International Journal of Hydrogen Energy 32 (2007) 5005 5014

www.elsevier.com/locate/ijhydene

Preparation of activated carbons from Zonguldak region coals by physical

and chemical activations for hydrogen sorption
Turkan Kopac , Atakan Toprak
Department of Chemistry, Zonguldak Karaelmas University, 67100 Zonguldak, Turkey
Received 13 May 2007; received in revised form 4 August 2007; accepted 4 August 2007
Available online 25 September 2007

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.

E-mail address: turkankopac@yahoo.com (T. Kopac).

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

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T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

their properties such as adsorption, electrochemical, catalytic,

acidbase, redox, hydrophiloushydrophobic, etc. [4].
The sorption characteristics of activated carbons are closely
related to their particular pore size distribution, and these characteristics are dependent on the overall preparation process.
mesoIn general, pores are principally microporous (< 20 A),
and macroporous (< 500 A).
Activated carporous (20500 A)
bons are mainly microporous, but besides micropores they may
also include meso and macropores, which are very considerable
in facilitating crossing of the adsorbate molecules to the interior
of carbon particles [3].
There are two main processes for the preparation of activated
carbons: chemical and physical activations [1,15]. Chemical
activation consists of a carbonization step at a specic temperature in the presence of chemical agents such as KOH, NH4 Cl,
ZnCl2 , etc. These chemical reagents may promote the constitution of cross-links, leading to the constitution of rigid matrix, less prone to volatile loss and volume contraction upon
heating to high temperatures [1,1517]. The physical activation process consists of a preliminary thermal treatment of the
carbonaceous precursor in an inert environment, called pyrolysis followed by suitable activation of the resulting char using
steam or carbon dioxide [1820]. It was reported in literature
that air is not widespread used as oxidant, although lower activation temperatures could be used, as carbonoxygen reactions are exothermic and can result in thermal runaway and
extreme burn off [21]. Many complex activation processes have
also been reported [1621]. One of the important advantages
of the chemical process over the physical process is that the
yield tends to be greater as carbon burn off is not required in
chemical process.
The methods for the preparation of activated carbon attracted
the attention of researchers for characteristics of surface area
and the capturing capabilities of many pollutants. Shchipko and
Kuznestsov [22] observed that the type of gassolid contact in a
uidized bed reactor promoted the formation of mesopores during the activation process. Linares-Solano et al. [23] observed
that physical activation carried out in a uidized bed reactor,
either with steam or with carbon dioxide, considerably reduced
the necessary reaction time compared to xed bed conditions.
As for the activating agent, it is mostly admitted that although
carbon dioxide develops mainly microporosity, steam produces
a wider pore size distribution with larger development of wide
micropores and mesopores [23,24]. Davini [25] obtained activated carbons from a bituminous coal both from pyrolysis
and CO2 activation and reduced ash content by HCl and HF
treatments. It was claimed that sorbent characteristics were improved by increasing their degree of burn off and the sorbent
characteristics were related to their content of surface sites with
acidic and basic features, their surface area and their pore size
distribution. The ash content was reduced from 16.8% to 3.4%.
BET surface area of the raw, ash reduced and burn off of coals
were found as 4.8, 5.1 and maximum 965 m2 /g, respectively.
Tsubouchi and Ohtsuka [26] investigated ash reduction of low
rank coals by a xed bed quartz reactor. In their work, temperature programmed pyrolysis of low rank coals were performed

