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PRODUCTION OF ACTIVATED CARBON WITH LARGE

SPECIFIC SURFACE AREA FROM A SAWDUST MIXED WITH A


NITROGEN COMPOUND BY CHEMICAL ACTIVATION USING
POTASSIUM CARBONATE

Junichi Hayashi
1
, Osamu Okuma
2
, Toshihide Horikawa
3


1
Department of Chemical, Energy and Environmental Engineering, Kansai University
3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan
hayashi7@kansai-u.ac.jp
2
Research Department 3, The New Industry Research Organization (NIRO)
1-5-2 Minatojima Minamimachi, Chuo-ku, Kobe 650-0047, Japan
okuma@ri.niro.or.jp
3
Department of Advanced Materials, Institute of Technology and Science,
The University of Tokushima,
2-1 Minami-jyousanjima-cho,Tokushima 770-8506, Japan
horikawa@chem.tokushima-u.ac.jp


ABSTRACT
In this paper, the sawdust was used as the starting material. A urea or a melamine was
added to sawdust as the nitrogen compound, and K
2
CO
3
was added to this mixture as an
activation reagent. We tried to produce the activated carbon with large specific surface
area from this mixture by chemical activation. The result was that we succeeded in
production of the activated carbon with the large specific surface area of about 3000
m
2
/g. Especially, the mesopore volume was well developed when a melamine was used
as the nitrogen compound. It was concluded that the activated carbon with large
specific surface area can be produced even from the starting material with low nitrogen
content like the sawdust by adding the nitrogen compound. This was due to the
modified carbonization behaviour by the interaction between the sawdust, the added
nitrogen compound and K
2
CO
3
. Consequently, the disordered carbon layer structure
was formed and the specific surface area and the pore volume were large.
INTRODUCTION
Activated carbons have their well-developed porosity and large surface area. Therefore,
they are used as not only adsorbent, but also catalyst and catalyst support. They are the
useful material and are used in the various fields, such as the separation process, the
purification process and the water treatment process.
Activated carbons are produced by two methods: physical activation and chemical
activation. In physical activation, the raw material is carbonized and subsequently is
gasified by CO
2
(Yang & Lua 2003) or steam (Bacaoui et al 2001). In chemical
J.Hayashi, O. Okuma, T. Horikawa

activation, the raw material is impregnated with activation reagent such as H
3
PO
4

(Haimour & Emeish 2006) and ZnCl
2
(Tsai et al 1997) and the impregnated raw
material is carbonized.
Recently, activated carbons with large specific surface area are produced by chemical
activation using KOH as activation reagent (Vilaplana-Ortego et al 2009). These
activated carbons are expected to be a useful material for the energy device such as a gas
storage and electric double-layer capacitor. However, in order to get large specific
surface area, a large amount of KOH, which is strong reagent, has to be used and the
activated carbon is produced under the very severe condition. In order to produce the
activated carbon under the milder condition, we have used K
2
CO
3
, which is not strong
reagent, as activation reagent. We reported that activated carbons with large specific
surface area were able to be produced from urea-formaldehyde (Hayashi et al 2002)
resin and polyurethane (Hayashi et al 2005). But, when phenol-formaldehyde resin was
used as raw material, the specific surface area was not large (Hayashi et al 2002). Urea-
formaldehyde resin and polyurethane contain a large amount of nitrogen, while phenol-
formaldehyde resin contains no nitrogen. We presumed that in order to get large
specific surface area, the raw material has to contain large amount of nitrogen. Thus,
the raw material is limited in order to produce the activated carbon with large specific
surface area by K
2
CO
3
activation.
The aim of this paper is to produce the activated carbon with large surface area from the
raw material with low nitrogen content by addition of nitrogen compound. In this paper,
we selected sawdust as raw material with low nitrogen content. And urea or melamine
was added to the sawdust as nitrogen compound. We tried to produce the activated
carbon with large specific surface area from the sawdust with the nitrogen compound by
K
2
CO
3
activation. And the influence of production conditions on the pore structure of
the activated carbon was examined.
EXPERIMENT
Production of activated carbon
The result of the elemental analysis for the sawdust used in this paper is shown in Tab.1.
The sawdust is very low nitrogen content as shown in Tab.1. The sawdust, the additive
(urea or melamine) and K
2
CO
3
were mixed using water. The mixing weight ratio of the
sawdust, the additive and K
2
CO
3
was 1:1:2. This mixture was heated up to the
carbonization temperature at the heating rate of 10 K/min and it was maintained at the
carbonization temperature for 1 h. The carbonization temperature was changed between
773 and 1273 K. The produced char was washed using hot water to remove K
2
CO
3
in
the char. And then the activated carbon was obtained.

