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Abstract
Activated carbons were prepared by physical and chemical activations from coals collected from two mines (Kilimli and Armutcuk) in
Zonguldak region, Turkey under different conditions. Ash content was reduced considerably by use of HCl and HF treatments. Pyrolytic
thermal treatments in a temperature range of 600900 C under N2 ow and chemical treatments using different chemical agents such as
KOH, NH4 Cl, ZnCl2 were applied to the coal samples from the two mines. N2 adsorption isotherms were obtained at 77.4 K for the thermally
and the chemically treated samples and the data were used for the evaluation of the specic surface area, total pore volumes and the average
pore sizes of the samples. Higher surface area values were obtained from Kilimli coal samples than Armutcuk. The BET surface area of the
Kilimli coal samples which were initially have a value of 1.20 m2 /g were increased to 52.62 m2 /g after pyrolytic heat treatments at 800 C and
increased to a value of 830.5 m2 /g by treating the coals with KOH + NH4 Cl mixture at 750 C followed by oxidation of the samples mixed
with ZnCl2 . The activated carbon samples were prepared for the purpose of their evaluation in hydrogen sorption studies.
2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Coal; Activated carbon; Adsorption isotherms; Pyrolysis; Chemical treatment; Hydrogen sorption
1. Introduction
Zonguldak is a major centre of coal production situated on
the North of Turkey, on the Black Sea coast with reserves of
1.3 billion tons of easily accessible coal. Most types of industrial activated carbons are produced from naturally happening
carbonaceous materials like coal, wood, corn, petroleum, peat
and other biomass [13]. These materials are impressive adsorbents for several organic compounds of interest, both in gas and
liquid phase treatment processes. In recent years, many studies are also being conducted for the investigation of hydrogen
storage properties of carbonaceous materials. Hydrogen storage
studies in carbon nanostructures including carbon nanotubes
have been increased since the discovery of carbon nanotubes,
but the production cost of the carbon nanotubes is still one of
the important factors to be considered. Recent increasing interest in the use of active carbons obtained from coals has been
instigated by low cost of production and abundant resources
Corresponding author. Tel.: +90 3722572070; fax: +90 3722574181.
as well as specic benecial properties, such as: very welldeveloped surface area, high mechanical and chemical resistance, ease of degradation of the used material and good
ion-exchange properties, which are sometimes much better than
those of synthetic and mineral substances [4,5]. Furthermore,
coal products are in greater demand since they have greater
density, corrosion endurance, hardness and more durable than
other carbons [6].
Activated carbons have a high degree of wide surface area
and porosity. The adsorption capacity of activated carbons is
usually determined by their microtexture and is also strongly
inuenced by the surface functionality [7,8]. The activation
process together with the nature of the precursor strongly determine the characteristics of the resulting activated carbons.
However, they can often have the disadvantage of containing a
high percentage of ash and the activating agents are more expensive (KOH and NaOH versus CO2 and H2 O) and it is also
necessary to apply an additional washing stage [914].
Modication of the active carbon or its precursors changes
the physical and chemical properties of the product. The chemical structure of the active carbons surface signicantly affects
0360-3199/$ - see front matter 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.08.002
5006
to develop activated carbons with high surface area and micropore volumes (up to 2700 m2 /g and 1 cm3 /g). Lyubchik et al. [7]
prepared activated carbons from anthracite by the combination
of a chemical treatment with HClO4 or Mg(ClO4 )2 and a physical activation with CO2 at 850 C. The inuence of chemical
treatment parameters were analysed by means of XPS, FTIR,
TGA, mass spectrometry, elemental analysis and gas adsorption techniques. The optimal conditions for producing activated
carbons from chemically modied anthracites were identied.
It was claimed that increasing the temperature of anthracite
step by step up to 160 C and treatment by HClO4 was the best
way raw anthracite chemically modied by Mg(ClO4 )2 to obtain a precursor of highly activated carbon with well-balanced
micro and mesoporosity. Jurewicz et al. [3133] claimed that
the exposure of the carbon material to a mixture of ammonia
and air at the ratio of 1:3 was very effective for introduction of
nitrogen into the carbon structure and also caused its effective
oxidation. The effects of temperature regime of ammoxidation
and activation on the content of nitrogen and oxygen in the
materials were investigated.
In this study, the effects of activation conditions on the coal
mine type, chemical and nitrogen adsorptive properties of the
activated carbons from coal were analysed. Coals from Zonguldak region, which has the largest coal mines in Turkey, were
chosen as precursors of activated carbons and different activating agents, including ZnCl2 , NH4 Cl, KOH and NaOH, were
used in the preparation. Development of surface characteristics with the effect of different carbonization temperature and
chemical treatment were investigated. The activated carbons
produced by pyrolytic thermal and chemical treatments in this
study were used for the investigation of the hydrogen sorption
properties and the results of hydrogen sorptions will be reported
in our further study.
