Energy Conversion and Management 52 (2011) 762–769

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Energy Conversion and Management

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Alkaline hydrothermal de-ashing and desulfurization of low quality coal

and its application to hydrogen-rich gas generation
Anggoro Tri Mursito a,b,⇑, Tsuyoshi Hirajima c, Keiko Sasaki c
a
Research Centre for Geotechnology, Indonesian Institute of Sciences (LIPI), Jl. Sangkuriang Komplek LIPI, Gd. 70, Bandung 40135, Indonesia
b
Department of Earth Resources Engineering, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, Japan
c
Department of Earth Resources Engineering, Faculty of Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, Japan

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

Article history: This paper describes experimental research and a fundamental study of alkaline hydrothermal treatment
Received 5 October 2009 of high-sulfur, high-ash coal from Banten, Java-Indonesia. Experiments were carried out on a laboratory-
Received in revised form 21 July 2010 scale 0.5 L batch reactor. The alkaline hydrothermal treatment gave upgraded clean coal with low sulfur
Accepted 8 August 2010
content (about 0.3 wt.%) and low ash content (about 2.1 wt.%). A zero carbon dioxide and pure hydrogen
Available online 21 September 2010
gas were produced at 330 °C by introducing an alkali (sodium hydroxide, NaOH) to the hydrothermal
treatment of raw coal. X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques were used to test
Keywords:
for the removal or reduction of major inorganic elements in the coal, and changes in carbon-functional
Hydrothermal treatment
Upgrading
groups and their properties were determined by Fourier transform infrared spectroscopy (FTIR) and Car-
Desulfurization bon-13 of nuclear magnetic resonance (13C NMR) tests on the product of the hydrothermal upgrading and
Hydrogen demineralization process.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction Hydrothermal treatment of coals was first studied by Fischer

Ash and sulfur content in coal create problems during coal uti-
lization. It is generally well known that mineral material in low
quality coal inhibits its effective utilization. The increasing require-
ment to use low quality coal in Indonesia is part of the govern-
ment’s energy development program. Indonesian coal deposits
are located throughout Sumatra, Kalimantan and Papua, with small
amounts also occurring in Java. Available estimates indicate the to-
tal quantity to be about 62 billion tons, of which 7 billion tons are
estimated reserves. The coal quality varies between low rank coal
or lignite (58%), sub-bituminous (27%), bituminous (14%) and small
quantities of anthracite [1]. High-sulfur, high-ash coal emits vari-
ous oxides of sulfur (SOx) when burnt; it produces large quantities
of fly ash and exhibits low energy efficiency when used directly in
coal-fired power plants. Therefore, demineralization and desulfur-
ization of coal prior to utilization have been extensively investi-
gated for the purpose of solving the energy efficiency and ash
problems. Optimal processing of coal would eliminate many of
the problems; the endpoint is the substitution of clean fuel for
the direct utilization of unprocessed coal.
⇑ Corresponding author at: Research Centre for Geotechnology, Indonesian
Institute of Sciences (LIPI), Jl. Sangkuriang Komplek LIPI, Gd. 70, Bandung 40135,
Indonesia. Tel.: +62 22 2503654; fax: +62 22 2504593.
E-mail addresses: anggoro@geotek.lipi.go.id, anggorotrim@yahoo.com (A.T.
Mursito).
and Schrader in 1921. This treatment of heating coal at 320–
400 °C in the presence of water in an autoclave was adopted for
coal upgrading. Hydrothermal treatment of coal has been exten-
sively studied, with varying results such as partial elimination of
carboxyl groups, carbonyl groups, ether bridges and sulfides [2].
Also, the decreases of oxygen in the organic matter of coals are
of greatest interest in hydrothermal process [3]. Some other report
shows that the sulfur content and selected trace elements of some
coals are reduced by 50% or more by water at conditions above the
critical temperature but below the critical pressure [4]. Using alka-
line solution for sulfur removal called oxydesulfurization treated at
low temperature of 200 °C and with pressurized of oxygen at
1.7 MPa was investigated for total sulfur, pyritic and organic sulfur
removal [5]. Some other techniques have been applied to coal to
remove its inorganic materials from the organic part such as froth
flotation for removal of pyritic sulfur from coal. By using alkali
desulfurization and oxydesulfurization also are effective applicable
methods for high sulfur coals [6]. Therefore, demineralization and
desulfurization of coals by using alkaline solution with many
methods are of greatest interest.
Technologies optimizing the conversion of fossil fuels into gas
are well developed; of these, coal gasification has been studied
thoroughly [7]. Steam gasification and pyrolysis of coal at 750 °C
will increase the evolution of CO, CO2 and H2. Hydrogen is produced
either from fossil fuels, or from non-fossil energy sources using
methods such as water electrolysis, photolysis and thermolysis

