Carbon Vol. 34, No. 1, pp.

77-82, 1996
Pergamon Copyright 0 1995 Elsevier Science Ltd
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000%6223(95)00137-9

PREPARATION AND CHARACTERIZATION OF ACTIVATED

CARBON FROM A LOW RANK COAL

TANZIL HAIDER USMANI, TAMOOR WAHAB AHMED, S. ZAFAR AHMED

and A. H. K. YOUS~FZAI
Industrial Chemicals Research Centre, PCSIR Laboratories Complex, Karachi-75280, Pakistan

(Received 19 May 1994; accepted in revised form 25 Ju/y 1995)

Abstract-Powdered activated carbon has been prepared from lignitic coal of Lakhra (Pakistan) by a
chemical activation method using ZnCl, as an activating agent. Different process variables have been
established after a series of experiments and an impregnation ratio of 1: 2, an activation temperature of
650°C and a duration of 1 hour have been found to be appropriate for its preparation. It has been found
that the char is obtained in high yield with iodine and methylene blue numbers of 990 and 205,
respectively. Different parameters based on adsorption of benzene at 293 K under reduced pressure have
been calculated using DR equation with micropore volume W,=O.46 cm3/g, an average pore width L=
0.98 nm and a microporous surface area S,, = 942 m2/g. The nonporous surface area S, calculated by the
t/F method is 142 m’/g. FTIR spectra of this sample show the presence of acidic functional carboxylic
groups developed on its surface after activation. Their predominance is further confirmed by neutralization
with different alkalis.

Key Words-Lignitic coal, chemical activation, activating conditions, ZnCl,, adsorption, DR equation,
activated carbon.

1. INTRODUCTION paper deals with the coal deposits of Lakhra situated

on the western side of river Indus in the province of
The total estimated coal deposits of Pakistan are
Sindh. According to a recent survey, these deposits
23 345million (m) metric tons, out of which 11 166 m
represent 2464 m metric tons [ 11. The coal is gen-
metric tons have so far been inferred[l]. The coals
erally friable and largely reduced to fines during the
of Pakistan range from lignitic to sub-bituminous
course of handling, storage and transportation. The
rank and are chemically immature, non-coking and
study has been carried out on the preparation of
relatively rich in mineral matter and sulphur ranging
powdered activated carbon from this coal by chemical
from 8 to 36 and 2to 7%, respectively[2]. Most
activation. Moreover, appropriate working condi-
deposits are also relatively low in calorific content
tions-activating agent, impregnation ratio, activa-
(3000-6000 kcal/kg), thus they fall into the low rank
tion temperature and time-have been established in
category. Due to the low calorific value of indigenous
relation to different physical and chemical character-
coal, at present it is only being used as fuel in brick
istics of the products.
kilns. It is thus evident that extensive research and
development input is required for exploiting appro-
priate industrial uses of these coals. 2. EXPERIMENTAL
The literature is replete with references to util- 2.1 Sample preparation
ization of low rank coals for the production of The coal sample used was obtained from M/S
powdered and granular activated carbons. Durie and Pakistan Mineral Development Corporation. It was
Schafer[3] prepared activated carbon in high yield pulverised in an SS ball mill to a particle size of
by activation of brown coal with a potassium salt. 0.09-0.125 mm and then oxidised in air at 170°C for
Murti [ 41 prepared granular activated carbon by acid 2 hours. The detailed chemical analysis of the original
leaching, reconstitution and, thereafter, physical and oxidised coal samples was carried out using
activation of low grade fat coal. Lukyanova and standard methods [ lo].
Mazina [ 51 obtained activated carbon suitable for
vapour phase adsorption by chemical activation of 2.2 Product preparation
brown coal with a zinc salt. Nining et a!.[61 used One kilogram of the oxidised coal sample (W, in
chlorides of different metals for activation of each set of experiments) was mixed with 0.5, 1.0, 1.5
Indonesian coal. and 2.0 kg (IV’) of ZnCl,, NaCl, KC1 and CaCl,,
Systematic research and development work has predissolved in 1.4 1 of distilled water containing
already been carried out by the present authors for 450 g of HCl to facilitate the dissolution of these salts
the preparation of activated carbon from raw materi- and was dried at 110°C for 24 hours. The dried mass
als of vegetable origin [ 7-91. The study has now been in each case was then carbonized in a stainless steel
extended to Pakistani coals on which no work has vessel at 750°C for 2 hours in an inert atmosphere of
yet been carried out in this particular aspect, and this Nz and weighed (W,). The solids were then refluxed
cm 34: I-0 77
78 T. H. USMANI et al

