Carbon Vol. 34, No. 4, pp. 471-479.

1996
Pergamon Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0008.6223/96 $15.00 + 0.00

0008-6223( 95)00204-9

THE PREPARATION OF ACTIVE CARBONS FROM COAL BY

CHEMICAL AND PHYSICAL ACTIVATION

A. AHMADPOUR, and D. D. Do,*

Department of Chemical Engineering, University of Queensland, Brisbane, Qld 4072, Australia

(Receiaed 17 March 1995; accepted in revised firm 10 October 1995)

Abstract-A series of activated carbons was prepared from bituminous coal by chemical activation with
potassium hydroxide and zinc chloride and also by physical activation with carbon dioxide. The effect
of process variables such as carbonization time, temperature, particle size, chemical agents, method of
mixing and impregnation ratio in the chemical activation process was studied in order to optimize those
preparation parameters. Partial gasification of the high surface area carbon obtained by zinc chloride
activation in CO, with different exposure times shows some improvement in adsorption. The physical
properties of the chemically activated carbon was also compared with those obtained purely by physical
activation. The most important parameter in chemical activation of coal with both of the chemical agents
was found to be impregnation ratio. Carbonization temperature is another variable which had a high
effect on pore volume evolution. While increasing the carbonization temperature enhances surface area
and pore volumes of KOH-activated carbon, it destroys carbon structure in the ZnCI, carbon series.
Under the experimental conditions investigated, the optimum conditions for high surface area carbons
with KOH and ZnCl, activation are identified. Copyright 0 1996 Elsevier Science Ltd

Key Words-Coal, chemical activation, physical activation, activated carbon, KOH, ZnCl,.

1. INTRODUCTION such as KOH, K,CO,, NaOH, Na,CO,, AlCl,,

ZnCl,, MgCl, and H,PO,.
Activated carbon which is a versatile adsorbent
Physical activation of coal and lignocellulosic
because of its good adsorption properties, can be
materials has been extensively studied in the past and
produced from a variety of raw materials. Among
chemical activation has been a subject of investigation
them, coal is the most commonly used precursor due
by a number of workers [l-22]. Some authors
to its low cost and large supply, and also activated
studied the combination of these two methods
carbon prepared from coal is superior to those
[ 10,14,17] to obtain high surface area adsorbents.
derived from lignocellulosic materials in terms of
In the case of chemical activation, the effects of KOH
mechanical properties. Basically, there are two
[4,7,13,23] and ZnCl, [1,2,5,6,8,10,11,14-181 on
different processes for the preparation of active
carbonization of coal and other precursors have been
carbon: physical and chemical activation. Physical
of particular interest, and zinc chloride in particular
activation involves carbonization of a carbonaceous
is the widely used chemical agent in the preparation
precursor followed by activation of the resulting char
of activated carbon [14]. However, the effects of
in the presence of some activating agents such as
these two chemicals on a single precursor have not
carbon dioxide or steam. Chemical activation, on the
been thoroughly investigated in the literature.
other hand, is a single step method of preparation of
The objective of the present work was to study the
active carbon. This step being the carbonization of
effect of different parameters on the preparation of
the precursor in the presence of chemical agents. In
activated carbon from bituminous coal by carboniza-
physical activation, elimination of a large amount of
tion with KOH and ZnCl,. Subsequent activation of
internal carbon mass is necessary to obtain a well
some of the resulting activated carbon with carbon
developed carbon structure, whereas in the chemical
dioxide was also studied. These results were then
activation process all the chemical agents used are
compared with those obtained by COz physical acti-
dehydrating agents that influence pyrolytic decompo-
vation of the same source of raw material. In order
sition and inhibit formation of tar, thus enhancing
to study the influence of the mineral matter present
the yield of carbon [ 11. The temperatures used in
in the coal on the pore evolution during chemical
chemical activation are also lower than that used in
activation, some samples were treated with acid prior
the physical activation process, and therefore the
to impregnation with chemical agents.
development of a porous structure is better in the case
of the chemical process. The chemical agents used in
the chemical process are normally alkali and alkaline 2. EXPERIMENTAL
earth metal containing substances and some acids
Bituminous coal with medium ash content from
Ipswich, Queensland, Australia was used as a precur-
sor in the present study. According to ASTM stan-
*To whom all correspondence should be addressed. dards the coal is a high volatile A-bituminous coal,
471
472 A. AHMADPOUR and D. D. Do