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.08.001
 A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769
[8]. Steam–nitrogen mixture gasification of biomass char at 1000 °C
was also interested as the production of hydrogen increased [9].
Hydrogen gas production is normally operated at very high temper-
atures. At supercritical condition of water at 28 MPa and 740 °C
results show that the energy efficiency from thermodynamic calcu-
lation reaches 60% when considering hydrogen, carbon monoxide
and methane as valuable species in the ideal case [10]. However,
hydrothermal treatment of carbonaceous materials commonly pro-
duces lower-value gas products. The addition of an alkali to acceler-
ate the chemical process in hydrothermal treatment of coal is
highly attractive since it would allow the production of a higher
output of upgraded products at lower temperatures than would
be otherwise practicable. The aim of the present work was to inves-
tigate the hydrothermal treatment of coal, with and without added
alkali, as a means of removing or reducing the major inorganic con-
stituents. Selective and partial gasification of low quality coal for
hydrogen-rich gas production, as well as CO2 capture by alkaline
hydrothermal treatment, were also studied.
2. Materials and experimental methods
2.1. Materials
Coal samples were obtained from Bayah–Banten, Java–Indone-
sia. Coal in this area is classified as low quality coal with high
ash and high-sulfur content. Typical properties of Bayah coal are
shown in Table 1, along with XRF ash analysis. The ash consisted
mainly of silica and alumina, accompanied by iron, potassium, cal-
cium and trace elements. The presence of iron oxide and sulfur tri-
oxide indicated the presence of sulfur in the coal. The other oxides
present affected the total ash content.
2.2. Apparatus and experimental procedure
The experiments were conducted in a 0.5 L batch-type reactor
(Taiatsu Techno MA22) equipped with automatic temperature con-
trol, capable of producing a maximum pressure of 30 MPa at 400 °C
as described in Fig. 1 and also in [11]. Coal (40 g), water (260 g) and
increments of added alkali (NaOH) in the range 0–0.025 mol/g
were placed in the reactor. Initial experiments compared the effec-
tiveness of adding different quantities of alkali, and the mixture
without added alkali. The reactor was purged and pressurized with
nitrogen to 2.0 MPa at ambient temperature. The coal slurry was
then brought to the required temperature of 330 °C at an average
heating rate of 1.4 °C/min. while being agitated at 200 rpm. After
the desired reaction time of 30 min, the reactor was rapidly cooled.
The reaction time of 30 min and temperature of 330° C were cho-
Table 1
Calorific value, proximate, total sulfur and ash analysis of raw
Bayah coal.
Calorific value (kJ kg1) (d.b) 25,361
Proximate analysis (wt.%)
Moisture (a.r) 5.4
Volatile matter (d.a.f) 45.5
Fixed carbon (d.a.f) 54.5
Ash (d.b) 17.7
Total sulfur (wt.%) (d.a.f) 3.1
Ash analysis (wt.%) (d.b)
SiO2 48.5
Al2O3 42.8
Fe2O3 3.9
K2O 2.6
CaO 1.1
TiO2 0.7
SO3 0.3
d.b = dry-base; a.r = as received basis; d.a.f = dry ash free basis.
763
sen based on previous studies on a variety of carbonaceous mate-
rials [12]. Purging of N2 gas in all experiments were only due to
minimize the oxidation of coal sample by the air. Although, the fi-
nal pressure, residual gas pressure and total gas quantity at room
temperature will be affected by the initial N2 pressure and
amounts and the results will be recalculated.
2.3. Analysis
After cooling down, the gas products were released through a
gasometer (Shinagawa DC-1) and the volume was determined by
collection into a gas micro syringe (ITO MS-GANX00). The evolved
gas composition was then determined by gas chromatography (GC)
using a GC equipped with a thermal conductivity detector (Shima-
dzu GC-4C) using molecular sieve 5A and Porapak Q columns. Col-
umn temperature was set at 60 °C and argon was used as the