with 0.1 N HCl for 4 hours, filtered and washed Table 1. Proximate analysis and sulphur contents of Lakhra
coal
initially with tap water and finally with distilled
water, to eliminate the acid and the chloride ions. Constituent analysed (%) Original Oxldised
The solids were finally dried to a constant weight (W,).
Moisture 10.44 2.68
2.3 Product characterization Ash 8.43 10.69
The loss in weight (LW), the corresponding yield Volatile matter 39.99 25.7 I
Fixed carbon 35.14 51.40
(loo-LW) of the various products and the reagent Sulphur 7.00 9.52
recovery (RR) of each of the activating agents [ 111
were calculated by
seen here that on mild oxidation of coal at 170°C
w,-w,
LW=p x 100 (1) undesirable sulphur contents have also increased
w,
from 7 to 9.5%, along with significant loss of vola-

RR=-
e-w, x 100
tile matter.
(2)
w, The data in Table 2 indicate the effect of ZnCl,,
NaCl, KC1 and CaCl, used as activating agents on
The ash content and pore space of these samples
different physical and chemical parameters of the
were determined [ 121. The conventional methods
finished products and are denoted by Z, S, P and C,
based on adsorption of iodine and methylene blue
respectively. As for the reagent recovery and yield,
were used for the liquid phase characterization of
these increased with the increase in impregnation
these products[ 131. The surface area of pores greater
ratio in all cases except CaCl,. However, highest
than 10 and 15 A were determined from the adsorp-
yield with lowest reagent recovery is obtained in
tion data[ 14,151.
ZnCl,, which may be due to its lower boiling point
All the adsorption measurements were carried out
and higher vaporization effect. It may be seen in
with benzene at 298 K on a conventional gravimetric
Fig. 1 that the degree of higher burnoff in ZnCl,
McBain apparatus at relative vapour pressures of
activated chars ranges from 13 to 59% and decreases
p/p0 < 0.05-o. 1[ 161. The charcoal sample was origi-
with the increase in impregnation ratio of activating
nally outgassed in situ under toe5 Torr at 300°C for
agent. Moreover, this lower degree of burnoff results
3 hours.
in the development of a microporous structure[20].
The elemental analysis of the raw coal and of the
It is also evident that micropores in these chars are
samples prepared under the established conditions of
least affected by the degree of impregnation as com-
impregnation ratio, temperature (T) and time (t)
pared to pores of larger diameter[ 161. The increase
was carried out on a PerkinElmer 240 elemental
in impregnation ratio has also shown a gradual
analyzer.
decrease in ash content, except in KC1 where no effect
FTIR spectra of these two samples were recorded
is observed. However, CaCl, has shown an overall
on a Perkin-Elmer 1800 FTIR. The spectra were
better ash reducing action, both in lower and higher
run as KBr pellets and generated by co-adding
impregnation ratios. The ash reducing action of
four hundred ‘scans’ (interferograms) at 2 cm- ’
ZnCl,, as observed in raw materials of vegetable
resolution[ 171.
origin [ 211, is not so prominent in the case of mineral
Standard neutralization techniques with HCl,
coals. The data on adsorptive capacities of these
NaOH, Na,CO, and NaHCO, were performed[ 181
carbons when compared with the unactivated coal
for quantitative characterization of acidic and basic
sample, against adsorbates of different molecular
groups present on the carbon surface.
dimensions in Table 2, point out that only ZnCl, has
2.4 Establishing process variables produced samples with pronounced activity against
A particular activating agent and its impregnation adsorbates of iodine and methylene blue, and this
ratio (as established in Sections 2.2 and 2.3) were activity, of course, increases with the increase in its
used in further studies by carrying out a series of impregnation ratio. All the other samples of S, P and
experiments at 650, 7.50, 850°C and 1, 2, 3 hours for C class have failed altogether to produce any reason-
the selection of appropriate activation temperature able activity against either of these adsorbates. The
and time. reason for the low activity in these samples is the
higher boiling points of NaCl (1413°C) CaCl,
(1600°C) and KC1 (> 15OOC) as compared to ZnCl,
3. RESULTS AND DISCUSSION
(732°C). The higher boiling points hinder the mobility
Table 1 shows the chemical analysis of the Lakhra and reactivity of these activating agents during the
coal in its original and oxidised form. According to process of activation[22]. In the light of this study,
the Regnault-Gruner classification of coals[ 191, it ZnCl, in the impregnation ratio of 1:2 has been
borders on being lignitic in nature. The pretreatment selected as an appropriate activating agent for the
of coal was carried out so that after removal of a preparation of powdered activated carbon from
certain amount of volatile matter the maximum pos- Lakhra coal and used in further studies for optimum
sible amount of fixed carbon might be available for temperature and time selection. ZnCl, as an activa-
the process of chemical activation. It may also be ting agent in the ratio of 1: (l-2) has also been used
 Activated carbon from a low rank coal 19