2. Experimental
Coal samples from Kilimli and Armutcuk coal mines from
Zonguldak in Turkey were selected for this research. The following procedures were applied for activated carbon preparation:
1. The samples were milled and sieved to a ne powder
(100150 m). The volatile matter and ash content were
measured using standard methods ASTM D 3175 and
3174, respectively.
2. In order to decrease the ash content, the raw coal was treated
with an aqueous solution of 15% HCl at 60 C for 1 h,
3.
4.
5.
6.
5007
Table 1
Characteristics of starting coals
Samples
Density (g/cm3 )
Fixed C (%)
V.M. (%)
Kilimli (raw)
Armutcuk (raw)
Kilimli (processed)
Armutcuk (processed)
1.393
1.351
1.346
1.347
4.50
4.95
0.52
0.48
62.00
64.05
65.33
67.42
33.50
31.00
34.15
32.10
1.197
0.0008
1.204
0.95
5008
22
16
20
14
18
12
16
10
12
V(cc/g)
V(cc/g)
14
10
8
6
K600
K700
K800
K900
-2
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
8
6
A600
A700
A800
A900
4
2
0
0.0
0.2
0.6
0.4
0.8
1.0
P/P0
Armutcuk mines were found as 1.204 and 0.95 m2 /g, respectively. Furthermore, the combined treatment with aqueous solution of 15% HCl and 25% HF caused a considerable reduction
in the ash content. The raw coal from Kilimli and Armutcuk
mines had ash contents of 4.5 and 4.95 wt%, respectively. After the acidic treatments, the ash contents were decreased to
0.52 and 0.48 wt%, for Kilimli and Armutcuk mine samples,
respectively. There is a very slight change in the solid densities
of the samples. Similar results were also reported in the literature. As a consequence of the acidic attack to a high ash coal,
a redistribution of part of the metallic components contained
in the original mineral matter occurs within the carbonaceous
matrix.
5009
Table 2
BET and Langmuir isotherm parameters for N2 adsorption on Armutcuk samples
Armutcuk
Parameters
Raw
Processed
600 C
700 C
800 C
900 C
BET
C
Wm (g/g)
Area (m2 /g)
R2
130.25
0
0.0008
0.41
50.02
0.0003
0.95
0.98
70.52
0.01
34.95
0.99
105.20
0.01
34.39
0.99
117.70
0.012
41.55
0.99
900.35
0.008
24.85
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
50.55
0
0.0001
0.40
20.05
0.0004
1.441
0.94
25.46
0.014
51.74
0.98
30.39
0.014
50.45
0.98
31.55
0.017
60.92
0.99
85.84
0.01
35.45
0.99
Table 3
BET and Langmuir isotherm parameters for N2 adsorption on Kilimli samples
Kilimli
Parameters
Raw
Processed
600 C
700 C
800 C
900 C
BET
C
Wm (g/g)
Area (m2 /g)
R2
181.20
0.0004
1.197
0.99
53.49
0.0004
1.204
0.98
77.13
0.012
40.46
0.99
99.65
0.014
48.44
0.99
86.15
0.015
52.62
0.99
479
0.008
27.24
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
87.52
0.0005
1.86
0.98
21.54
0.0005
1.80
0.95
26.70
0.017
59.56
0.98
29.88
0.020
72.46
0.98
28.50
0.022
77.06
0.98
66.89
0.011
39.03
0.99
18
18
16
16
14
14
12
12
10
10
V(cc/g)
V(cc/g)
K600
A600
0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
Fig. 3. N2 adsorption on Kilimli versus Armutcuk coal samples at 77.4 K
(Tpyrolysis = 600 C).
volumes were estimated to be the liquid volume of N2 at a relative pressure (P /P0 ) of 0.9814. The t-plot method was applied
to calculate the total pore volume. The average pore diameters
were estimated from the BET surface area and total pore volume assuming an open-ended cylindrical pore model without
pore networks. Total pore volume also increases with temperature showing a development of porosity (Table 8). In the case of
K700
A700
0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
Fig. 4. N2 adsorption on Kilimli versus Armutcuk coal samples at 77.4 K
(Tpyrolysis = 700 C).
20
20
15
15
1/(W((P0 /P)-1))
V(cc/g)
5010
10
10
5
K800
A800
0
0.0
0.2
0.4
0.6
0.8
0
0.00
1.0
0.05
0.10
P/P0
0.15
0.20
0.25
0.30
P/P0
16
12
14
10
12
10
P/P0 /W
V(cc/g)
8
6
4
8
6
4
2
K900
A900
0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
0
-2
0.00
0.05
0.10
0.15
0.20
0.25
0.30
P/P0
200
200
150
150
V(cc/g)
V(cc/g)
100
50
0.0
0.2
0.4
0.6
0.8
100
A650(1)
A650(2)
K650(1)
K650(2)
50
A650(1)
A650(2)
A750(1)
A750(2)
0
0.0
1.0
0.2
0.4
0.6
0.8
1.0
P/P0
P/P0
Fig. 9. N2 adsorption isotherms on Armutcuk coal samples at 77.4 K (chemical
treatment at 650750 C).