carrier gas at a rate of 30 mL/min. Analysis results were recorded
by a (Shimadzu C-R8A) Chromatopac data processor. The Shima-
dzu standard gases used to calibrate the GC were CO2, CO, H2,
CH4, N2 and O2 and the confidence limits of analysis were 99%.
The solid and liquid products were then collected from the reactor
and separated by filtration using a water aspirator. The liquid prod-
uct was analyzed for total organic carbon (TOC) and total inorganic
carbon (TIC) using a TOC analyzer (Shimadzu TOC-5000A VCSH).
These results are discussed elsewhere.
The elemental composition of the coal sample was determined
prior to acid washing using an elemental analyzer (Yanaco CHN
Corder MT-5 and MT-6). Additionally, proximate analysis (based
on JIS M 8812), total sulfur analysis (based on JIS M 8819) and cal-
orific value analysis (based on JIS M 8814) were conducted sepa-
rately. In order to obtain clean upgraded coal products, the solid
product was washed with water, followed by heating to 60 °C in
1 M hydrochloric acid and further water washing. The clean coal
products were analyzed by Fourier transform infrared spectros-
copy (FTIR) (JASCO 670 Plus), X-ray fluorescence (XRF) (Shimadzu
EX-700) and X-ray diffraction (XRD) (Rigaku Multiflex). The pri-
mary components and chemical structure of the raw coal and clean
coal product were further analyzed by FTIR using diffuse reflec-
tance infrared Fourier transform spectroscopy (DRIFTS) and JASCO
IR Mentor Pro 6.5 software for spectral analysis. JASCO IR Mentor
Pro 6.5 is able to search for unknown spectra or user-generated
databases by full spectrum, limited range, peak, name, property
or structure and browse the functional groups. The measurement
parameters for the XRD analysis were as follows: X-ray source
Cu Ka; voltage 20 kV; current 20 mA; scanning speed 1°/min;
scanning step 0.02°; and scanning range (2h) 5–85. The cross polar-
ization/magic angle spinning (CP/MAS) 13C NMR spectrum of the
clean coal product was measured using a solid state spectrometer
(JEOL CMX-300). The measurement conditions were as follows:
spinning speed >12 kHz; contact time 2 ms; pulse repetition time
7 s; and scan number 10,000. Chemical shifts in ppm are refer-
enced to hexamethylbenzene. The curve-fitting analysis of the
spectrum was conducted using GRAMS/AI 32 Ver. 8.0 software
(Galactic Industries Corp., USA). GRAMS/AI software is a compre-
hensive processing, visualization and reporting package for data
of spectroscopic instruments as well as calculating of the fitted
spectrum peaks area.
3. Results and discussions
3.1. Upgraded clean coal products
XRD was used to study the structural changes in the coal min-
erals. Fig. 2 shows the XRD pattern for the raw coal and solid prod-
ucts treated by alkaline hydrothermal treatment at different
764 A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769
Vent
Gas Collector
Gasometer
H2O out
Sealed &
Screw
N2 Stirrer
Fig. 1. Schematic figures of hydrothermal batch-type reactors [11].
proportions of added NaOH. Kaolinite (Al2(Si2O5)(OH)4), pyrite
(FeS2) and quartz (SiO2) were detected by XRD in raw coal. In the
absence of added alkali, kaolinite and pyrite were retained in the
solid product. The carbonate sodalite (Na8(Al6Si6O24)(CO3)) was
present for all alkaline conditions, suggesting that it occurs as a re-
sult of a thermal decomposition reaction between the coal, the
mineral materials and the added NaOH. Precipitated carbonates
are possibly the product of CO2 gas dissolved during the alkaline
hydrothermal treatment. Sodalite may be the product of dissolved
kaolinite and CO2 in alkaline conditions. CO2 produced by the
chemical reaction of coal with water in the hydrothermal process,
as described below, dissolves to form carbonate. The ability of CO2
to dissolve in the liquid phase was also proportional to the pH and
partial pressure: pH increased with increasing NaOH addition from
3.2 to 13.4. In the liquid phase, HCO 3 ions and CO3
2
ions are in
equilibrium with dissolved CO2 and carbonic acid (H2CO3) [13].