Tab.1 Elemental analysis of sawdust used in this paper



C H N O(diff.)
Sawdust 50.75 6.24 0.12 42.89
Elemental analysis [wt%(d.b.)]
J.Hayashi, O. Okuma, T. Horikawa

Characterization of activated carbon
Pore structure
Adsorption and desorption isotherms of N
2
on the produced activated carbon were
measured at 77 K by using the automatic gas adsorption measurement apparatus
(BELSOPR-mini, BEL Japan Inc.). Before measuring, the activated carbon was
degassed in vacuo at 473 K for 2h. The specific surface area was calculated by B.E.T.
method (Brunauer, Emmett, & Teller 1938) using the data of the adsorption isotherm.
Total pore volume was calculated from the adsorption amount at the relative pressure of
0.95. Micropore volume was calculated by
s
-method (Sing 1989), and mesopore
volume was calculated by subtracting micropore volume from total pore volume.
Mesopore size distribution was calculated by Dollimore-Heal method (Dollimore &
Heal 1964) using desorption isotherm data.
Thermo gravimetric analysis
The carbonization behaviour was measured by using thermobalance (TGA-50,
Shimadzu Corporation) on the aspect of the weight loss behaviour. The sample was
dried at 383 K and heated up to 1273 K at heating rate of 10K/min and the weight loss
behaviour was measured for this period.
XRD analysis
The structure of the produced activated carbon was analysed by using XRD (RINT-
TTRIII, Rigaku Corporation).
RESULTS AND DISCUSSION
Specific surface area of produced activated carbon
Figure 1 shows the influence of
carbonization temperature on the
specific surface area of produced
activated carbon. The specific
surface area of the activated
carbons increased with an
increase of carbonization
temperature at less than 1073 K,
and they increased rapidly
between 873 and 973 K, and they
decreased slightly at more than
1073 K. That is, the specific
surface area reached the
maximum value at about 1073 K
and the values were more than
2000 m
2
/g, which were very large
specific surface area.
4000
3000
2000
1000
0
S
p
e
c
i
f
i
c

s
u
r
f
a
c
e

a
r
e
a

[
m
2
/
g
]
1300 1200 1100 1000 900 800 700
Carbonization temperature [K]
Sawdust-Urea-K
2
CO
3
Sawdust-Melamine-K
2
CO
3
Sawdust-K
2
CO
3
Fig. 1 Influence of carbonization temperature on
the specific surface area
J.Hayashi, O. Okuma, T. Horikawa

The specific surface area of the activated carbon produced without urea or melamine
was about 1300 m
2
/g, which was normal value for the general activated carbon. Though
not shown in Fig.1, this surface area was much larger than that of sawdust char (260
m
2
/g). This indicated that K
2
CO
3
worked as activation reagent, and it was clarified that
the specific surface area was increased further by adding a nitrogen compound such as
urea or melamine.
Pore volume of produced activated carbon
Figures 2(a), (b) show the influence of carbonization temperature on the pore volume.
The total pore volume of the produced activated carbon increased with an increase of
carbonization temperature. The micropore volume was well-developed in the activated
carbon produced with urea. On the other hand, the mesopore volume was increases with
an increase of carbonization temperature in the activated carbon produced with
melamine, and the mesopore volume increased rapidly between 1073 and 1173 K.







