatment low rank coals, WO 2010/081191, PCT/AU2010/
[94] P.J. Hall, J.W. Larsen, Use of Einstein specific heat models to elucidate coal structure 000026.
and changes in coal structure following solvent extraction, Energy Fuel 7 (1993) [127] A. Cottrell, P. Scaife, L. Wibberley, CCSR Report: Systems Assessment of Hypercoal
42–46. for Electricity Supply in Japan, 2007 (http://www.ccsd.biz/publications/files/TA/
[95] D. Smook, Removal of mineral material from solvent-refined coal by solvent ex- TA%2065%20Hypercoal_web.pdf).
tractions, Fuel Process. Technol. 88 (2007) 795–798.

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