Table 2. Effect of impregnation ratio of different activating agents on the physical and chemical
characteristics of activated carbon samples

Reagent Methylene
Sample* recovery Yield Ash Iodine No. blue No.
code (%) @) content @g/g) (msk)

Zl 31.9 41.5 11.28 695 57

Z2 35.3 51.7 10.17 802 125
Z3 40.6 79.8 8.58 810 167
Z4 47.8 87.8 7.22 856 212
S, 92.0 49.7 12.43 15 ND**
S2 88.3 52.1 12.08 22 ND
S3 81.1 53.3 9.30 30 ND
Sd 12.0 54.3 4.51 35 ND
PI 51.3 42.4 9.28 33 ND
P2 61.3 47.0 9.35 34 ND
P3 64.7 54.0 9.21 36 ND
P4 66.1 51.2 9.92 39 ND
Cl 50.2 51.3 7.20 42 ND
G 56.3 56.1 6.33 46 ND
C3 64.4 61.7 4.39 49 ND
Cd 67.5 63.3 3.21 55 ND
Blank 12.69 188 10

* The subscripts l-4 indicate the impregnation ratios-1 : 0.5,l: 1,l: 1.5 and 1:2_of activating agents.
**ND. not detectable.

60 Table4. Effect of activation temperature and time on

adsorptive characteristics of activated carbon samples
50
Methylene
40 Iodine blue No.
No.
30 Sample code (mg/g) (mgig)

20 Z,T, 909 212

GT, 873 206
10 Z,T, 700 186
: Z,T,t, 990 205
Z,T,t, 915 189
0050 100 150 200 Z,T,t, 875 182
% Impregnation -

Fig. 1. Relationship between degree of impregnation of ature of 650°C (Z,T’) overall produces the best
ZnCl, and percent burnoff. results. Its yield and reagent recovery are higher than
for the samples activated at higher temperatures
by Sung et ~I.[231 for the preparation of activated (Z,T, and Z,T,). It is also notable that reagent
carbon from coal. However, ZnCl, has a highly recovery drops in Z,T,, which may be due to the
corrosive nature and may cause problems of handling vaporization effect of this particular activating agent
and material of construction with 35-40% reagent at 850°C. The pattern of a gradual increase in ash
loss due to evaporation during the process. content with the increase of temperature, as seen in
The data on effect of activation temperature and Table 3, is due to the remnants of oxidation products
time on different chemical and physical characteristics of ZnCl, that have adhered to the finished product
of the samples are presented in Tables 3-5. They and are not easily leachable by acid during the
reveal that the sample activated at a lower temper- refluxion process [ 241. As for physical parameters

Table 3. Effect of activation temperature and time on yield, activating agent recovery
and ash content of activated carbon samples

Reagent Ash
Sample Temperature Time Yield recovery content
code (“C) (hour) (%) W) (So)

Z,T, 650 2 72.7 58.3 6.2

Z,T, 750 2 63.5 48.3 7.0
Z,T, 850 2 59.8 11.7 7.4
Z,T,t, 650 1 72.4 12.2 6.3
Z,T,t, 650 2 70.3 51.3 6.5
Z,T,r, 650 3 71.0 49.2 7.7
80 T. H. USMANI et al.

