Fuel 118 (2014) 915

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Granular KOH-activated carbons from coal-based cokes and their CO2

adsorption capacity
Katarzyna Labus, Stanisaw Gryglewicz, Jacek Machnikowski
skiego 27, 50-370 Wrocaw, Poland
Division of Polymer and Carbonaceous Materials, Faculty of Chemistry, Wrocaw University of Technology, Wybrzez_ e Wyspian

h i g h l i g h t s
 Facile way of producing granular KOH-activated carbon.
 Impact of coal rank and coking temperature on strength and porosity.
 Attractive CO2 uptake of resultant GACs.

a r t i c l e

i n f o

Article history:
Received 25 July 2013
Received in revised form 17 October 2013
Accepted 17 October 2013
Available online 31 October 2013
Keywords:
Coal-coke
KOH activation
Granular adsorbent
CO2 capture

a b s t r a c t
Granular activated carbons (>0.5 mm) have been prepared by KOH activation at 800 C of cokes, size fraction of 0.631.25 mm, from high volatile bituminous coals. The most suitable coal is distinctive by the
volatile matter content of about 33 wt.% and negative dilatation in the AudibertArnu test. The highest
mechanical strength of granules is found for the activated carbons from cokes produced at 800850 C.
They are microporous materials with porous texture parameters decreasing as the KOH/coke ratio varies
from 4:1 to 2:1 in the range: surface area SBET 18001200 m2 g 1, micropore volume VDR 0.710.48 cm3
g 1 and mean micropore size L0 1.120.76 nm. The granular activated carbons represent interesting properties for gas adsorption application. CO2 uptake measured at 273 K amounts to 140 cm3 g 1 under atmospheric pressure and 370 cm3 g 1 under 3.5 MPa, corresponding to 6.2 and 15.7 mmol g 1, respectively.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Some drawbacks, including energy intensity, related to the
absorption in amines induces urgent need for an alternative technology for CO2 separating from ue gas and gasication stream.
Recently published reviews [14] have shown that development
of innovative processes and materials for CO2 capture is an active
research eld in many laboratories. Using functionalized solid sorbents is one of the realistic solutions for feasible and more economic capture [4]. However, making the adsorption a viable
industrial process requires adsorbent of high selectivity and capacity, efcient packing structure and also improved operating conditions [5].
Activated carbons and zeolites are two families of microporous
materials widely studied as potential CO2 adsorbents. In common
opinion, advantages of activated carbons are low cost, hydrophobicity and exibility in terms of porous texture and surface properties. In contrast, the capacity and selectivity favor using zeolites.
The comparison of CO2 uptake on zeolite 13X and conventional
activated carbon of BET surface area of 900 m2 g 1 shows,
Corresponding author. Tel.: +48 71 320 6350; fax: +48 71 320 6203.
E-mail address: jacek.machnikowski@pwr.wroc.pl (J. Machnikowski).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.10.042

however, that the zeolite is preferred only under a low pressure

[6]. At 2 MPa the capacity of 13X amounts to 5.2 compared to
8.5 mmol g 1 for the activated carbon. As high as 18 mmol g 1 uptake has been reported at 25 C and 2 MPa for the activated carbon
of SBET 2800 m2 g 1.7 Moreover, in favor of carbon adsorbent is a
moderate attractive force, which facilitates desorption [7].
In general, the adsorption capacity of permanent gases is controlled by the microporous texture of adsorbent [8]. The recent
study using carbide derived carbons (CDC) has clearly demonstrated that optimizing micropore size distribution for a given
pressure can be more effective in enhancing adsorption capacity
and selectivity than enlarging pore volume and BET surface area
[9].
Activation with potassium hydroxide is well-known as an efcient method for producing microporous carbons of tailored porous texture from a variety of organic and carbonaceous precursor
[1012]. It has been recently reported that some KOH-activated
carbons can absorb at 25 C and atmospheric pressure near
5 mmol g 1 CO2, compared to 1.72.5 mmol g 1 in case of physically activated carbons [13,14].
Since the early work [10], it has been generally accepted that
KOH-activated carbons are powders of very low packing density.
Such a nature is a serious drawback in practical gas-phase

