OXJX-6223192 $5.00 + .

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Copyright Q 1992 Pergamon Press Ltd.

Cdxx~ Vol Xl. No. 4. pp. 601-604. 1992

Printed in Great Britain.

EFFECT OF THE PREPARATION METHOD ON THE

PORE SIZE DISTRIBUTION OF ACTIVATED
CARBON FROM COCONUT SHELL
JORGE

LAINE

Laboratorio de Fisico-Quimica de Superficie, Instituto Venezolano de Investigaciones

Cientificas, Apt. 21827, Caracas 1020-A, Venezuela
and
SIMON YUNES
One Micromeritics Drive, Norcross, GA

30093,

U.S.A.

(Received 19 August 1991; accepted in revise~~or~~ 9 December

1991)

Micromeritics,

Abstract-The pore size distribution of activated carbon prepared from coconut shell employing different activation methods was investigated. Physical activation with pure CO? at 8aOC resulted in a
bimodal pore size distribution featuring both the widest macropores and the narrowest micropores
among the samples studied. The introduction of potassium phosphate as a catalyst for the gasification
with CO: led to a decrease in macropore volume and diameter, and to a slight increase in micropore
diameter. Wider micropores and significant mesoporosity resulted when employing chemical activation with phosphoric acid at a lower temperature (500C). Surface area was found to increase with
increasing median micropore diameter between about 7-15 A. Three simple schemes were proposed
depicting the effect of the preparation method on pore size distribution.

1. INTRODUCTION

2. EXPERIMENTAL

The pore size distribution of activated carbon is an

important factor for application in specific process
operations. However, the control of pore sizes in the
synthesis of activated carbons is an aspect not clarified in scientific literature.
Practically, the type of porosity is dictated by the
type of raw material employed. However, the
method of activation is another parameter that may
influence the final pore size distribution. In general,
both large surface area and wide pores are desirable.
Large surface area allows large adsorption amounts,
and wide pores enhance diffusion, which influences
the overall kinetics of adsorption.
Two general methods are used for the preparation
of activated carbon[l-31. One, the physical activation, consists of heating at a high temperature
(e.g., 800C) under a carbon gasification reactant
(HZ0 or CO,). The use of a catalyst for gasification
(e.g., K, Na salts) is a variation of this method. The
other method, chemical activation, consists of
heating at a relatively lower temperature
(e.g.,
5OOC) with the addition of a dehydration agent
(e.g., HJOJ.
Within the above scope, we have devoted this
work to study changes in pore size distribution in
activated carbons prepared from a single raw material-coconut
shell-employing
the three activation procedures above classified (i.e., the physical
with or without the catalyst K,PO,, and the chemical methods using H,POJ.

The coconut shell employed was ground and

sieved to obtain the fraction of about 0.2-0.5 mm.
Three types of carbons were prepared:
Carbon Cl was physically activated by passing
the fresh coconut shell through a small scale cocurrent flow rotary kiln using CO, as activator gas at
800C. Details of the apparatus and procedure have
been given elsewhere[4].
Carbon C2 was also prepared by activating with
CO> at 8OOC, but employing potassium phosphate
as a catalyst for carbon gasification. The potassium
salt solution was impregnated on the fresh shells (5.5
wt% K), to follow an activation procedure described
elsewhere[5].
Carbon C3 was prepared using a low temperature
chemical activation with H,PO, as described elsewhere[b]. Brietly, the acid solution was impregnated
on the fresh shell (30 wt% acid) and then heated at
500C in a muffle.
Both C2 and C3 were subjected to extensive washing for the extraction of the catalyst and chemical,
respectively. Burnoff values referred to the fresh
coconut shell were about 80,85, and 70 wt% for Cl.
C2, and C3, respectively.
The real densities of the activated carbons were
measured employing a helium p~cnometer Micromeritics model 1330.
Microporosity was investigated from argon adsorption isotherm at liquid argon temperature (87.3
K). using a Micromer~tics ASAP 2000 apparatus.