Table 5. Effect of activation temperature and time on physical characteristics of

activated carbon samples

Surface Surface
Bulk True Pore area of area of
Sample density density space pores0 pores-
code (g/cc) (g/cd w100 g) > 10 A >15A

Z,T, 0.6399 1.9892 106 834 606

Z‘IT, 0.6218 2.1120 113 800 589
ZIT, 0.6111 1.9512 112 638 532
Z,T,t, 0.4655 2.0247 165 909 587
Z,T,t, 0.5363 1.9929 136 839 541
Z,T,t, 0.5052 1.9734 147 802 521
Blank 0.8532 1.5781 72 160 29

O-
shown in Tables 4 and 5, it is evident that Z,T, has
shown comparatively better adsorptive properties
-0.2 -
with respect to iodine and methylene blue, and the
surface areas of pores greater than 10 and 15 .&
developed in this sample are comparatively higher
than Z,T, and Z,T,. The decrease in micro- and l
;..o_.
mesopore areas of these two samples suggests a 3 =*\
sintering effect of ZnCl, at higher temperature[22].
-0.8 -
These facts suggest that a lower temperature (650°C)
is suitable for the activation process, and this is -1.0 -
utilized in further studies. I I .
I
In the selection of variable of time, three sets of 0 0.1 0.2 0.3 0.4
experiments carried out at 1, 2 and 3 hours indicate Y/IO6
that an increase in time has an overall adverse effect
Fig. 2. DR plot for the adsorption of benzene at 293 K by
on the physical characteristics of the finished pro- activated carbon prepared from Lakhra coal. Variable
ducts. So an activation time of 1 hour is found to be Y= (T/B)’ log’ PO/P.
suitable for these studies.
The Dubinin-Radushkevich equation is used for pared from raw materials of mineral origin. A good
the calculation of characteristic adsorption energy E, correlation is also found between the surface area of
(kJ/mol) and micropore volume w,, of the product micropores S,i of this sample (942 m”/g) calculated
prepared under established conditions [ 161. by DR equation with the corresponding value
The average pore width L[25] is given by (909 m’/g) given in Table 5 calculated on the basis
L(nm)=10.8/(&-11.4) of iodine adsorption[ 151. However, a strong devia-
(3)
tion is found between the values of S, derived by the
The microporous surface area & has been calcu- t/F method and corresponding surface area of
lated [ 261 by the relation mesopores in this sample calculated on the basis of
2 x 103 x w, methylene blue adsorption [ 141.
LiW/d= L Table 7 depicts the elemental analysis of raw coal
and activated carbon prepared from it under the
The external surface area S,, correlated with meso- established working conditions. It may be seen here
and macropores of the product, is calculated by the that in the latter the fixed carbon shows a prominent
t/F method [ 271. increase with a proportional decrease of the other
Table 6 lists the main characteristics of selected chemical constituents. This substantial increase in the
activated carbon samples prepared from Lakhra coal. fixed carbon with subsequent removal of undesirable
The micropore volume W, of this sample calculated matter plays a pivotal role in enhancement of activity
from DR plot (Fig. 2), has been found to be in the finished product manifold.
0.46 cm3/g. This value is in quite good agreement The FTIR spectra of the unactivated and activated
with the corresponding values derived by Huber samples reveal that the aromatic polynuclear and
et al.[28] for several activated carbon samples pre- aliphatic bands present in the raw coal are altogether

Table 6. Main characteristics of the selected activated carbon sample prepared from
Lakhra coal derived from absorption experiments

Sample
code E, (kJ/mol) W, (cm3/g) L (nm) Smi (m’/g) S, (m’ig)

Z,T,h 22.4 0.46 0.98 942 142

 Activated carbon from a low rank coal 81

Table 7. Elemental analysis of Lakhra coal and selected activated carbon samples

Elemental analysis (%)

Oxygen by
Sample C H N S Ash difference

Lakhra coal 45.79 5.11 1.44 7.00 8.43 32.23

Z,T,t, 79.25 1.62 1.31 3.42 6.30 8.10

Table 8. Neutralization capacities of the selected activated carbon sample prepared

from Lakhra coal for hydrochloric acid and different alkalis

Sodium Sodium Sodium Hydrochloric

hydroxide, bicarbonate, carbonate, acid,
neutralized neutralized neutralized neutralized
Sample (mBq/lC@ 8) (mBq/lm 8) (mBq/lOO 8) (mEq/l(@ 8)

Z,T,r, 138 286 35 0

(original)
Z,T,t, 103 239 1.2 0
(300°C)
(Outgassed)

removed upon activation, and a new group appears carbon sample by absorption spectra shows the pres-
at 1575 cm-’ on the surface chemical structure of the ence of carboxylic groups developed on its surface,
activated sample[ 17,291. It may be explained by the and their predominance is further confirmed upon
fact that polynuclear and carbonyl groups having reaction with different alkalis.
absorption at 1615 and 1710 cm-r in the parent coal
merge upon activation at 650°C with emergence of a
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