its proximate and ultimate analysis being given in (b) “impregnation” method and (c) “acid washed
Table 1. The precursor was ground and sieved to two (AW) + impregnation” method.
different particle sizes 212-250 and 500-600 pm. In The resulting chemical loaded samples were heated
the physical activation process, about 15 g of the coal (SC/min) to the final carbonization temperature in
sample (particle size of 212-250 pm) was subjected a nitrogen flow of 150 cm3/min STP. Samples were
to pyrolysis in a vertical quartz reactor (ID = 25 mm) held at the final temperature for different carboniza-
prior to activation. Samples were heated (3”C/min) tion times of 1,2 or 3 h before cooling under nitrogen.
to the final temperature of 750°C in a nitrogen flow An inert atmosphere during the carbonization has
of 100 cm3/min STP and held for 2 h to ensure been recommended [S]. The products were washed
removal of all the volatile matter and tarry materials. sequentially with 0.5N HCl, hot water and finally
A weight loss of about 40% was observed. About 5 g cold distilled water to remove residual organic and
of the resulting char was then located in another mineral matters, then dried at 110°C. All weight
vertical quartz reactor and was heated at a rate of losses were calculated on a chemical free basis. One
lS”C/min to 800 or 900°C in a flow of nitrogen of the activated carbon samples prepared from
(100 cm3/min STP). After the reaction temperature ZnCl, activated was then subjected to partial gasifi-
was reached, nitrogen was replaced with carbon cation in CO, at 800°C for different exposure times
dioxide (150 cm3/min STP) for different exposure to study the effect of activation on pore evolution of
times to obtain activated carbon of different degree this series of activated carbon. In all runs of chemical
of burn-off. The detailed procedure and diagram of activation, heating rate and nitrogen flow were kept
the activation rig is available elsewhere [20]. Weight constant, and in all runs (physical and chemical),
losses in this series of experiments were calculated on gases (N2 and CO,) were passed through a copper
the dried char basis. turning bed at 480°C and a molecular sieve bed to
Chemical activation was performed with KOH or reruove the traces of oxygen and water content in the
ZnCl,. Three different methods of preparation were gases before entering the reactor.
chosen: Weight loss and chemical recovery (CR) which are
the indicators of the process efficiency in the chemical
(a) Dried coal (10 g) was physically mixed with
activation process were calculated. Weight loss was
ground KOH or ZnCl, and placed in a hori-
calculated based on the chemical-free coal precursor,
zontal quartz reactor.
and chemical recovery was estimated according to
(b) Dried coal (10 g) was well mixed with a concen-
trated solution of KOH or ZnCl, with the c51:
chemical ratio range from 25 to 200% for about (wt of product prior to washing) -
5 min and then the resulting homogeneous (wt of product after washing)
slurry was dried at 110°C for about 14 h. CR= x 100
(wt of chemical agent used)
(c) Dried coal (10 g) was soaked in a 1N solution
of HCl:H,SO, (1:1) for 2 days in order to Adsorption of N, at - 196°C and benzene at 30°C
reduce the ash content of the coal, then washed were performed to evaluate the adsorptive properties
with distilled water and dried at 110°C for of the activated carbon. The adsorption isotherms
about 14 h. The dried sample was then mixed were determined in a conventional high accuracy
with a solution of chemical agents according to volumetric adsorption rig. The values of BET surface
method (b). area and micropore volume are those obtained from
adsorption of N, at - 196°C using Micromeritics,
It has been found that drying of the mixture of ASAP 2000. Also, micropore volumes have been
coal and chemicals in the oven at 110°C prior to calculated in another way by using the low pressure
carbonization dehydrates the sample and provides a isotherm data of benzene applied to the
uniform reaction [ 231. The above methods of mixing DubininRadushkevich (DR) equation [ 241. Benzene
will be referred hereafter as: (a) “physical” method, saturation adsorption capacities and pore half-width
in carbons are calculated from the fitting of experi-
Table 1. Proximate and ultimate analysis of bituminous coal mental adsorption isotherms to the thermal adsorp-
tion equation of Dubinin-Stoeckli (DS) [24] for
Proximate
non-homogeneous microporous activated carbon
Moisture (ARB) 10.0%
Volatile matter (ADB)b 39.0% using a non-linear optimization technique.
Fixed carbon (ADB) 42.0%
Ash (ADB) 11.5%
3. RESULTS AND DISCUSSION
Total sulfur (ADB) 0.65%
Ultimate (D/W) We first discuss the results obtained by chemical
Carbon 80.18% activation and then those by physical activation.
Hydrogen 6.04%
Nitrogen 1.51% 3.1 Chemicul activation
Oxygen 11.63%
Sulfur 0.64%
Chemical activation of carbonaceous materials has
been the subject of considerable interest in the past
a As received basis.” Air dried basis.” Dried ash free basis. because activated carbon with a well developed
 The preparation of active carbons from coal by chemical and physical activation 473