10

K. Labus et al. / Fuel 118 (2014) 915

application. Making carbons in the form of granules of sufcient

mechanical resistance is a real challenge. The approaches which
have been reported in the literature consisted on molding the mixture of KOH and mesophase pitch powder under high pressure [15]
or extruding paste made by blending pre-oxidized coal with KOH
solution [16]. Subsequent thermal treatment resulted in pellets
with developed microporosity. An alternative is pressing the activated carbon powder with a suitable polymer binder followed by
baking [17,18]. The disadvantage is in this case an unavoidable
partial pore blockage by binder.
The mechanism of porosity generation in reaction of carbonaceous materials with KOH involves oxidation of carbon to carbonate followed by activation with CO2 from K2CO3 decomposition
[19,20] and potassium metal intercalation between the graphene
layers [10,2123]. Potassium penetration is responsible for breaking of particles to the extent which depends on the precursor nature. It was showed that strong cross-links between constituting
basic structural units of the coalcoke allow particle integrity to
be partially preserved [24].
The above observation has become the motivation to study the
KOH activation of coal-derived cokes in the form of relatively large
particles as a potential route to granular activated carbons. The
rst part of the study is concerned with the selection of suitable
parent coal, based on the mechanical strength of the resultant activated carbon. Size fraction 0.631.25 mm of laboratory cokes was
prepared from different rank coals at 800 C and activated at
800 C using KOH/coke ratio of 3:1. The second part is focused on
optimizing carbonization degree of coke from the selected coal in
terms of porosity development and mechanical strength of activated carbons particles. The produced granular KOH activated carbons are assessed as potential CO2 adsorbents under pressure up to
3.5 MPa.
2. Materials and methods
2.1. Materials
Materials used for granular activated carbons production were
cokes prepared at a laboratory scale from different rank bituminous coals and anthracites. The coals were from following polish
mines: Krupinski (CKr), Szczygowice (CS), Marcel (CM), Knurw
(CK), Pniwek (CP), Borynia (CB) and JasMos (CJ). The anthracites
were from Sverdlovsk (CA) and Listviansk (CL) mines in Russia.
The proximate analysis and the determination of coking properties
of coals were performed according to standard methods: ash content A ISO 1171:2010, volatile matter content VM ISO
562:2010, free-swelling index SI ISO 501:2003, caking power RI
(Roga test) ISO 335:1974) and dilatation b (AudibertArnu test)
ISO 349:1975). Two step procedures were used to prepare a series of cokes of different carbonization degree. The parent coals
were rst pyrolyzed in a vertical glass retort at 520 C for 2 h under
argon (heating rate of 5 C min 1). The resultant semi-cokes were
ground and sieved to prepare size fraction of 0.631.25 mm, which
was next carbonized at appropriate nal temperature in the range
of 700900 C for 2 h in a horizontal tube reactor. The cokes are labeled XX700, . . ., XX900, where XX is a coal symbol followed by
heat-treatment temperature. The carbonization degree of cokes
was assessed based on volatile matter content and H/C atomic ratio. The elemental composition (CHNS) was determined using Vario El elemental analyzer.
2.2. Preparation of activated carbon
To produce activated carbon a physical mixture of anhydrous
KOH and a given coke (size fraction 0.631.25 mm) in the weight