601

:.
1

J. LAINEand S. YUNES

602

Argon was used instead of nitrogen to avoid the

diffusion problems that accompany the use of nitrogen, thus allowing a larger number of isotherm
points (e.g., 150 for C3). Data obtained were processed to calculate pore volume and surface area by
Langmuir[7] and Harkins & Jura t-plots[8], as well
as median micropore diameter by the Horvath-Kawazoe method[9]. The latter is an approach to avoid
the doubtful use of the Kelvin equation at the smallest pores.
Macroporosity was investigated by mercury intrusion, using a Micromeritics Autopore 9220 apparatus. The pressure employed ranged from about 1.6
to 60,000 psia (corresponding to pore diameters between about 110 p,rn and 30 A), taking about 250
measurements of incremental mercury volume vs.
pressure, with equilibrium time of 10 seconds.
3. RESULTS

Figure 1 shows that the isotherms are type I. However, upon examination of the very low pressure
range (P/PO < 0.1) in a semi-log plot (Fig. 2), it
appears that the isotherm shape varies from one sample to another. According to classification referred
to elsewhere[7], they may be assigned to either type
V (Cl and C2) or type III (C3).
Tables 1, 2, and 3 summarize data derived from
characterization of the activated carbons.
Real density values (Table 1) suggest that the porosity increases in the order Cl > C2 > C3. This
trend is also followed by the micropore volume (Table 2). However, macropore volume follows an opposite order (Table 3), indicating that real density is
not affected by the macropore, but by the micropore
volume.
As expected, micropore surface areas (Table 2)
are significantly larger than macropore surface area
(Table 3); however, macropore volumes (about 0.61 g/cc) are larger than micropore volumes (about
0.2-0.5 g/cc).
Table 2 shows that the Langmuir plot produces
larger surface areas than the t-plot, and the latter
produces smaller pore volumes than the HorvathKawazoe method. Table 2 also shows that surface
area increases with increasing median micropore
diameter.

tln 1
400

,.
..

I-

+-J-j , , , , , , , , , 1
0.1

0.2

0.3

RELATIVE

Fig. 1. Adsorption

0.4

c3,::
;

__:r,A
::

IO-

10-a

RELATIVE

PRESSURE,

0.5

PRESSURE,

06

0.7

0.8

0.9

(P/PO)

isotherm of argon (87.3 K).

_,

IO-'
(P/P,)

Fig. 2. Adsorption isotherm of argon (87.3 K) at low relative pressures.

The range of relative pressures employed in the

Langmuir plot were 0.05-0.20, obtaining correlation
coefficients higher than 0.9990.
Thickness (t) values employed in the least-square
analysis for the t-plots were 5 to 6 8, for Cl, 6 to 8
A for C2, and 12 to 14 A for C3, obtaining correlation coefficients higher than 0.990.
Figure 3 shows the curves derived from the Horvath-Kawazoe method. It is seen that the peak tail
is wider moving from Cl to C2 to C3. This fact causes
higher values of the median micropore diameter, as
indicated in Table 2.
Macropore diameter distributions are shown in
Figure 4. The three curves present two peaks suggesting two main macropore diameters. However,
the location of the peaks is quite different in each
case: Cl shows them at about 30 and 3 pm, C2 at 2
and 0.4 km, and C3 at 4 and 0.006 pm. The latter
diameter (6OA) may be included in the mesopore
class (20-500 A).
4. DISCUSSION

The results reported above demonstrate that the

pore size distribution of activated carbons prepared
from coconut shell can be significantly affected according to the activation method employed.
Macropore diameters are shifted to narrower values moving from Cl to C2 to C3 (Fig. 4), but micropore diameter follows an opposite trend (Fig. 3).
This suggests the transition from a bimodal (narrowmicro + wide-macro) porous structure (Cl) to a
mainly mesoporous one (C3).
Figure 5 schematizes possible microstructural
models for the three carbons presently studied. Aromatic sheets, similar to those formed in graphite,
is the common characteristic in the models. The in-

......
..,..,.................
,......... c3

350
....,....
0
300
.........
\
_____----i 250 /_-_---c2
<f
d 2(JrJ
;
:
Cl
6 150
::
4 100
...