porosity can be produced by this process in a single mum yield of carbon) for the ZnCl, series is observed
operation [ 141. Also, it has been found [l,S] that at 500°C while for the KOH series it occurred between
the effect of some chemicals on carbon precursor is 600 and 700°C. Surface area and micropore volume
to yield more char and less tar than the untreated continuously increase with carbonization temper-
sample. In the present study a number of experiments ature for the KOH series, but for the ZnCI, series
were carried out to compare the physical characteris- the trend is a decrease with temperature, and this
tics of activated carbons obtained by chemical activa- rate of decline is not as fast as the rate of increase in
tion of coal with KOH and ZnCl,. The effects of the KOH series. Caturla et al. [ 141 in their study of
different parameters such as carbonization time activation of peach stones with ZnCl, observed a
(AtCAR& carbonization temperature (T), chemical decrease in BET area with temperature. In our
ratio (R), coal particle size (d), method of mixing and ZnCl, activated carbon series, the increase in temper-
also mechanism of the reactions and partial gasifica- ature from 500 to 800°C may induce a shrinkage in
tion of chemically activated carbon are discussed. the carbon structure, resulting in a reduction in
3.1.1 Carbonization time The variations in porosity. A temperature of 500°C for ZnCl, activation
weight loss, surface area, micropore volume and has also been recommended by other workers
benzene adsorption capacity for KOH and ZnCl, [ 5,8,16] in carbonization of precursors with different
activated carbons versus the carbonization time are conditions. Chemical ratio (KOH/coal or
shown in Fig. 1. For the KOH series (Fig. l(a-d)), ZnCl,/coal) of 100% used in studying the effect of
the particle size range is 212-250 pm, temperature of temperature is found to be the optimum ratio for
carbonization is 700°C and chemical ratio of KOH both series of activated carbons, and this will be
to coal is 100% (mass basis). For the ZnCl, series discussed in detail in the next section. Chemical
(Fig. l(e-h)), the parameters are the same as those recovery (CR) was observed to decrease at higher
used in the KOH series except the temperature of temperatures, which is attributed to chemical evapo-
carbonization is 500°C. These temperature were ration. In the KOH series, the chemical recovery
found to be the optimum temperatures in chemical decreases from 84 to 74% in the temperature range
activation with KOH and ZnCl,. This will be dis- of 500~8OO”C, while it drops significantly from 45 to
cussed in Section 3.1.2. As seen in the figure, while 1.5% in the ZnCl, series. It should be noted that
carbonization time does not have much effect on the during the carbonization of the ZnCl, activated
weight loss in the KOH series, it increases weight carbon series an increase in back pressure of gases in
loss of the carbons in the ZnCl, carbon series. On the reactor was observed at about 300°C which is
the other hand, by increasing the carbonization time, consistent with the finding of Bodily et al. [25] that,
properties like BET surface area, pore volume and due to the presence of ZnCl,, the hydrogen evolution
benzene capacity of carbons in the KOH series began below 200°C and peaked at about 350°C.
increase for both impregnation and physical mixing 3.1.3 Chemical ratio Figure 3 shows the effect
methods. In the ZnCl, series, the carbonization time of chemical ratio on the physical properties of the
has a negative effect on the above parameters. Also, chemically activated carbons. It is seen that, by
not presented here, the chemical recovery decreases adding chemical agents to the coal (up to 25%),
with the time of activation. weight loss is decreased as a result of the inhibition
As seen in Fig. 1, it seems the physical method of of tar production by these chemicals, hence enhancing
mixing enhances the weight loss of carbons in the carbon yield. With increasing KOH and ZnCl, to
ZnCl, series to a higher extent than the other two coal ratio further from 25 to 75%, the weight loss
methods. Although the methods of physical mixing increases and beyond 75% chemical ratio the weight
and AW + impregnation increase carbon weight loss loss is again reduced. The dispersion of the weight
in the KOH series, it causes reduction on the other loss values after 75% could be due to experimental
physical properties of the resulting carbons. In the error but the general trend is in reducing these values.
ZnCl, series the same behaviour could be observed, A similar trend has been reported by Ruiz Bevia et al.
but the AW + impregnation method is superior to [S] in their study of carbonization of almond shells
the physical mixing method, and these two methods with ZnCl,. The behaviour in the weight loss between
yield inferior activated carbon compared to the 25 and 75% ratio is due to the larger evolution of
impregnation method. So, it is concluded that in volatiles. As discussed by Rodriguez-Reinoso and
these two activated carbon series the impregnation Molina-Sabio [ 171 in carbonization of lignocellulosic
method can produce products with well developed materials with zinc chloride, by increasing the chemi-
porosity and in the KOH series prolonged time of cal ratio the mechanism of pore evolution is changed
carbonization is recommended, although it has a and the dependence of the pore evolution on the
negative effect on the chemical agent recovery. chemical ratio can be divided into three different
3.1.2 Carbonization temperature The effects of zones. In the first zone in which R < 50% (in our
temperature on carbonization of both series of acti- case), there is a predominance of microporosity cre-
vated carbons are presented in Fig. 2. In the temper- ation, as reflected by the sharp rise in the micropore
ature range studied in this paper (500~8OO”C), the volume versus chemical ratio (Fig. 3), and for the
behaviour of these two activated carbon series are range 50% < R < 100% there is a competition
totally different. The minimum weight loss (or maxi- between the microporosity creation and the widening
474 A. AHMADPCXJK
and D. D. Do