ratio of 2:1, 3:1 and 4:1 was placed in a nickel boat and heated
at a rate of 10 C min 1 to the nal temperature of 800 C and
soaked for 1 h. The treatments were carried out in a horizontal
tube oven with an inner diameter of 46 mm under inert gas ow
of 30 dm3 h 1. The reaction products were washed repeatedly with
10% solution of HCl and distilled water and dried at 120 C for 3 h.
For analysis were used granular activated carbons (GAC), i.e. the
fraction of size above 0.5 mm. Its weight proportion is given as F.
The symbol of GAC, e.g. A-CS700-2, describes in sequence: coal
(CS), carbonization temperature (700 C) and the KOH:coke weight
ratio (2:1).
2.3. Characterization of activated carbons
GACs were characterized in terms of mechanical strength and
porosity development. The modied MarshRagan method [25]
was used to determine so called microstrength of coke and activated carbon grains. The test measures the resistance of grains to
grinding with steel balls during rotating in a sealed stainless steel
cylinder of length 305 mm and internal diameter of 25.4 mm. In
our test 1.5 g of sample was rotated for 2 minutes with 12 steel
balls (8 mm diameter) at a speed of 25 rev/min. The results are expressed as microstrength index MS which is calculated in the study
as a percentage of grains with size above 0.5 mm in the sample
after tumbling. MS dened in that way can vary between 0 and
100. The porous texture of GACs was characterized by N2 adsorption at 77 K using ASAP2020, Micromeritics, in SolGel Nanotechnology Materials Laboratory of Lower Silesian Centre for
Advanced Technologies in Wrocaw. Before the analysis the sample
was degassed overnight at 300 C. N2 adsorption isotherms were
used to determine the total micro- and mesopore volume VT, BET
surface area SBET and microporosity development. The micropore
volume VDR and the average micropore width L0 were calculated
from the application of the DubininRadushkevich and Stoeckli
equations [26], respectively, up to p/p0 < 0.015. The QSDFT method
[27] was applied to the N2 adsorption data obtained using ASAP to
determine the pore size distribution and micropore surface area
(SQSDFT). The isotherms of CO2 adsorption at 273 K under pressure
<10 kPa (NOVA2200, Quantachrome) were used to compute the
ultramicropores (0.330.7 nm) volume VDR CO2.
2.4. Determination of CO2 adsorption capacity
NOVA2200 (Quantachrome) apparatus was used to measure
CO2 uptake under atmospheric pressure. Before analysis the sample was degassed overnight at 300 C. Adsorption capacity under
a higher pressure, up to 3.5 MPa, was determined using a homemade Sievert-type volumetric apparatus. Before the analysis a
sample was degassed for 0.5 h at 250 C. All measurements were
performed at 273 K.

3. Results and discussion

3.1. Evaluation of coals as precursors of granular KOH activated
carbon
Proximate analysis and coking properties of coals used are given
in Table 1. The Table gives also the proportion of fraction above
0.5 mm F and microstrength index MS of GACs produced from
coal-derived cokes. The data refer to activated carbons from cokes
heat-treated at 800 C and activated at 800 C using KOH/coke ratio
3:1. Anthracites were activated without any pre-treatment.
Based on the volatile matter content most of the coals, CKr, CS,
CM, CKn and CP can be classied as high volatile bituminous, CB

11

K. Labus et al. / Fuel 118 (2014) 915

after activation with KOH. The proportion F of size fraction

>0.5 mm in the activation product varies between 77 and 93% of.
There is a weak tendency to increase F with coke HTT but any clear
effect or KOH/coke ratio could not be noticed.
Fig. 1 shows the effect of heat-treatment temperature of coal CS
on microstrength index MS of GACs. The results indicate that GACs
are characterized by a moderate strength. The variation of MS with
HTT of precursor follows, in principle, the trend occurring for
cokes. The microstrength clearly increases with coal carbonization
temperature and reaches a maximum at 800850 C, then slightly
decreases. In case of A-CS800 and ACS850 activation increasing
KOH/coke ratio results in a weakening of grains. This rather expected trend is not obvious when microstrength of GACs from
other cokes is compared.
Fig. 2 presents representative isotherms of N2 adsorption at 77
K on GACs produced from CS-derived cokes. Proles of all isotherms prove the microporous nature of the activated carbons.
Nitrogen uptake clearly decreases with increased carbonization
temperature of precursor (Fig. 2a) and with reduced KOH/coke ratio (Fig. 2b) thus indicating diminishing porosity development.
QSDFT analysis applied to N2 adsorption isotherms (Fig. 3) indicates that all GACs have predominantly narrow micropores of size
smaller than 1 nm. Increasing coke HTT from 700 to 900 C while
keeping KOH/coke ratio 3:1 induces gradual narrowing pore size
distribution (Fig. 3a). QSDFT prole of A-CS700-3 suggests considerable contributions of larger micropores and some mesopores. It
is evidenced by humps corresponding to pores of size about 0.9
and 1.3 nm, which gradually disappear in A-CS-800-3 and A-CS900-3. Decreasing KOH/coke ratio during activation of CS800
(Fig. 3b) induces similar effect in pore size distribution. A-CS8002 practically does not contain pores wider than 1.7 nm.
Figs. 4 and 5 demonstrate the effect of coke HTT on BET surface
area SBET and micropore volume VDR, calculated from N2 adsorption
isotherms at 77 K, of activated carbons produced using different
KOH/coke ratio. The linear decrease with HTT occurs also for Smicro
and VT (see Figs. S1 and S2 of the Supporting material). The best
correlation is observed in case of parameters characterizing