at 10 C/ min heating rate at temperatures up to 1350 C under

N2 atmosphere. Raw coals were rstly demineralized with acid
washing and Ca ion was then added to the demineralized coals,
and pyrolysis results for the resulting samples were compared.
Castello et al. [27] claimed that highly activated carbons could
be prepared with homogeneous micropore size distribution by
chemical activation. Activated carbons were prepared from anthracite and bituminous coals. Initially, samples were mixed
with KOH then resulting mixture was pyrolysed in a horizontal
furnace using nitrogen atmosphere. Consequently, the best BET
surface area was found 2021 m2 /g for coal mixed with KOH
at 800 C. Hsu et al. [28] prepared activated carbons by chemical activation from bituminous coals with different chemical
reagents, such as ZnCl2 , H3 PO4 and KOH, carbonization was
followed in nitrogen at various temperatures. The surface areas obtained from the activation with ZnCl2 , H3 PO4 and KOH
were 960, 770 and 3300 m2 /g, respectively. It was reported that
the method applied was not suitable for preparing high-porosity
carbons from bituminous coal, while carbons with very high
porosity could be produced with bases such as KOH. An increase in particle size of the coal precursor was found to cause
a reduction in both yield and porosity of resulting carbons.
Teng et al. [3] produced activated carbons by mixing coal with
phosphoric acid followed by carbonization under nitrogen. It
was noted that the surface area and pore volume of the resulting carbons increased with the chemical ratio, H3 PO4 /coal.
The chemically activated carbons prepared from carbonization
at 500 C for 3 h was found to have maximum surface area and
pore volume values. The best BET surface area and pore volume
was found as 551 m2 /g and 0.300 cm3 /g, respectively. Ganan
et al. [21] showed that activated carbons could be prepared
from bituminous coal pitches by combining chemical and physical activations. Chemical activations method used potassium
hydroxide. Coal pitches were mixed with KOH followed by
carbonization in nitrogen atmosphere, the optimum KOH:pitch
ratio was xed to realize a physical activation process in order
to increase the textural parameters of the KOH-activated carbons. Finally, carbons with areas as high as 2346 m2 /g were
obtained for KOH:pitch ratio (3:1) and temperatures around
800850 C. However, gasication process with air at 300 C
resulted in no signicant improvement of the textural characteristic of the carbons. Yang et al. [29] prepared activated carbons
by heat treatment of a mixture of coal char and KOH under the
protection of an inert argon ow and the inuence of operating conditions on the properties of adsorbents was investigated.
Based on the experimental results, a new model of graphitic
crystallites containing hydrogen atoms was proposed and they
claimed that the idealized surface area of carbon adsorbents
could be precisely calculated with the aid of X-ray diffraction.
Lillo-Rodenas et al. [30] reported that physical mixing produced larger pore volumes by KOH activation than by NaOH
activation. The preparation method was optimized through the
analysis of diverse experimental variables. Among them, activating agent/coal ratio, drying process, method of mixing of the
activating agent and coal, nitrogen ow during pyrolysis and
mineral matter content of the coal were studied. It was shown
that chemical activation with NaOH could be successfully used

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

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

followed by ltration and washing with distillated water

until the chloride ion content in the ltrate solution was
entirely eliminated. Then, following this rst step, a second
treatment was applied with an aqueous solution of 25% HF
at 60 C for 2 h, followed by ltration and washing with
distillated water until the uoride ion content in the ltrate
solution was entirely eliminated.
This sample was then accurately extracted in a Soxhlet apparatus containing 1 M NaOH solution. The extracted sample was dried in a laboratory oven at 120 C and stored in
a desiccator. This process was applied to all coal samples.
Afterwards, coal samples were then subjected to a pyrolytic
thermal treatment under N2 ow at different temperatures
in a temperature range of 600900 C. The process was
performed by heating the coal samples in an electronically
controlled tubular oven (at a heating rate of 30 C/min)
to the desired temperature and keeping the samples at this
temperature for 120 min. The resulting chars were then left
to cool down under N2 ow.
Coal samples were washed with KOH at 85 C for 2 h and
were then left to dry at 120 C for 1 day, after then they
were ltrated and washed with distillated water. After these
processes, ZnCl2 and coal sample were mixed in a crucible
at a ZnCl2 :coal ratio of 3:1 and the coal sample was oxidized
in a furnace for 1 h at 650 and 750 C temperatures.
Coal samples were also prepared according to the procedure
explained in step 4 by washing the samples with a mixture
of saturated solution of KOH and then NH4 Cl at 85 C and
following this they were washed.
Nitrogen adsorption experiments were carried out at 77.4 K
by using Quantachrome NOVA 2000 Multi-Station High
Speed Gas Sorption Analyzer. The solid densities of the
samples were measured by helium displacement with Quantachrome Ultrapycnometer 1000 QA. The characteristics of
the starting coals were given in Table 1.