60 120 160 60 120 166

lime (min) Time (min)

11001 1100

p 1000
5 r
e 900 2 900
la z
8 900 t 800

s 700 s 700
111
600 t; 600
m
600 500
60 120 180 60 120 180

Time (min) Time (min)

0.5

g 0.4 Ei
g 0.4

2E 0.3 s 0.3
5! v
E 0.2 Et 0.2
g 8
.K 0.1 .o
2 0.1
B H
0 0
60 120 180 60 120 180

lime (min) lime (min)

I
g
g 4.8
L
f 4.2

tf 3.8 % 3.8
t t
$ 3.4 3 3.4

$
dl 3 3
60 120 $89 60 120 180

lime (min) Time (min)

Fig. 1. Effect of carbonization time on physical characteristics of active carbons obtained by KOH and ZnCl, activation.
(a-d) KOH series carbon (d = 212-250 itm, T = 7Oo’C, R = 100%); (e-h) ZnCI, series carbon (d = 212-250 pm, 7’ =
5OO’C, R = 100%).

of microporosity into the range of mesoporosity.
Enhancing of surface area is the result of mostly
mesopore creation in this range, and for this reason
the pore evolution is gradual (see the plots of BET
area and micropore volume of Fig. 3). Benzene iso-
therms (type I) of these carbons (not presented) with
chemical ratio less than 100% show that the resulting
carbons are mainly microporous. In the third zone
where the chemical ratio (R) is greater than lOO%, a
larger widening of porosity, mainly in mesopore
range, increases the surface area and pore volume to
some extent. In the case of KOH. although the same
 The preparation of active carbons from coal by chemical and physical activation 415