Table 1
Properties of coals and strength of derived granular activated carbons.

a
b

Coal

Aa (wt.%)

VMb (wt.%)

RI

SI

b (%)

F (wt.%)

MS (wt.%)

CKr
CS
CM
CKn
CP
CB
CJ
CA
CL

7.0
5.3
6.1
5.7
9.3
5.8
4.9
4.1
2.8

36.8
33.2
32.4
31.6
28.5
24.5
21.6
3.2
2.2

41
36
54
72
62
49
56
0
0

2
2
5.5
7
7.5
3.5
4
0
0

15
30
22
10
49
19
n.d.
n.d.
n.d.

82.0
92.4
92.6
88.6
64.0
72.3
12.9
5.9
5.4

43.1
51.5
49.8
33.6
12.6
25.6
0.0
0.0
0.0

Dry basis.
Dry and ash free basis.

and CJ are medium volatile bituminous coals. CA is anthracite and

CL metaanthracite.
In case of anthracites the treatment with KOH resulted in almost complete disintegrations of the grains. In contrast, coal cokes
preserve to different extent the form of granules with some
mechanical strength. The most promising seem to be high volatile
bituminous coals, especially CS and CM. Cokes from the coals give
on activation more than 90% of unbroken granules, which show
relatively good mechanical resistance. Characteristic of coals CS
and CM are volatile matter content of about 33 wt.% and strong
negative dilatation, 30 and 22 %, respectively. Neither swelling
index nor caking power appeared to be specic features of the
coals. The strength of activated carbon granules should be related
to that of coke. Therefore, in addition to parent coal properties,
the carbonization variables which inuence on the mass and heat
transfer processes can be essential to the strength of GACs.
Evaluation of strength of KOH activated carbon granules points
to coal CS as most promising parent material for the study on optimizing coking temperature.
3.2. Effect of coal CS carbonization temperature on the properties of
cokes and activated carbons

60

Increasing the heat-treatment temperature of coal from 700 to

900 C induces signicant reduction of hydrogen (from 1.6 to 0.8
wt.%) and oxygen (from 3.5 to 1.8 wt.%) contents in coke (Table 2).
H/C atomic ratio gradually decreases from 0.21 to 0.10. The
abstraction of peripheric hydrogen and oxygen functionalities promotes the condensation and cross-linking of structural units. A
consequence is structural shrinkage and enhanced strength. Microstrength index MS increases from 62.6 in CS700 to maximum of
74.7 in CS850.
The evaluation of mass balance during KOH activation of granular cokes shows that the burn-off varies from 34 to 17 wt.% and
depends mostly on reagent proportion. For KOH/coke ratio of 4:1
it is bigger than for 2:1 by 1113 wt.%. With increasing coke HTT
from 700 to 900 C, burn-off decreases, for a given KOH/coke ratio,
by 46 wt.%. Interestingly, most of coke grains preserve integrity

50

MS

40
30

KOH/coke ratio
2:1
3:1
4:1

20
10
0
700

750

800

850

900

HTT ( C)
Fig. 1. Changes of microstrength of KOH activated carbons in dependence on
temperature of coal CS carbonization.

Table 2
Properties of cokes produced from coal CS.
Sample

CS700
CS750
CS800
CS850
CS900
a
b

VMa (wt.%)

5.2
3.5
3.4
3.2
1.6

Dry and ash free basis.

Calculated by difference.