Bicarbonate alkalinity exists naturally in most water with a pH
range of 6.5–8.0 and carbonate alkalinity can exist if the
pH P 8.3 [14]. The overall reaction can be divided into the follow-
ing reactions:
CO2 ðgÞ () CO2 ðaqÞ
CO2 ðaqÞ þ H2 OðlÞ () H2 CO3 ðaqÞ
H2 CO3 ðaqÞ () Hþ ðaqÞ þ HCO3 ðaqÞ
HCO3 ðaqÞ () Hþ ðaqÞ þ CO2
3 ð4Þ
3Al2 Si2 O5 ðOHÞ4 þ 8Naþ þ 2HCO3 () Na8 ðAl6 Si6 O24 ÞCO3
þ CO2 þ 4H2 O þ 6Hþ
Kaolinite may also affect the capture of CO2 in alkaline hydro-
thermal treatments. Analcime (Na(Si2Al)O6H2O) was found only
in the pH range 9.1 6 pH 6 9.9 for added alkali concentrations of
0.002 and 0.005 mol/g. Increasing the alkaline concentration in-
creased the quantity of OH ions, suggesting an increase in pH in
the liquid phase. For the high pH values 12.6–13.4 occurring at
added alkali concentrations of 0.007–0.025 mol/g, respectively,
hydroxycancrinite (Na8Al6Si6O24(OH)22H2O) predominated,
although sodalite was also found in all solid products. The amount
of sodalite was restricted by the presence of CO2 produced during
alkaline hydrothermal treatment, as mentioned below.
Rotary
Temperature
Stirrer 100 V
Control
H2O in
Vessel
Heater Elements
Fig. 3 shows the XRD patterns for raw coal and clean coal prod-
ucts at different NaOH addition rates. In the absence of added alka-
li, mineral material was evident in the clean coal; however, no
mineral material was detected in the clean coal by XRD analysis
for any of the alkaline conditions. It was found that sodalite, anal-
cime and hydroxycancrinite were easily dissolved out by acid
washing.
Fig. 4 shows the effect of NaOH addition on the ash content of
upgraded clean coal. When no alkali was added the ash content
of clean coal was slightly lower than for raw coal. With the addi-
tion of 0.002 mol/g alkali, the ash content of the clean coal was
4.6 wt.%, a significant decrease of 74%. The highest concentration
of added NaOH (0.025 mol/g) produced the lowest ash content of
2.1 wt.%, an 88% reduction in the original ash content of the raw
coal.
Fig. 5 shows XRF analysis results for ash content of the clean so-
lid product before and after acid washing. Sodium oxide concentra-
tion in the solid products increased with an increase of added
NaOH, but was completely removed by washing in all the clean
coal products. Aluminum, silica and iron oxides contributed most
to the ash. Silica (silicon dioxide, SiO2) was the main constituent
ð1Þ of the ash content of the upgraded clean coal products. Silica (sili-
con dioxide, SiO2) derives from quartz, which is relatively insoluble
ð2Þ by alkaline hydrothermal treatment and acid washing.
Fig. 6 shows the effect of NaOH addition on total sulfur content
ð3Þ of clean coal product. Sulfur was present in the raw coal, mainly in
the form of pyritic and organic sulfur at approximately 1.3 and
1.2 wt.%, respectively, and the remainder as a sulfate. Before the al-
kali was added, total sulfur content was about 1.7 wt.%, and de-
creased as NaOH concentration increased. The lowest total sulfur
content observed was about 0.3 wt.% in the clean coal produced
at alkali concentrations of 0.020 and 0.025 mol/g. Acid washing
ð5Þ
may affect the leaching of sulfur in its sulfate form rather than
the pyritic and organic sulfur content [15]. Alkaline hydrothermal
treatment and acid washing with HCl promote the leaching of min-
erals and decrease the amount of sulfur in the coal in the form of
pyrite, adding to the desulfurization process.
Thermal processing of coal at 330 °C is known to affect the
chemical composition of the solid product. To examine such
changes following the alkaline hydrothermal treatment of Banten
coal at different rates of NaOH addition, the dried treated coal
was analysed: Table 2 compares the changes in the chemical com-
position of the raw coal and of the solid products. Carbon content
increased with increase of added alkali up to 0.005 mol/g, then
 A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769 765