40

35

30

25

20

I5

IO

0 0

.
-iTi
” 1200
I ma

‘1. /‘O oE
- 1000

,
800 ti

600

J
7
/
‘\. Y
2
lu

z
cd
800

600

I
400
/ 5 400

200
/ v,

&
m
200

0 ___ _I_- 0
- -
i ,M 0.55
m
E 040
Cc i ,“;;
0
- 0.35
y 0.40
0.30 ; 0 35
ti
2 a.25 zl 0.30
-z z3 025
> 020
k 0.20

0 015

0 KOH 1 g 0.10
0 ZnCI, b 005
i 5 000
4iic) 500 6ao 700 ROCI 900 SC! 100 150 200

Temperature, (‘C)
Chemical ratio, (%)

Fig. 3. Effect of chemical ratio on physical properties of

Fig. 2. Effect of temperature on physical properties of chemi-
chemically activated carbons under the conditions: d =
cally activated carbons under the conditions: d =
212-250 pm, AtcARs = 60 min, impregnation method; T =
212-250 pm, dtCARB = 60 min, R = 100% and impregnation
500°C in ZnC1, series and T = 700°C in KOH series.
method.

trend in the surface area and pore volume can be contribution in this series is almost constant. The
observed, the mechanism of the activation is different. mechanism of these processes will be discussed later.
To clarify this point, mesopore volumes and pore It is concluded that an impregnation ratio of 100%
half-width of these carbons have been plotted versus can be taken as the optimum value for both series,
chemical ratio in Fig. 4. The mesopore volumes are considering the chemical agent recovery, microporos-
calculated by subtracting the micropore volumes ity development, the process economics and the yield
(deduced from the DR equation) from the amount of carbon.
adsorbed at P/P,,= 0.95of the N, isotherm at 77 K 3.1.4 Particle size Table 2 and Table 3 are the
and pore half-widths are obtained using the DS results of experiments for 500-600 pm coal particles
equation. This figure shows that the high ratio of activated with KOH and ZnCl,, respectively. From
ZnCl, increases mesoporosity in the resulting carbon comparison of Table 2 with Figs. l-3 it can be seen
while KOH creates more micropores, and mesopore that, in most of the conditions, coal with a larger
 A. AHMADPOUR and D. D. Do

:: 5i 1100 , “_ ,‘ , _,_‘_
_I ‘, ~‘, : t: -, : c 1 ‘1, rs 152 y,-,
__ 2x

Chemical ratio, (7) Chernlcal ratlo. (“_)

Fig. 4. Effect of chemical ratio on mesopore volume and pore half-width of chemically activated carbons under the conditions:
d = 212_250pm, dt cARB = 60 min, impregnation method; 7’ = 500°C in ZnCl, series and T = 700°C in KOH series.

Table 2. Physical characteristics of carbons prepared by KOH activation of coal with a particle size of 500.-600 pm

Method R (wt%) T(-Cl f (min) Weight loss (%) SBET (m’/g) vN2 (cm3!g) v,, (cm3!g)

Impregnation 1:l 700 60 27 602 0.281 0.318

Impregnation 1:l 700 120 28 612 0.293 0.332
Impregnation 1:l 800 60 41 799 0.359 0.422
Impregnation 1:2 700 60 32 925 0.424 0.43 1
Physical 1:l 700 60 32.5 343 0.148 0.180
AW + imp. 1:I 700 60 22 602 0.274 0.290

AW + imp., acid washed and impregnation method; R, chemical ratio; V,,. micropore volume from N, Isotherm;
V DR, micropore volume from benzene isotherm using DR equation.