Elemental analysisa (wt.%)

C

Ob

92.7
93.1
94.3
94.6
95.2

1.6
1.5
1.2
1.1
0.8

1.9
1.9
1.8
1.8
1.8

0.3
0.4
0.4
0.3
0.4

3.5
3.1
2.3
2.2
1.8

(H/C)at

MS (wt.%)

0.21
0.19
0.15
0.14
0.10

62.6
63.5
70.1
74.7
70.5

700

(a)

-1

600

500

500

(b)

700

-1

600

Volume of N2 (cm g STP)

K. Labus et al. / Fuel 118 (2014) 915

Volume of N2 (cm g STP)

12

400
300

A-CS700-3
A-CS750-3
A-CS800-3
A-CS850-3
A-CS900-3

200
100
0
0.0

0.2

0.4

0.6

0.8

400
300
200

A-CS800-2
A-CS800-3
A-CS800-4

100
0

1.0

0.0

0.2

0.4

p/p0

0.6

0.8

1.0

p/p0

Fig. 2. N2 adsorption isotherms at 77 K of activated carbons produced from CS-derived cokes: effect of coke HTT for KOH/coke ratio 3:1 (a); effect of KOH/coke ratio for CS800
activation (b).

0.20
0.15
0.10
0.05
0.00

(b)

A-CS800-2
A-CS800-3
A-CS800-4

0.20

A-CS700-3
A-CS800-3
A-CS900-3

Pore volume (cm /g)

0.25

(a)

Pore volume (cm /g)

0.25

0.15
0.10
0.05
0.00

0.5

1.0

1.5

2.0

2.5

0.5

1.0

1.5

2.0

2.5

Pore size (nm)

Pore size (nm)

Fig. 3. Pore size distribution determined by applying a QSDFT analysis to the N2 adsorption isotherms of activated carbons produced from CS-derived cokes: effect of coke
HTT for KOH/coke ratio 3:1 (a); effect of KOH/coke ratio for CS800 activation (b).

1.2

-1

SBET (m g )

2000
1600

-1

2400

KOH:coke ratio
2:1
3:1
4:1

1.0

KOH : coke ratio

2:1
3:1
4:1

VDR (cm g )

2800

0.8
0.6
0.4

1200
0.2
700

800
700

750

800

850

900

750

800

850

900

Coke HTT ( C)

Coke HTT ( C)
Fig. 4. Changes in the BET surface area SBET of granular KOH activated carbons with
the carbonization temperature of coal CS.

microporosity development (VDR and Smicro). The variation of L0

(Fig. 6) suggests that narrowing of micropores is associated mostly
with increase in coke HTT between 700 and 800 C. Reducing the
KOH/coke ratio from 4:1 to 2:1 results in the considerable shift
of plots to lower values. Porosity parameters (SBET, VT, VDR and L0)
determined here are quite similar to those reported in our earlier
work [28] concerning activation of cokes of the same thermal history but of particle size of 0.10.63 mm. It means that using precursors of twice larger average particle size has not restricted
porosity development.
The carbonization temperature of coal and KOH/coke ratio have
a minor effect on the ultramicropore (0.330.7 nm) volume,

Fig. 5. Changes in the micropore volume VDR of granular KOH activated carbons
with the carbonization temperature of coal CS.

determined from isotherms of CO2 adsorption (Fig. S3 of the Supporting material). VDR CO2 decreases with HTT from 0.55 to 0.45
cm3 g 1.
3.3. CO2 adsorption capacity of coal-based GACs
GACs produced from cokes of different carbonization degree
using the KOH/coke ratio of 3:1 were assessed as CO2 adsorbents
under pressure up to 3.5 MPa. The measurements under atmospheric pressure and 273 K show a gradual decrease in CO2 uptake
with coke HTT, from 139 to 113 cm3/g (STP), however most of the
capacity loss is associated with carbonization above 800 C

13

CO2 adsorption capacity (cm g )

K. Labus et al. / Fuel 118 (2014) 915

-1

1.8

L0 (nm)

1.4
1.2
1.0
0.8
0.6
700

750

800

850

900

Coke HTT ( C)

200
100

0.1 MPa

0
650

700

750

800

850

900

Fig. 8. Variation of CO2 uptakes of GACs in relation to coke carbonization

temperature for measurements performed under different pressure.