q[101]
k = coal - Al2(Si2O5)(OH)4 (kaolinite)

q[101]
k = coal - Al2(Si2O5)(OH)4 (kaolinite)

k[-110]
k[-110]

q[100]
q[100]

k[002]
k[002]
p = coal - FeS2 (pyrite) p = coal - FeS2 (pyrite)
q = coal - SiO2 (quartz) q = coal - SiO2 (quartz)

k[001]
k[001]

k[130]
k[130]

p[210]
p[210]

p[200]
p[200]

p[311]
p[311]
Raw Coal Raw Coal
k[002]

q[101]
q[101]
k[-110]
q[100]

q[100]
k[002]
k[-110]
k[001]

k[001]
k[130]

k[130]
p[200]

p[210]
p[200]
p[210]

p[311]

p[311]
0.000 mol/g
s[211]

0.000 mol/g
a[300]

Intensity (a.u)
a[211]

a = coal - Na(Si2Al)O6.H2O
Intensity (a.u)

s[110]

s = coal - Na8(Al6Si6O24)(CO3)
a[332]

h = coal - Na8Al6Si6O24(OH)2.2H2O
a[431]
s[311]

a[611]
s[332]

a[651]
s[431]

0.002 mol/g
0.002 mol/g
h[400] h[002] h[211]
s[211]
h[101]
s[110]

s[222]
h[401]
s[411] h[321]
h[330]

0.012 mol/g
h[210]

0.012 mol/g
h[402]
h[430]
h[520]
h[440]

h[403]
h[313]
h[400] h[002] h[211]
s[211]
h[101]

0.025 mol/g
s[110]

s[222]
h[401]
h[321]
h[330]
h[210]

0.025 mol/g 20 40 60 80
s[411]
h[402]
h[430]
h[520]
h[440]

h[403]
h[313]

Diffraction angle, 2θ [CuKα]/degree

Fig. 3. Typical XRD patterns derived from raw coal and clean coal at selected alkali
concentrations.

20 40 60 80
Diffraction angle, 2θ [CuKα]/degree
20
Fig. 2. Typical XRD patterns derived from raw coal and solid products at selected
alkali concentrations.
15
Ash Content (wt.%)

decreased with higher alkali concentrations. On the other hand, the

amount of oxygen decreased with an increase of alkali addition up
10
to 0.005 mol/g, then increased with higher alkaline concentrations,
suggesting that oxidation of the solid product was occurring. The
maximum carbon and minimum oxygen contents were 77.1 wt.%
and 15.6 wt.%, respectively, both at an alkaline concentration of 5
0.005 mol/g. Fig. 7 compares the effect of NaOH addition on the
atomic H/C and O/C ratios of the raw coal and the treated coal
~
~

products: the atomic H/C ratio of coal products decreased in the 0

-0.005
Raw 0.000 0.005 0.010 0.015 0.020 0.025
absence of alkali to a minimum of 0.83, then increased with
NaOH Addition (mol/g)
increasing alkali concentration to a maximum of 1.03. These trends
indicate dehydrogenation of the solids in the absence of alkali fol- Fig. 4. The effect of added alkali (NaOH) on ash content of raw coal and clean coal
lowed by hydrogenation with increasing alkali concentration. The products.
atomic O/C ratio progressively decreased to a minimum of 0.15
at an alkali concentration of 0.005 mol/g, then increased with
increasing alkali concentration to a maximum value of 0.33 at dration and reduction of the coal products, followed by oxidation
0.025 mol/g. Decrease in the atomic O/C ratio was caused by dehy- that caused the O/C ratio to increase again.
766 A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769

16 1.10
Na2O-i = oxide element in solid product
14 Na2O-f = oxide element in clean coal
1.05
Raw Coal
Content in Coal (wt.%)

12
0.000 mol/g
1.00
10 0.002 mol/g

H/C Ratio
0.005 mol/g
8 0.007 mol/g 0.95
0.012 mol/g
6 0.020 mol/g 0.90
0.025 mol/g
4
0.85
2

0 0.80
TiO2-f
Fe2O3-f

CaO-f
Na2O-f

SiO2-f

Al2O3-f

K2O-f

TiO2-i

SO3-f

SrO-f
Na2O-i

CaO-i
SiO2-i

Al2O3-i

Fe2O3-i

K2O-i

SO3-i

SrO-i
Fe2O3-f
Fe2O3-i
O-f

Al2O3-f
Na O-i

2O3-i

0.35
CaO-f
2-f

CaO-i

2-f
2-i

2-i
K2O-f

3-f

SrO-f
K2O-i

3-i

SrO-i
SiO
SiO
2

TiO
TiO
SO
SO
Na

Al

Oxide Elements in Ash 0.30

Fig. 5. XRF analysis results for ash content in raw coal, solid and clean coal
products.