Table 3. Physical characteristics of carbons prepared by ZnCl, activation of coal with a particle size of 500-600 pm

Method R (wt%) T (“C) t (min) Weight loss (%) SSET (m’ig) V,, (cm3ig) v,, (cm3/g)
_
Impregnation 1:0.75 500 60 21 728 0.317 0.375
Impregnation 1:l 500 60 31 810 0.339 0.383
Impregnation 1:1.2 500 80 26 865 0.369 0.388
Physical 1:l 500 60 22 779 0.333 0.348
AW + imp. 1:l 500 60 28 864 0.362 0.381

AW + imp., acid washed and impregnation method; R, chemical ratio; VNz, micropore volume from N, isotherm;
V DRImicropore volume from benzene isotherm using DR equation.

particle size shows a small increase in weight loss N2 adsorbed at P/P, = 0.1 at 77K (V,,) are also
and in all cases reductions on surface area and compared. In all cases VDR values are greater than
micropore volume of the resulting carbons are those of V,, and this could be due to the activated
observed. This can be explained by the fact that for diffusion effect of nitrogen at low temperature.
larger particles, less wall surface area is exposed to 3.1.5 Method of mixing As discussed in the
the action of chemical agent and as explained before previous sections, the results of the present study
one of the most important effects of the chemical show the impregnation method has advantages over
agent is to reduce tar formation and enhance the the physical mixing method and this is due to the
yield of carbon and porosity development. Therefore, better distribution of chemical agents into the carbo-
for smaller particle size, weight loss is higher and naceous particle mass. The same finding has been
surface area and pore volume are more developed. reported by Ibarra et al. [ 151 in studying chemical
Kirubakaran et al. [16] in studying the effect of activation of coal with ZnCl,. This is less pronounced
H,PO, and ZnCl, on coconut shell in static and in the case of KOH due to its different reaction
fluidized beds also found that small particles show mechanism with coal. Acid pre-treatment of the coal
better activation in the case of ZnCl, using a static shows some advantages in some cases, but for the
bed. In Table 2 and 3 the micropore volumes deduced coal with low ash content, like the one used in this
from the DR equation (V,,) using benzene adsorp- study, the effect is negligible.
tion isotherm data with those from the amount of After carbonization with chemicals the products
 The preparation of active carbons from coal by chemical and physical activation 477