pressure region a higher KOH proportion in the reacting mixture

enhances to a certain extent the adsorption capacity.
Table 3 gives carbon dioxide uptakes of A-CS800-2, A-CS800-3
and A-CS800-4, measured at 273 K under pressure of 0.1, 1.0 and
2.0 MPa. The results show that enhancement of the uptake by
increasing KOH/coke ratio is moderate, especially under 0.1 MPa.
Taking into account lowered both, the packing density and
strength of granules with increased porosity development, the
activation using KOH/coke ratio around 2:1 seems to be more realistic. The comparison of CO2 adsorption capacity at 2 MPa of GACs
and some commercial granular activated carbons [29,30] (Table 4)
shows, that KOH activated materials of the study are fully competitive to the best commercial carbon adsorbents.
4. Conclusions
Microporous activated carbons in the form of granules >0.5 mm
with acceptable mechanical strength (GACs) were successfully prepared using activation with potassium hydroxide of coal-based
cokes of particle size of 0.631.25 mm. The most suitable high volatile bituminous coal is distinctive by the volatile matter content of
about 33 wt.% and negative dilatation in the AudibertArnu test.
While elevating carbonization temperature of the coal results in
the gradual decrease in porosity development, the mechanical
strength of GACs achieves a maximum at coke HTT of 800
850 C. GACs prepared from heat-treated at 800 C coal (CS800)
are microporous materials with porous texture parameters
decreasing, as the KOH/coke ratio varies from 4:1 to 2:1, in the
range: surface area SBET 18001200 m2 g 1, micropore volume
VDR 0.710.48 cm3 g 1 and mean micropore size L0 1.120.76 nm.
The carbons represent interesting properties for gas adsorption

400

(b)

-1

Adsorbet amount of CO2 (cm g STP)

(a)

100

-1

300

(Fig. 7a). All high pressure isotherms represent characteristic prole (Fig. 7b). CO2 adsorption capacity continues to increase fast
up to 0.71.2 MPa, next there occurs a clear plateau and increases
again above about 2 MPa due to contribution from the capillary
condensation. A-CS900-3 of relatively narrow micropore size distribution reaches the plateau at about 0.7 MPa, A-CS700-3 of most
developed porosity at 1.2 MPa.
Fig. 8 shows the variation of CO2 uptake on GACs in relation to
coke carbonization temperature for measurements performed under different pressure. The slope of plots becomes steeper with elevating pressure, so indicating enhanced inuence of porosity
development on the uptake. It means that a considerable increase
in pore volume and surface area (Figs. 4 and 5), results in a moderate enhancement of CO2 uptake under 0.1 MPa. In contrast, at
3.5 MPa A-CS700-3 adsorbs almost twice more CO2 than ACS900-3. In other words, highly developed microporosity is more
protable when adsorption occurs under elevated pressure, e.g.
for the removal of CO2 from gas generated from gasication [29].
The linear relationship of SBET, S0, VT and VDR with coke HTT allows
to anticipate that for this series of microporous GACs the CO2 uptake could be correlated with any of the porous structure parameters, but rst of all with S0 and VDR.
Presented so far results point to CS800 as precursor of optimal
properties for preparation of GACs which combine an acceptable
mechanical strength and a high CO2 uptake. This coke has been
used to assess the effect of KOH/CS800 ratio during activation on
the CO2 uptake of resultant GACs. The adsorption isotherms of
GACs prepared using KOH/CS800 ratio 4:1, 3:1 and 2:1, follow
under pressure up to 3.5 MPa the same trend characteristic of
the series of microporous carbons (Fig. 9). Except for the low

Volume of CO (cm g STP)

3.5 MPa
2.0 MPa
1.0 MPa
0.5 MPa
0.3 MPa

Coke HTT ( C)

Fig. 6. Changes in the micropore width L0 of granular KOH activated carbons with
the carbonization temperature of coal CS.

120

400

600

140

500

KOH:coke ratio
2:1
3:1
4:1

1.6

80
60

A-CS700-3
A-CS750-3
A-CS800-3
A-CS850-3
A-CS900-3

40
20
0
0

20

40

60

80

Pressure (kPa)

100

300

200

100

A-CS700-3
A-CS750-3
A-CS800-3
A-CS850-3
A-CS900-3
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Pressure (MPa)

Fig. 7. CO2 adsorption isotherms measured at 273 K under pressure up to 100 kPa (a) and 3.5 MPa (b) for activated carbons produced from CS derived cokes using 3:1 KOH/
coke ratio.