400

Table 1. Pycnometer data

Sample

Average density (g/cc)

Cl
c2
c3

2.131
1.987
1.834

603

Activated carbon from coconut shell

Table 2. Data from adsorption isotherm of argon
Horvath-Kawazoe

plot

r-plot

Langmuir plot
Sample

Area (mig)

Area (mz/g)

Pore volume (cc/g)

Pore volume (cc/g)

Median pore
diameter (A)

Cl
C2
c3

750.6
1014.2
1360.4

696.1
959.4
1341.2

0.222
0.312
0.491

0.255
0.359
0.521

7.x
8.h
14.7

terplanar distance of graphite (n

ably not reached after activation
idizing atmosphere
and relatively
factors favoring the formation of

= 3.35 A) is probbecause of the oxlow temperature,

oxygen functional

groups at the sheet edges, which avoids either by

steric or electronic effects the close packing of the
sheets, hence forming wider interplanar spaces-the
slit micropores. Closer to reality, a scheme featuring
twisted aromatic sheets has also been proposed elsewhere[lO] as a generalized structure for activated
carbons.
It may be also interesting to remark that the lubricant characteristic of graphite, arising from the
weak (Van-Der-Waal)
attraction
forces among
sheets, is absent in activated carbons, most likely as
a result of the interaction of the oxygen groups at
adjacent sheets.
As seen in Figs. 3 and 4. sample Cl presents pores
distributed toward both the narrowest micropores
and the widest macropores. These latter were most
likely formed as a result of the preservation of the
lignocellulose tissue arrangement after carbonization. Confirming this, microscopy analysis of similar
physically activated carbon reported elsewhere[4]
showed the presence of aligned honeycomb-like
groups of pores on the order of 10 pm diameter,
most likely the carbonaceous skeleton from the biological capillary structure of the raw material.
In case of sample C2, the partial destruction of
the widest macropores, implied from Fig. 4, was
probably the result of a faster gasification effected
by the catalyst leading to a more extended burnoff85% as compared to 80% of Cl.
In contrast to its catalytic function, the potassium
phosphate appears to protect the edges of the aromatic sheets from excessive gasification by forming
linear polyphosphates linked to sheet edges, as reported earlier[S,ll].
Such protection of these most
reactive sites leaves the aromatic sheets available for
a progressive CO1 basal attack for mesopore formation, as illustrated in Fig. 5-C2 thus contributing
to a larger median micropore diameter (Table 2) and

to a larger proportion of mesopores (Fig. 4. C2),

compared to sample Cl.
In the case of sample C3, a less ordered stacking
of aromatic sheets should be expected as a result of
the lower activation temperature. Notice in Table 2
that median micropore diameter of C3 is about twice
that of Cl. This could be the result of an incomplete
slide stacking of aromatic sheets as shown in Fig.
5. C3. Nevertheless, the greater oxygen and hydrogen content of C3 reported previously[b] also suggests a more complex structure, probably with the
participation of significant aliphatic character.
Therefore. a large degree of disorder in sample

Cl
-.

-4

1
i

Table 3. Mercury intrusion data

Sample

Total intrusion
volume (ml/g)

Cl
C2
C3

0.990
0.667
0.645

Total macropore
area (mig)
51.0
105.2
138.3

Fig. 3. Pore size distributions from the Horvath-Kawazoe

method.

J. LAINE and S.
l.O-

YUNES

Graphite : diPi

3*35B

0.2-

0.6-

0.4-

izi33+

cp:

0.2-

o.o-1.0-

c,

: //.-5T-

10-20;

0.*-

Fig. 5. Micropore models.

0.4

also be the cause of differences in isotherm types

shown in Fig. 2: type III for C3 and type V for Cl
and C2.

0.2

0.0
1.0

Acknowledgements-The

authors would like to thank Alvaro Calafat and Santiago Simoni for the preparation of
the carbons.

0.8

~FERENCES

0.6

1.

0.4

Properties

0.2

0.0

M. Smisek and S. Cerny, Active Carbon Manufacture,

2.
I ,

too

,,/,,,,,
$0
DIAMETER,

,,,

/,,,,,,
0.1

,/,,,,

0.01

3.
4.

(mIcrometera)

Fig. 4. Pore size distributions from mercury intrusion.

5.
6.
7.

8.

C3 is most likely the cause of the large proportion

of mesopores (20-500 A) observed in both Figs. 3
(C3) and 4 (C3).
Finally, the different structure of C3 with respect
to the more slit-shaped structures of Cl and C2 could

9.
10.
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