are normally subjected to washing with acid and
water. Washing with acid removes all the alkali and
alkaline earth metals, and washing with water
removes all basic and water soluble components in
the carbon. It is known [4,17] that removing the
chemicals left in the carbonized sample by washing
will yield porosity in the carbon structure and the
distribution of these chemicals in the precursor prior
to carbonization govern the pore size distribution in
the final products. To test the above finding, adsorp-
tion of nitrogen at -196°C was performed on two
activated carbon samples with low and high chemical
ratio in both the KOH and ZnCl, series before and
after washing. The results presented in Table 4 clearly
show that the porosity created in the carbon samples
is mostly occupied by the chemicals in the structure.
Low surface areas of the unwashed carbons are
because of potassium and zinc salts left in the carbon,
blocking pore entrances to the nitrogen molecules.
Also seen in the Table 4 is that for high chemical
ratio the effect of washing is more pronounced.
3.1.6 Mechanisms of the reactions Although a
lot of work has been done in the area of chemical
activation, the mechanisms of the process are still not
well established [7,14]. Kadlec et al. [2] observed
that the shapes of the pores in activated carbons were
different when obtained by chemical and physical
activation methods. The pores were usually bottle
shaped in the case of chemical activation and cone
shaped in physical activation. They concluded that
the bottle shaped pores in the former should be
attributed to the fact that during the course of
chemical activation at temperatures around 500°C
the carbonized carbonaceous material is in a plastic
state. The gases released on thermal decomposition
create voids in the plastic matter from which they
escape through small passages and this may be the
cause of the bottle shaped pores.
In respect to the effect of ZnCl, on carbonization
of carbonaceous materials, some mechanisms have
been proposed. It is generally believed that ZnCl,
acts as a dehydration agent [ 193. Caturla et al. [ 141
and Rodriguez-Reinoso and Molina-Sabio [ 171
pointed out the impregnation with ZnCl, first results
in dehydration of the cellulosic material and on
carbonization produces dehydration that results in
charring and aromatization of the carbon skeleton
and creation of the pore structure. They also deduced
that the porosity created in the carbon structure is
the result of the ZnCl, left in the particles after
removal by intense washing. Using a high concen-
tration of zinc chloride and impregnation followed
by drying before carbonization they concluded that
some portion of ZnCI, in the external part of the
particle widens the porosity by a localized decomposi-
tion of the organic matter and therefore creating
meso and macroporosity. Ibarra et al. [ 151 in analysis
of hydrogen evolved from the pyrolysis of impreg-
nated coals concluded that ZnCl, promotes dehydro-
genation reactions of coal and hydrogen is evolved
below 400°C in the presence of ZnCl,. Thus, ZnCl,
seems to cause a specific dehydrogenation of coal
during the early stages of pyrolysis and prior to the
release of tar.
Marsh et al. [4] in studying the effect of KOH on
different cokes stated that the presence of oxygen in
the alkali results in the removal of cross-linking and
stabilizing of carbon atoms in crystallites. They con-
cluded that potassium metal liberated at the reaction
temperatures may intercalate and force apart the
separate lamellae of the crystallite. Removal of these
potassium salts (by washing) and carbon atoms (by
activation reaction) from the internal volume of the
carbon creates the microporosity in the structure.
Ehrburger et al. [ 73 in studying the physico-chemical
reactions during the carbonization of coals with
alkaline salts concluded that there are three major
reactions occurring between the hydroxide and the
coal. They are: formation of carbonate, evolution of
CO, and formation of CO. They also found that in
the reaction of coal with carbonate some surface salt
complexes are formed which act as active sites in
gasification and hence their presence enhances the
activation process. Recently, Otowa et al. [22,26]
studied the activation mechanism of high surface area
carbon, MAXSORB, produced by KOH activation.
While their results confirm the above mechanisms of
KOH activation, they have found that considerable
amounts of carbonate and hydrogen and only small
amounts of CO, are formed. Also, they have con-
cluded that high temperature and high KOH/carbon
ratio produce large pores in the carbon structure.
Fig. 4, that clarifies the action of these two chemicals
on pore formation in the coal, clearly shows the
difference in the mechanism of KOH and ZnCl,. The
pore width and mesopore volume increases steadily
with increasing ZnCl, ratio while it is almost constant
in the case of KOH. The results presented in this

Table 4. Variation in properties of carbons prepared by KOH and ZnCl, activation before and after intensive washing

Chemical agent R (wt%) Treatment

KOH 25 Unwashed 6.2 0.001

25 Washed 188 0.077 0.040
100 Unwashed 2.1 0.0005
100 Washed 770 0.338 0.334
ZnCI, 2s Unwashed 117 0.048
25 Washed 216 0.095 0.082
100 Unwashed 70 0.026
100 Washed 1062 0.456 0.456
478 A. AHMAUPOUR
and D. D. Do