3. Results and discussion

3.1. Preparation of coal samples with demineralization
The characteristics of the raw coal samples and the samples
treated with HCl and HF solutions for ash reduction were
reported in Table 1. The BET surface areas of the raw coal
samples from Kilimli and Armutcuk mines measured by N2
adsorption at 77.4 K were found as 1.197 and 0.0008 m2 /g,
respectively. After the demineralization step, the BET surface
areas of the demineralized coal samples from Kilimli and

Table 1
Characteristics of starting coals
Samples

Density (g/cm3 )

Ash content (%)

Fixed C (%)

V.M. (%)

BET S.A. (m2 /g)

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

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T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

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

Fig. 1. N2 adsorption isotherms on Kilimli coal samples at 77.4 K (Tpyrolysis =

600900 C).

Fig. 2. N2 adsorption isotherms on Armutcuk coal samples at 77.4 K

(Tpyrolysis = 600900 C).

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.

samples from Kilimli (K900) and Armutcuk (A900) coal mines

at 900 C were decreased to 27.27 and 24.85 m2 /g, respectively.
In Figs. 36, the comparison of the N2 adsorption isotherms
for samples from Kilimli and Armutcuk mines were drawn for
600, 700, 800 and 900 C temperatures, respectively. Nitrogen
sorption capacity of Kilimli (K600900) coals were higher than
Armutcuk (A600900) coal mines. BET and Langmuir parameters were calculated by using the portion of the data up to
P /P0 = 0.3. The comparison of the experimental adsorption
isotherm data with the BET and Langmuir adsorption isotherms
were shown in Figs. 7 and 8, respectively, for Kilimli samples
pyrolysed at 800 C which was used for the evaluation of the
adsorption isotherm model constants at 77.4 K for N2 . The experimental adsorption isotherm data were in good agreement
with the BET and the Langmuir adsorption isotherm models
with R 2 values of 0.99. According to the results, pyrolysis process applied to the raw and the ash reduced coal samples in a
temperature range of 600900 C under N2 ow affected considerably the N2 adsorption parameters at 77.4 K. The increase
in surface area with an increase in temperature up to 800 C
can be attributed to the release of volatiles to leave the space
that was previously occupied by the decomposed samples, and
hence causes an increase in the adsorption capacity. Decrease
of surface area at temperatures higher than 800 C can be due to
the breakdown of cross-links in the carbon matrix with a consequent rearrangement of carbonaceous aggregates and collapse
of pores as also pointed out in literature [28]. Also the extensive gasication at high temperatures results in destruction of
pore structures.
According to the IUPAC classication [34], the N2 adsorption isotherms on activated carbon samples shown in Figs. 1
and 2 conform to Type I isotherm showing that these activated
samples are microporous carbons. Only when there is a high
microporosity development the knee of the isotherms widens.
The knee of the isotherms gets wider with increasing temperature (under N2 ow) but decreases after 800 C. The total pore

3.2. Effect of pyrolytic thermal treatment under N2 ow

The pyrolysis process of the coal samples from Kilimli and
Armutcuk mines under N2 ow in a temperature range of
600900 C produced coals that have a commonly microporous
structure. When the temperature of the pyrolysis process was
increased, BET surface areas of the samples from Kilimli and
Armutcuk mines showed a maximum at 800 C, as shown in
Figs. 1 and 2. The differences in the samples of Kilimli
(K600900) and Armutcuk (A600900) coal mines did not
appear to be particularly signicant. From the experimental
adsorption isotherm data given as volume of adsorbed, V versus relative pressure, P /P0 plots shown in Figs. 1 and 2, the
BET and the Langmuir isotherm parameters were calculated
for N2 adsorption on Kilimli and Armutcuk coal samples and
were reported in Tables 2 and 3, respectively, for different temperatures. Highest surface areas were obtained at 800 C for
both samples from Kilimli (K800) and Armutcuk (A800) coal
mines. At 800 C, the BET surface area of activated carbon
samples were 52.62 and 41.55 m2 /g, for Kilimli and Armutcuk
mines, respectively. For both samples the surface areas were
found to decrease after 800 C. BET surface areas of the

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

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

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

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)

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

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).

N2 ow at 800 C, the sorption capacity and the proportion of

micropores obtained are considerable. The plateau observed in
the nitrogen adsorption isotherms of the samples exposed to pyrolytic thermal treatments in a temperature range of 600900 C
showed that the mechanism of nitrogen adsorption on the samples exposed to pyrolytic heat treatments could be considered
a pore lling mechanism rather than surface coverage.

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

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

Fig. 5. N2 adsorption on Kilimli versus Armutcuk coal samples at 77.4 K

(Tpyrolysis = 800 C).