K. Labus et al. / Fuel 118 (2014) 915

400

(b)

-1

(a)

120
100

-1

Volume of CO2 (cm g STP)

140

Adsorbed amount of CO2 (cm g STP)

14

80
60
40
A-CS800-2
A-CS800-3
A-CS800-4

20
0
0

20

40

60

80

100

300

200

100

A-CS800-2
A-CS800-3
A-CS800-4

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Pressure (MPa)

Pressure (kPa)

Fig. 9. CO2 adsorption isotherms measured at 273 K under pressure up to 100 kPa (a) and 3.5 MPa (b) for activated carbons produced from CS800 using different KOH/coke
ratio.

Table 3
CO2 uptakes under different pressures for GACs produced from CS800.
Activated carbon

0.1 MPa
(cm3 g

A-CS800-2
A-CS800-3
A-CS800-4

1.0 MPa

(mmol g

128
132
140

(cm3 g

5.7
5.9
6.2

2.0 MPa

216
238
276

(mmol g

9.6
10.6
12.2

(cm3 g
225
249
295

(mmol g

10.0
11.0
13.1

Table 4
Comparison of carbon dioxide uptake at 273 K and 2 MPa for GACs produced from CS800 and commercial granular activated carbons.
Activated carbon

SBET (m2 g

A-CS800-2
A-CS800-3
A-CS800-4
Picazine
Norit R1 Extra
BPL (Calgon)

1375
1620
1830
1390
1450
1150

VT (cm3 g
0.54
0.67
0.79
0.91
0.47
0.43

application. CO2 uptake of A-CS800-4, prepared using KOH/CS800

ratio of 4:1, amounts at 273 K to 140 cm3 g 1 under atmospheric
pressure and 295 cm3 g 1 under 2.0 MPa, corresponding to 6.2
and 13.1 mmol g 1, respectively. Lower by 1030 % adsorption
capacities are measured for A-CS8002 (KOH/CS800 ratio 2:1),
however, enhanced packing density and somewhat higher
mechanical strength are in favor of activation with a smaller excess
of KOH.
Acknowledgments
The work was performed in the frame of the project The development of coal gasication technology for the efcient production
of fuels and electricity, task 2.3.2, nanced by NCBiR (Poland).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2013.10.042.
References
[1] Aaron D, Tsouris C. Separation of CO2 from ue gas: a review. Sep Sci Technol
2005;48:32148.
[2] Figueroa JD, Fout T, Plasynski S, McIlvried H, Srivastava RD. Advances in CO2
capture technology The US Department of Energys carbon sequestration
program. Int J Greenhouse Gas Control 2008;2:920.

Capacity (mmol g
10.0
11.0
13.1
4.8
11.8
8.8

Literature

29
30
30

[3] DAlessandro DM, Smit B, Long JR. Carbon dioxide capture: prospects for new
materials. Angew Chem Int Ed 2010;49:605882.
[4] Drage TC, Snape CE, Stevens LA, Wood J, Wang J, Cooper AI, et al. Materials
challenges for the development of solid sorbents for post-combustion carbon
capture. J Mater Chem 2012;22:281523.
[5] Plaza MG, Garcia S, Rubiera F, Pis JJ, Pevida C. Post-combustion CO2 capture
with a commercial activated carbon: comparison of different regeneration
strategies. Chem Eng J 2010;163:417.
[6] Siriwardane RV, Shen MS, Fisher EP, Poston JA. Adsorption of CO2 on molecular
sieves and activated carbon. Energy Fuels 2001;15:27984.
[7] Zhang Z, Zhang W, Chen X, Xia Q, Li Z. Adsorption of CO2 on zeolite 13X and
activated carbon with higher surface area. Sep Sci Technol 2010;45:
7109.
[8] Rodriguez-Reinoso F. Porous carbons in gas separation and storage. In:
Loureiro JM, Kartel MT, (editors.). Combined and Hybrid Adsorbents.
Springer, 2006: p. 13344.
[9] Presser V, McDonough J, Yeon S-H, Gogotsi Y. Effect of pore size on carbon
dioxide sorption by carbide derived carbon. Energy Environ Sci
2011;4:305966.
[10] Marsh H, Yan DS, OGrady TN, Wennerberg AN. Formation of active carbons
from cokes using potassium hydroxide. Carbon 1984;22:60311.
[11] Linares-Solano A, Lozano-Castello D, Lillo-Rodenas MA, Cazorla-Amoros D.
Carbon activation by alkaline hydroxides: preparation and reactions, porosity
and performance. In: Radovic LR, editor. Chemistry and Physics of Carbon, vol.
30. New York: CRC Press; 2008. p. 162.
[12] Krl M, Gryglewicz G, Machnikowski J. KOH activation of pitch-derived
carbonaceous materials effect of carbonization degree. Fuel Process Technol
2011;92:15865.
[13] Sevilla M, Fuertes AB. Sustainable porous carbons with a superior performance
for CO2 capture. Energy Environ Sci 2011;4:176571.
[14] Hu X, Radosz M, Cychosz KA, Thommes M. CO2-lling capacity and selectivity
of carbon nanopores: synthesis, texture, and pore-size distribution from
quenched-solid density functional theory (QSDFT). Environ Sci Technol
2011;45:706874.