O/C Ratio
0.25

3.5 0.20
Total Sulfur Content (wt.%) (d.a.f)

3.0
0.15
2.5

~
~
0.10
2.0 Raw
-0.005 0.000 0.005 0.010 0.015 0.020 0.025
NaOH Addition (mol/g)
1.5
Fig. 7. The effect of added alkali (NaOH) on H/C and O/C ratio of raw coal and
1.0 hydrothermally treated coal products.

0.5
~
~

0.0
3740
3670
3430

2970
2910

1750
1650
1490

1150
960
870
Raw
-0.005 0.000 0.005 0.010 0.015 0.020 0.025
NaOH Addition (mol/g)

Fig. 6. The effect of added alkali (NaOH) on total sulfur content of raw coal and
clean coal products.

Raw coal
Table 2
Ultimate analysis of raw Banten coal and hydrothermally upgraded coal.

Properties Raw NaOH addition (mol/g)

0.000 mol/g

0.000 0.002 0.005 0.007 0.012 0.020 0.025

Ultimate analysis (wt.%) (d.a.f)
Abs. (a.u.)

C 71.0 73.2 76.4 77.1 74.7 68.1 70.7 64.8 0.002 mol/g
H 5.6 5.1 5.4 5.6 5.7 5.4 5.9 5.5
N 1.6 1.7 1.8 1.8 1.7 1.4 1.6 1.4
O (diff.) 21.8 20.1 16.4 15.6 17.9 25.0 21.8 28.3
0.007 mol/g
d.a.f = dry ash free basis; diff. = differences.

3.2. FTIR and 13C NMR structural analyses during alkaline 0.020 mol/g
hydrothermal treatment

Fig. 8 shows FTIR spectra results for the raw coal and clean coal 0.025 mol/g
at different NaOH concentrations. Determination of the peaks in
each spectrum of the main functional groups were obtained using
JASCO IR Mentor Pro 6.5 software and reference to several publica-
tions [16,17]. Other peaks in each spectrum obtained for minerals
and related inorganic compounds have been determined in other 4000 3500 3000 2500 2000 1500 1000
published studies [18,19]. The strong bands in the 3670 and
Wavenumbers (cm-1)
3740 cm1 regions are due to the Si–OH stretching modes of silicate
clay minerals (kaolinite). The clay was also identified in the OH Fig. 8. Typical FTIR spectrum for raw coal and clean coal products at all alkali
stretching absorption 3700–3400 cm1 region, and in particular concentrations.
 A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769 767

the band at 3670 cm1, distinguishes kaolinite in the raw coal and Aromatic carbons
clean coal spectra. Decreasing relative intensity of Si–OH stretching
with increasing NaOH concentration is clearly seen in the upgraded Aliphatic carbons
clean coal. The peak for clean coal is less than for raw coal, possibly
due to demineralization by the alkaline hydrothermal treatment.
The bands observed in the FTIR spectrum of the raw coal were in
agreement with the minerals identified by XRD.
Organic OH stretches occur around 3430 cm1, while aliphatic Raw coal
CH2 and CH3 stretching vibrations can be recognized at 2970 and
2910 cm1, respectively. In addition, significant changes in the
0.000 mol/g
oxygen content of the functional groups can also be observed in
the 1800–1100 cm1 zone. The carbonyl stretching vibration of
C@O and ester at 1750 cm1 is clearly seen for NaOH concentra- 0.002 mol/g
tions from 0.007 to 0.025 mol/g. The relative intensities of the
C@O highly conjugated at 1650 cm1 were observed under all con-
0.005 mol/g
ditions. Aromatic ring stretching vibrations are also observed at

a.u
1490 cm1. C–O–R structures of ethers were observed at
1150 cm1, vanishing with increasing NaOH concentration due to 0.007 mol/g
decomposition by oxidation. Aromatic C–H out-of-plane bending
mode vibrations were observed at lower wave numbers (900–
700 cm1). 0.012 mol/g