Fig. 7. BET isotherms for N2 adsorption on Kilimli samples at 77.4 K

(Tpyrolysis = 800 C).

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

Fig. 6. N2 adsorption on Kilimli versus Armutcuk coal samples at 77.4 K

(Tpyrolysis = 900 C).

Fig. 8. Langmuir isotherms for N2 adsorption on Kilimli samples at 77.4 K

(Tpyrolysis = 800 C).

3.3. Effect of chemical activation with chemical reagents

Armutcuk and Kilimli mines were mixed with ZnCl2 with

ZnCl2 :coal ratio of 3:1, respectively. These samples were
then carbonized at 650 and 750 C temperatures. In Figs. 9
and 10, the effects of temperature and chemical reagent on
N2 adsorption isotherms for Armutcuk and Kilimli coal samples, respectively, were shown. The comparison of the N2
isotherms on Kilimli and Armutcuk coal samples at 77.4 K
which were chemically treated at 650 and 750 C temperatures were shown in Figs. 11 and 12. According to the IUPAC classication for characteristic of microporous solids,
all of the activated carbons obtained exhibited a steep Type
I isotherms. From the plot of V versus P /P0 , the BET and
the Langmuir isotherm parameters for N2 adsorption at 77.4 K
were calculated. The results for the samples from Armutcuk
and Kilimli mines at 650 C were reported in Tables 4 and 5,

The preparation of activated coal by chemical activation

mainly consists of two successive steps: impregnation of a
chemical reagent followed by carbonization. In order to examine how the differences in chemical reagent affects the
carbonization behaviour, the variation of surface characteristics of carbons with carbonization temperature was examined.
It was reported in the literature that the chemical activation
with KOH is an effective method to prepare activated carbon
materials. Coal samples were washed with KOH at 85 C for
2 h and dried at 120 C for 24 h. Then the carbonization of
the impregnated coal samples with ZnCl2 were carried out
under N2 environment. In the same way, coal samples were
washed with KOH and NH4 Cl, then the coal samples from

200

200

150

150
V(cc/g)

V(cc/g)

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

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).

Fig. 11. N2 adsorption isotherms on Kilimli versus 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

Fig. 10. N2 adsorption isotherms on Kilimli samples at 77.4 K (chemical

treatment at 650750 C).

Fig. 12. N2 adsorption isotherms on Kilimli versus Armutcuk coal samples

at 77.4 K (chemical treatment at 650750 C).

respectively. At 650 C, higher values of surface areas were

found for the samples from Kilimli mines (K650(1)) than
Armutcuk mines. The BET and the Langmuir isotherm parameters of coal samples at 750 C were shown in Tables 6
and 7, for Armutcuk and Kilimli samples, respectively. In
these tables, the parameters were calculated also using the
portion of the data given until P /P0 = 0.3. The experimental adsorption isotherm data were in good agreement with
the BET and the Langmuir adsorption isotherm models with
R 2 values of 0.99. The BET and the Langmuir isotherm
plots for Kilimli coal samples were given in Figs. 13 and 14,
respectively. The maximum surface areas were obtained at
750 C for samples washed with KOH + NH4 Cl by chemical agent (ZnCl2 ) with thermal treatment. According to the
BET and Langmuir isotherm analysis results, it can be said
that, changing the preparation variables, it was possible to

increase the BET surface area of coals from around 1 m2 /g to

more than 830 m2 /g by applying chemical treatments. It could
be possible to prepare high surface areas by chemical activation. To reach high BET surface areas is not easy, and it is even
more difcult if this surface area corresponds mainly to narrow microporosity. This type of microporosity cannot be obtained by physical activation because the increase in surface
areas occurs together with pore widening. The result obtained
with chemically treated activated carbons were compared with
the coal samples exposed to thermal pyrolysis under N2 ow
in a temperature range of 600900 C. That means for physical activation, even though high surface area activated carbons can be obtained, the development of narrow microporosity
reaches a maximum, which cannot be further exceeded. From
this maximum, further increase in micropore volume results
in an increase of the pore size. On the other hand, activated

5012

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

Table 4
BET and Langmuir isotherm parameters for N2 adsorption on Armutcuk samples (chemical treatments at 650 C)
Armutcuk