figure confirm the above mechanism of KOH activa- Table 6. Properties of activated carbons prepared by physi-
cal activation of coal at 800 and 900°C
tion that the potassium metal is responsible for the
pore creation in the carbon particle and in the case Temperature t Burn-off S,,, V,, V
of ZnCl, the porosity could be due to the zinc (‘C) (h) (%b) W/s) (cd/g) (cm%9
chloride left in the matrix, and at high
800 Char 10 0.002
ZnClJcarbon ratio creation of a large portion of
6 12 299 0.134 0.148
meso- and macropore is due to the external surface 10 16 437 0.196 0.205
decomposition. 31 41 705 0.308 0.285
3.1.7 Gasijication with CO, One of the acti- 60 64 754 0.316 0.310
vated carbon samples obtained by zinc chloride acti- 900 3 32 42X 0.186 0.202
8 57 751 0.310 0.312
vation was used to study the effect of subsequent 15 72 590 0.224 0.241
gasification on its pore structure. Table 5 shows the 20 80 149 0.055 0.095
physical properties of the starting sample as well as
the resulting “further physical activated” carbons. It
should be noted that burn-off of physically activated exposed to the reaction with carbon dioxide and
carbon is based on the starting chemically activated therefore more pore widening occurred. It should be
carbon. As seen in the table, the carbon burn-off noted that the carbon selected for the ZnCl, series
varies linearly with the time of activation as is the was obtained by using chemical ratio of 100% and
case for the physical activation process. Surface area as mentioned before the effect of chemical ratio is
and micropore volume decrease for low burn-off very important in the porosity development of the
carbon and then increase steadily with the burn-off carbon. This pointed to the fact that this carbon had
up to a value of 43% studied in this paper. The initial a relatively well developed pore structure, and after
decrease in surface area and pore volume compared exposing to CO,, widening of micropores developed
to the starting sample is due to the gasification to mesopores rather than creation of micropores are
temperature, which is higher than the carbonization more likely to happen. Table 6 also shows the evolu-
temperature used in the chemical activation step and tion of surface area and micropore volume for purely
this produces densification of carbon through a physically activated carbon. Activated carbons pre-
secondary carbonization process parallel to the gas- pared at both temperatures have a continuous
ification reactions [ 141. increase in porosity up to 50-60% of burn-off after
which destruction of the internal carbon structure
3.2 Physical activation causes reduction in the porosity and this is more
Physical activation of coal was carried out at two severe for carbons produced at higher temperature
temperatures of 800 and 900°C in a CO, atmosphere. (900°C). The results of benzene adsorption isotherms
These two temperatures and activation reagent were of the physically activated carbons indicate that
selected based on the previous experiments in our carbons with burn-off less than 30% are mainly
laboratory with coals and lignocellulosic materials. microporous and after that mesoporosity increases
The results of physical activation of coal are presented in the carbon structure, and for carbons with burn-
in Table 6. Comparing the rates of carbon burn-off off higher than 60% mesopores are more developed
at these two temperatures with those of chemically and change to macropores which has the negative
and subsequent physically activated sample in Table 5 effect on micropore surface area and micropore
shows that the rate of the chemically activated carbon volume.
physically gasified at 800°C (Table 5) falls between
the purely physical activation rates at 900 and 800°C
4. CONCLUSIONS
(Table 6). The low rate suggests that the microporos-
ity is more developed at 800°C compared to that at Chemical and physical activation processes were
9OO”C, and in the case of partial gasification of carbon used to prepare activated carbon from coal. Chemical
in the ZnCl, series, since the porosity in that carbon activation with two commonly used chemicals, KOH
has already been well developed, during the physical and ZnC12, produced activated carbon having well
activation more carbon atoms in the structure are developed porosities compared to those observed
from physical activation. The effects of different
parameters during chemical activation were investi-
Table 5. Partial gasification of chemically activated carbon
gated. Under the experimental conditions investi-
with CO, at 800°C
gated, the optimum values of the parameters for the
Method of Time Burn-off VN2 production of high surface area activated carbon by
activation $+;,
(h) (%I (cm3/g) chemical activation are: R = lOO%, T = 7OO”C,
Chemical 1062 0.456 &ARB = 2 h for 212-250 itrn particles activated with
Physical 4.5 12 763 0.331 KOH, and R = lOO%, T = 5OO”C, At,,,, = 1 h for
8.5 20 791 0.343 the same particles activated with ZnCl,. In those
10 23 897 0.391 runs, KOH and ZnCl, were impregnated into the
14.5 30 945 0.410
coal structure prior to the activation. Partial gasifica-
20.5 43 1203 0.508
tion of the resulting activated carbon with carbon
 The preparation of active carbons from coal by chemical and physical activation
dioxide shows some improvement in the adsorption
properties. Physical activation of coal char with
CO2 at two temperatures (800 and 900°C) showed
that a temperature of 800°C is more effective in the
development of the pore structure of the coal char.
Comparing the results of experiments of physical and
chemical activation indicates that the chemical activa-
tion is more flexible in the preparation of activated
carbons with desirable pore size distribution.
Acknowledgement~support from the Australian Research
Council is gratefully acknowledged.
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