240
250
220
200
200
180
160
140
150
V(cc/g)
V(cc/g)
5011
100
K650(1)
K650(2)
K750(1)
K750(2)
50
0
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
120
100
80
60
40
A750(1)
A750(2)
K750(1)
K750(2)
20
0
-20
0.0
0.2
0.4
0.6
0.8
1.0
P/P0
5012
Table 4
BET and Langmuir isotherm parameters for N2 adsorption on Armutcuk samples (chemical treatments at 650 C)
Armutcuk
Parameters
BET
C
Wm (g/g)
Area (m2 /g)
R2
1882.4
0.132
431
0.99
1635
0.127
388.6
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
80.3
0.155
615
0.99
133
0.16
548.1
0.99
Table 5
BET and Langmuir isotherm parameters for N2 adsorption on Kilimli samples (chemical treatments at 650 C)
Kilimli
Parameters
BET
C
Wm (g/g)
Area (m2 /g)
R2
1168
0.145
467
0.99
106 718
0.11
376.4
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
133.9
0.19
658
0.99
70.23
0.151
534.1
0.99
Table 6
BET and Langmuir isotherm parameters for N2 adsorption on Armutcuk samples (chemical treatments at 750 C)
Armutcuk
Parameters
BET
C
Wm (g/g)
Area (m2 /g)
R2
161
0.1
261.2
0.99
4118
0.09
277.7
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
88.5
0.102
358.2
0.99
106
0.111
391.7
0.99
Table 7
BET and Langmuir isotherm parameters for N2 adsorption on Kilimli samples (chemical treatments at 750 C)
Kilimli
Parameters
BET
C
Wm (g/g)
Area (m2 /g)
R2
175
0.15
504.2
0.99
1707
0.156
830.5
0.99
Langmuir
C
Wm (g/g)
Area (m2 /g)
R2
91.06
0.203
713.8
0.99
84.37
0.204
1200
0.99
In Table 8, total pore volumes and average pore sizes for the
Armutcuk and Kilimli coal mine samples exposed to pyrolytic
thermal and chemical treatments were presented. Total pore
1/((W(P0 /P)-1))
2.5
Table 8
Total pore volumes and average pore sizes for Armutcuk and Kilimli samples
2.0
Samples
Armutcuk (processed)
A800
A650(1)
A650(2)
A750(1)
A750(2)
0.0005
0.020
0.215
0.192
0.136
0.125
19.70
19.07
19.87
19.77
19.68
19.70
Kilimli (processed)
K800
K650(1)
K650(2)
K750(1)
K750(2)
0.0007
0.025
0.231
0.186
0.250
21.93
19.03
19.77
19.77
19.80
19.70
1.5
1.0
0.5
0.0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
P/P0
Fig. 13. BET isotherms for N2 adsorption on Kilimli samples at 77.4 K
(chemical treatment at 750 C).
1.6
1.4
1.2
1.0
P/P0 /W
5013
0.8
0.6
0.4
0.2
0.0
-0.2
0.00
0.05
0.10
0.15
0.20
0.25
0.30
P/P0
Fig. 14. Langmuir isotherms for N2 adsorption on Kilimli samples at 77.4 K
(chemical treatment at 750 C).
5014
4. Conclusions
Ash contents of coal samples from Kilimli and Armutcuk coal
mines were reduced from 4.5 and 4.95 to 0.52 and 0.48 wt%,
respectively, by treatment with aqueous solution of 15% HCl
for 24 h, then by applying treatment with an aqueous solution
of 25% HF (at 60 C for 2 h), followed by extraction with 1 M
NaOH at 120 C for 9 h. Surface areas and N2 sorption capacities of the samples were increased by pyrolysis under N2 ow
in the temperature range of 600900 C. The maximum BET
surface areas were obtained with pyrolysis thermal treatment
at 800 C for Kilimli coal samples. The BET surface areas of
Kilimli and Armutcuk coal samples were increased from 1.197
and 0.0008 to 52.62 and 41.55 m2 /g, respectively, after pyrolysis under N2 at 800 C. BET surface areas of the chemically
activated Kilimli coal samples were increased to 830.5 m2 /g by
treating the coals with KOH + NH4 Cl mixture at 750 C followed by oxidation of the samples mixed with ZnCl2 . It can be
concluded that in order to produce activated carbons with high
surface area and porosity, physical activation itself is not sufcient. Using ZnCl2 resulted with high surface area activated
carbons. All the activated carbon samples produced from coal,
collected from two mines in Zonguldak region, by pyrolytic
thermal and chemical treatments in this study were used for the
investigation of the hydrogen sorption properties and hydrogen
sorption results will be reported in our further study.
Acknowledgements
The experimental study of this work was carried out by
utilizing the Laboratory equipment facilities provided by the
project DPT2002K120640 funded by State Planning Organization (DPT), Turkey.
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