Parameters

650 C KOH + ZnCl2 A650(1)

650 C KOH + NH4 Cl + ZnCl2 A650(2)

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

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

Table 5
BET and Langmuir isotherm parameters for N2 adsorption on Kilimli samples (chemical treatments at 650 C)
Kilimli

Parameters

650 C KOH + ZnCl2 K650(1)

650 C KOH + NH4 Cl + ZnCl2 K650(2)

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

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

Table 6
BET and Langmuir isotherm parameters for N2 adsorption on Armutcuk samples (chemical treatments at 750 C)
Armutcuk

Parameters

750 C KOH + ZnCl2 A750(1)

750 C KOH + NH4 Cl + ZnCl2 A750(2)

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

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

Table 7
BET and Langmuir isotherm parameters for N2 adsorption on Kilimli samples (chemical treatments at 750 C)
Kilimli

Parameters

750 C KOH + ZnCl2 K750(1)

750 C KOH + NH4 Cl + ZnCl2 K750(2)

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

Wm : amount of gas adsorbed per gram of adsorbent; C : isotherm constants.

carbons can be prepared by only KOH activation and thermal

treatment (ow N2 ) of coals, choosing the suitable preparation
condition.

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))

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 5014

2.5

Table 8
Total pore volumes and average pore sizes for Armutcuk and Kilimli samples

2.0

Samples

Total pore volume (cc/g)

Average pore size (A)

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).

volumes of the demineralized samples were 0.00050.0007 cc/g

and increased to 0.020.025 cc/g when exposed to pyrolytic
treatment at 800 C for samples from both mines. Applying
chemical treatments with KOH at 650 C, total pore volume
increased to 0.215 and 0.231 cc/g, for Armutcuk and Kilimli
mine samples, respectively. The highest value of total pore volume was obtained as 0.25 cc/g for Kilimli coal sample treated
with KOH reagent which was pyrolysed at 750 C. By the reaction of carbonaceous materials with the chemical reagents,
a chemical activating effect takes place in the presence of carbon. The metals also penetrate on the carbon matrix resulting
in an increase in pore volume.
In the case of Armutcuk coals, the experimental results have
shown that surface area and total pore volumes decrease with
an increase in temperature from 650 to 750 C. This behaviour

was also reported by Ahmadpour and Do [35]. They reported a

decrease in the physical properties of carbon, especially chemical recovery, with temperature when zinc chloride was used
as activating agent due to the zinc chloride evaporation from
the precursors at higher temperatures. For the case of Kilimli
samples, the reverse was observed however. Surface area and
total pore volumes were increased with an increase in temperature from 650 to 750 C. In the case of Kilimli samples,
increase in BET surface area and total pore volumes with
the carbonization temperature are probably the result of the
progress of activation as more carbon atoms are retained at
higher temperatures caused by KOH. It was clear that different
reaction mechanisms occurred in the samples collected from
two different mines. Several mechanisms were proposed in literature on the effect of KOH and zinc chloride on porosity
creation [35]. These suggested mechanisms indicate that zinc
chloride which is a Lewis acid promotes the aromatic condensation reactions while potassium hydroxide which is a strong
base catalyses the oxidation reactions [35]. The details of the
effects of KOH and zinc chloride on the carbonization of carbonaceous materials have been reviewed by Ahmadpour and
Do [35]. According to this review, the results of experimental
work with ZnCl2 had shown that the evolution of molecular
hydrogen was more pronounced than other gaseous products,
and these H2 gases were evolved from the hydroaromatic structure of the precursor leaving behind some sites for reactions. It
was reported that at this stage some cross-linking or aromatization reactions were taking place among the adjacent molecules
which resulted in stabilizing some of the molecules that were
normally volatile at that temperature. The consequential effect
of these aromatization processes was an increase in the carbon yield [35]. In KOH activation, production of some surface
metal complexes which are responsible for further carbon gasication and release of gaseous products such as CO2 , CO and
H2 were reported. Also, a number of oxygen functional groups,
as a result of the oxidizing atmosphere, are found to be formed
on the carbon surface. It was reported that at a temperature
higher than 700 C, metallic potassiums are produced and they
intercalated to the carbon matrix. This phenomenon results in
widening of the spaces between carbon atomic layers and increasing the pore volume [35].

5014

T. Kopac, A. Toprak / International Journal of Hydrogen Energy 32 (2007) 5005 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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