In order to observe the structural changes during alkaline

hydrothermal treatment, solid-state 13C NMR spectra of raw coal
and clean coal were measured. These spectra and the peak area dis- 0.020 mol/g
tributions of the carbon-functional groups of raw coal and clean
coal products produced at different alkaline concentrations are
0.025 mol/g
shown in Fig. 9. Determination and assignment of the peak area
distribution of carbon-functional groups was based on several pub-
lished studies [20,21]. From these spectra and general observation, 300 200 100 0 -100
it can be seen that the relative area intensity of aliphatic carbons Chemical Shift (ppm)
decreases with increase in added NaOH when comparing the peaks
Fig. 9. 13C NMR spectra for raw coal and clean coal products at all alkali
assigned to aromatic carbons. concentrations.

3.3. Gaseous products and carbon balance

2.0 2.8
The gases found to be present in the experiments were CO2 and
H2
H2 in the proportions shown in Fig. 10. When the experiment was
CO2 2.7
at the zero NaOH stage, CO2 concentration was found to be the
1.5 Final Pressure

Final Pressure (MPa)

highest of these gases about 88.2 vol.% followed by H2 at
2.6
11.8 vol.%. This high CO2 concentration suggests that a significant
Quantity (L)

contribution to gaseous CO2 derives from decarboxylation, occur-

ring when carboxyl groups in raw coal split off from compounds, 1.0 2.5
or from partial elimination of carboxyl groups [2]. It is possible,
however, that CO2 results from a water–gas shift reaction. In prin- 2.4
ciple, when water (the reaction medium in hydrothermal treat- 0.5
ment) is passed over the carbon, the oxide of carbon first formed 2.3
is principally carbon monoxide (in a water–gas reaction (6)); car-
bon dioxide is then mainly formed in subsequent catalytic reac- 0.0 2.2
tions that tend to establish a water–gas shift reaction (7). When 0.000 0.005 0.010 0.015 0.020 0.025
water is not the reaction medium, it acts as a source of hydrogen NaOH Addition (mol/g)
which can be produced in situ by the water–gas shift reaction [22].
The water–gas reaction is endothermic: Fig. 10. The effect of added alkali (NaOH) on gas product quantities and final
pressures.
C þ H2 O ! H2 þ CO ð6Þ
The water–gas shift reaction is exothermic:
Fig. 10 also shows the effect of NaOH concentration on the final
CO þ H2 O ! CO2 þ H2 ð7Þ
pressure and total gas quantity at room temperature. The amount
CO2 concentration was seen to decrease with increasing NaOH of gas produced was significantly affected by increasing the con-
concentration, vanishing at 0.005 mol/g. Decrease in CO2 was due centration of NaOH. Residual gas pressure after the reactor was
to its solution in the alkaline conditions and precipitation as car- cooled to room temperature ranged from 2.3 to 2.7 MPa, although
bonates as shown in Fig. 2. The proportion of H2 increased with the initial N2 pressure was 2.0 MPa at room temperature in all
increasing NaOH concentration to a maximum of 100 vol.% at experiments. The final pressure at a NaOH concentration of
started from alkali concentration of 0.005 mol/g. Hydrogen is 0.005 mol/g dropped due to CO2 capture, and subsequently H2
formed preferentially until the water–gas shift conversion controls concentration increased with increasing alkali concentration.
the formation of both H2 and CO2. Hydrogen-rich gas was produced Approximately 1.55 L of hydrogen was produced when NaOH
without containing of CO2. was added at the rate of 0.025 mol/g.
768
100
Carbon Content (wt.%) (d.a.f)
80
60
40
20
0 were 77.1 and 15.6 wt.%, respectively, both occurring at a NaOH
0.000 0.005 0.010
NaOH Addition (mol/g)
Fig. 11. The effect of added alkali (NaOH) on total carbon balance.
Most of the organic carbon constituents of the raw coal were
decomposed by the alkaline hydrothermal treatment. Decomposi-
tion of coal was found to be proportional to increasing NaOH con-
centration, as shown in Fig. 11. Conversion of the carbon in the raw
coal into solids was relatively slower than for the liquid and gas
products. For NaOH concentration P0.005 mol/g, carbon was no
longer present in the gas product due to CO2 capture. Oxidation
of the coal by NaOH also affected the increased carbon concentra-
tion in the liquid product.
4. Conclusions
The experimental study of alkaline hydrothermal treatment of