Fig. 2 Influence of carbonization temperature on the pore volume of the produced
activated carbon from (a) sawdust with urea and (b) sawdust with melamine
Mesopore size distribution
Figure 3 shows the influence of carbonization temperature on the mesopore size
distribution of activated carbon produced with melamine. The mesopore was very small
at less than 973 K. Both the mesopore volume and mesopore size were increased with
an increase of the carbonization temperature at more than 973 K.







Fig. 3 Influence of carbonization temperature on the mesopore size distribution
2.5
2.0
1.5
1.0
0.5
0.0
P
o
r
e

v
o
l
u
m
e

[
m
l
/
g
]
773 873 973 1073 1173
Carbonization temperature [K]
Micropore
Mesopore
(a) Sawdust-Urea-K
2
CO
3
2.5
2.0
1.5
1.0
0.5
0.0
P
o
r
e

v
o
l
u
m
e

[
m
l
/
g
]
773 873 973 1073 1173 1273
Carbonization temperature [K]
(b) Sawdust-Melamine-K
2
CO
3
Micropore
Mesopore
12.0
9.0
6.0
3.0
0.0

V
/

l
o
g
(
r
)

[
m
l
/
g
]
1 10
Radius [nm]
Sawdust-Melamine-K
2
CO
3
773 K
873 K
973 K
1073 K
1173 K
1273 K
J.Hayashi, O. Okuma, T. Horikawa

TG analysis
Figures 4(a)(b) show the weight loss behaviours of sawdust, K
2
CO
3
, urea and melamine,
measured independently. There was no weight loss of K
2
CO
3
at less than 1173 K, and
the yields of both urea and melamine were almost zero at more than 673 K.








Fig. 4 (a)TG-curve and (b)dTG-curve of sawdust, K
2
CO
3
, urea and melamine

Figures 5(a)(b) show the weight loss behaviour of sawdust impregnated with K
2
CO
3
.
The calculated line was drawn with assuming that the both weight loss occurred
independently because of no-interaction between sawdust and K
2
CO
3
. The differences
between the experimental line and the calculated one were found at less than 773 K and
at more than 973 K. We reported that by adding K
2
CO
3
, the structure of the char was
modified at less than 773 K, and that K
2
CO
3
was reduced by reaction with carbon as
shown in eq.(1) at more than 973 K ((Hayashi et al 2002, 2005). The carbon was
consumed by this reaction and consequently, the specific surface area reached about
1300 m
2
/g.

K
2
CO
3
+ 2C -> 2K + 3CO (1)








Fig. 5 (a)TG-curve and (b)dTG-curve of sawdust-K
2
CO
3

Figures 6(a)(b) show the weight loss behaviour of the sawdust-urea-K
2
CO
3
mixture.
The calculated line was drawn with assuming that there is not an interaction between the
1.0
0.8
0.6
0.4
0.2
0.0
R
e
l
a
t
i
v
e

w
e
i
g
h
t

[
-
]
1200 1000 800 600 400
Temperature [K]
Sawdust
K
2
CO
3
Urea
Melamine
(a)
0.3
0.2
0.1
0.0
R
e
l
a
t
i
v
e

w
e
i
g
h
t

l
o
s
s

r
a
t
e

[
m
i
n
-
1
]
1200 1000 800 600 400
Temperature [K]
Sawdust
K
2
CO
3
Urea
Melamine
(b)
1.0
0.8
0.6
0.4
0.2
0.0
R
e
l
a
t
i
v
e

w
e
i
g
h
t

[
-
]
1200 1000 800 600 400
Temperature [K]
Sawdust-K
2
CO
3
(1:2)
Experimental
Calculated
(a)
0.10
0.08
0.06
0.04
0.02
0.00
R
e
l
a
t
i
v
e