K. Labus et al. / Fuel 118 (2014) 915

[15] Ramos-Fernandez JM, Martinez-Escandell M, Rodriguez-Reinoso F. Production
of binderless activated carbon monoliths by KOH activation of carbon
mesophase materials. Carbon 2008;46:3846.
[16] Alcaniz-Monge J, Perez-Cadenas M, Lozano-Castello D. Effect of the preoxidation of coals in the preparation of chemically activated carbon pellets.
Energy Fuels 2010;24:338593.
[17] Lozano-Castello D, Cazorla-Amoros D, Linares-Solano A, Quinn DF. Activated
carbon monoliths for methane storage: inuence of binder. Carbon
2002;40:9891002.
[18] Machnikowski J, Kierzek K, Torchaa K. Adsorption capacity enhancement by
activation with CO2 of monolithic adsorbents made of KOH-activated carbon
and polymer-derived binder. Energy Fuels 2012;26:3697702.
[19] Lillo-Rdenas MA, Cazorla-Amors D, Linares-Solano A. Understanding
chemical reactions between carbons and NaOH and KOH: an insight into the
chemical activation mechanism. Carbon 2003;41:26775.
[20] Martinez-Escandell M, Monteiro de Castro M, Molina-Sabio M, RodriguezReinoso F. KOH activation of carbon materials obtained from the pyrolysis of
ethylene tar at different temperatures. Fuel Proc Technol. 2013;106:4027.
[21] Raymundo-Pinero E, Azais P, Cacciaguerra T, Cazorla-Amoros D, LinaresSolano A, Beguin F. KOH and NaOH activation mechanisms of multiwalled
carbon nanotubes with different structural organization. Carbon
2005;43:78695.
[22] Xue R, Shen Z. Formation of graphitepotassium intercalation compounds
during activation with KOH. Carbon 2003;41:18624.

15

[23] Torchaa K, Kierzek K, Machnikowski J. Capacitance behavior of KOH activated

mesocarbon microbeads in different aqueous electrolytes. Electrochim Acta
2012;86:2607.
[24] Kierzek K, Gryglewicz G, Machnikowski J. Morphology of KOH activated
carbons prepared from coal- and pitch-derived precursors. CESEP05. Orlans
2005; Abstracts Book: 104.
[25] Ragan S, Marsh H. Carbonization and liquidcrystal (mesophase)
development. 22. Microstrength and optical textures of cokes from coal
pitch cocarbonizations. Fuel 1981;60:5228.
[26] Stoeckli F, Daguerre E, Guillot A. The development of micropore volumes and
widths during physical activation of various precursors. Carbon
1999;37:20757.
[27] Neimark AV, Lin Y, Ravikovitch PI, Thommes M. Quenched solid density
functional theory and pore size analysis of micro-mesoporous carbons. Carbon
2009;47:161728.
[28] Raymundo-Piero E, Kierzek K, Machnikowski J, Bguin F. Relationship
between the nanoporous texture of activated carbons and their capacitance
properties in different electrolytes. Carbon 2006;44:2498507.
[29] Drage TC, Blackman JM, Previda C, Snape TC. Evaluation of activated carbon
adsorbents for CO2 capture in gasication. Energy Fuels 2009;23:27906.
[30] Himeno S, Komatsu T, Fujita S. High-pressure adsorption equilibria of methane
and carbon dioxide on several activated carbons. J Chem Eng Data
2005;50:36976.