high-sulfur, high-ash Bayah coal by incrementally adding increas-
ing quantities of NaOH has led us to draw a number of conclusions.
Alkaline addition during the hydrothermal treatment process con-
tributes to an increase in coal quality by de-ashing and desulfuriza-
tion. It also represents a method of CO2 gas capture, and of
producing hydrogen-rich gas.
The main effect was to decrease the ash and total sulfur content
in the coal. By adding NaOH at a rate of 0.002 mol/g, the ash con-
tent of the processed clean coal was significantly decreased to
4.6 wt.%, which is a 74% reduction in the ash content of the raw
coal. At the highest rate studied (added NaOH 0.025 mol/g) the
experiment produced the lowest ash content coal (2.1 wt.%, or an
88% reduction in the ash content of the raw coal).
The total sulfur content in the raw coal, 3.1 wt.%, was lowered
significantly to 1.7 wt.% by hydrothermal processing without
added NaOH, and 1.3 wt.% at an added NaOH concentration of
0.002 mol/g. The lowest total sulfur content in the clean coal prod-
uct was observed to be about 0.3 wt.% for NaOH concentrations of
0.020 and 0.025 mol/g, a 90% reduction in the total sulfur content
of the raw coal. The lowest ash and lowest total sulfur content
were both observed at a NaOH concentration of 0.025 mol/g.
The experiments resulted in a zero CO2 in the high-purity
hydrogen gas produced at 330 °C. The volume of produced hydro-
gen increased with increasing NaOH concentration up to a maxi-
mum hydrogen proportion of 100 vol.% at started from alkali
concentration of 0.005 mol/g to the highest NaOH concentration
of 0.025 mol/g. CO2 concentration decreased with increasing NaOH
concentration, vanishing completely at a concentration of
0.005 mol/g.
The effect of NaOH addition on elemental composition and
atomic H/C ratio of the coal solids indicated that dehydrogenation
took place in the absence of alkali, and hydrogenation occurred
when alkali was present. Dehydration and reduction resulted in a
decrease in the atomic O/C ratio at zero or low NaOH concentra-
A.T. Mursito et al. / Energy Conversion and Management 52 (2011) 762–769
tions; higher NaOH concentrations oxidised the coal, which then
Solid Product increased the atomic O/C ratio.
Liquid Product The enhancement of hydrogen production by adding NaOH dur-
Gas Product ing the hydrothermal treatment process was also affected by a
water–gas shift reaction. The decrease in CO2 occurred as a result
of its dissolution in the alkaline conditions and precipitation as car-
bonates. Addition of NaOH is proposed as a means both of promot-
ing and accelerating hydrogen production, and of controlling the
distribution of gas products during the hydrothermal treatment
of coal. It also produces a thermal decomposition environment
for capturing CO2 gas. Kaolinite was also found to be an effective
material for CO2 capture in alkaline hydrothermal treatment.
The observed maximum carbon and minimum oxygen contents
0.015 0.020 0.025 concentration of 0.005 mol/g. The ash and total sulfur contents of
clean coal at a NaOH concentration of 0.005 mol/g were 4.4 and
1.0 wt.% respectively. Carbon dioxide was completely absorbed at
0.005 mol/g and resulted in zero CO2 gas emission. Several of the
experimental results indicate that the optimum NaOH concentra-
tion for the hydrothermal treatment of high-ash and high-sulfur
content coal is 0.005 mol/g. However, further investigation of the
optimum treatment conditions is necessary to determine the ef-
fects of alkaline hydrothermal treatment on product handling of
clean coal and its fuel properties.
Acknowledgments
Financial support was provided by a Grant-in-Aid for Science
Research (Nos. 18206092 and 21246135) from the Japan Society
for the Promotion of Science (JSPS), the Global-Centre of Excellence
in Novel Carbon Resource Sciences, Kyushu University and the New
Energy and Industrial Technology Development Organization
(NEDO). The authors gratefully acknowledge the contributions
and assistance of the Laboratory of Mineral Engineering and Chem-
istry; and Research Group of Coal and Energy – Research Centre for
Geotechnology LIPI, H. Soetjijo, M. Ulum A. Gani, R. Amelia and F.
Saebani for assisting the authors during the fieldwork.
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