w
e
i
g
h
t

l
o
s
s

r
a
t
e

[
m
i
n
-
1
]
1200 1000 800 600 400
Temperature [K]
Sawdust-K
2
CO
3
(1:2)
Experimental
Calculated
(b)
J.Hayashi, O. Okuma, T. Horikawa

sawdust impregnated with K
2
CO
3
and the urea. The large weight loss was found at
more than 973 K, and this weight loss was due to the reduction reaction (eq. (1)). By
the reduction reaction, the specific surface area and the pore volume were increasing, as
shown in Fig.1 and in Figs.2 (a)(b). However, the difference between the experimental
line and the calculated one was very small at the more than 973 K. This indicated that
the added urea gave no effect to the reduction reaction (eq. (1)). The large difference
was found at less than 573 K. In this temperature range, many complicated reactions
occur simultaneously and the base structure of the char was formed. Therefore, it was
presumed that the added urea gave effect to the carbonization behaviour at less than 573
K and that this led to the increase of the specific surface area and pore volume.








Fig. 6 (a)TG-curve and (b)dTG-curve of sawdust-urea-K
2
CO
3


Figures 7(a)(b) show the weight loss behaviour of the sawdust-melamine-K
2
CO
3

mixture. This calculated line was drawn as same assumption as in the case of the
sawdust-urea-K
2
CO
3
mixture. The tendency of the difference between the calculated
line and the experimental line was same as in case of the sawdust-urea-K
2
CO
3
mixture
as shown in Figures 6(a)(b). Therefore, it was concluded that the interaction between
the sawdust, the nitrogen compound and K
2
CO
3
at the beginning of carbonization was
very important in order to produce the activated carbon with a large surface area.








0.10
0.08
0.06
0.04
0.02
0.00
R
e
l
a
t
i
v
e

w
e
i
g
h
t

l
o
s
s

r
a
t
e

[
m
i
n
-
1
]
1200 1000 800 600 400
Temperature [K]
Experimental
Calculated
Sawdust-Urea-K
2
CO
3
(1:1:2)
(b)
1.0
0.8
0.6
0.4
0.2
0.0
R
e
l
a
t
i
v
e

w
e
i
g
h
t

[
-
]
1200 1000 800 600 400
Temperature [K]
Experimental
Calculated
Sawdust-Mealmine-K
2
CO
3
(1:1:2)
(a)
0.10
0.08
0.06
0.04
0.02
0.00
R
e
l
a
t
i
v
e

w
e
i
g
h
t

l
o
s
s

r
a
t
e

[
m
i
n
-
1
]
1200 1000 800 600 400
Temperature [K]
Sawdust-Mealmine-K
2
CO
3
(1:1:2)
Experimental
Calaulated
(b)
Fig. 7 (a)TG-curve and (b)dTG-curve of sawdust-mealmine-K
2
CO
3

1.0
0.8
0.6
0.4
0.2
0.0
R
e
l
a
t
i
v
e

w
e
i
g
h
t

[
-
]
1200 1000 800 600 400
Temperature [K]
Sawdust-Urea-K
2
CO
3
(1:1:2)
Experimental
Calculated
(a)
J.Hayashi, O. Okuma, T. Horikawa

Elemental analysis
The elemental analysis of the produced activated carbons from the sawdust-K
2
CO
3
, the
sawdust-urea-K
2
CO
3
and the sawdust-melamine-K
2
CO
3
are summarized in Tab. 2. All
activated carbon produced at 1073 K.
Nitrogen content of the activated carbons from sawdust with nitrogen compounds was
higher than that of the activated carbon from sawdust without nitrogen compounds.
This indicates that added nitrogen was taken in the carbon matrix and it was inferred
that this intake was due to the interaction at less than 573 K.

Tab.2 Elemental analysis of produced activated carbon at 1073 K





XRD analysis
Figure 8 shows the XRD patterns of the produced activated carbons at the carbonization
temperature of 1073 K. The broad peak was found at about 26.5 in the XRD pattern
of the activated carbon produced without nitrogen compound, but the peak was not
found clearly in the pattern of the activated carbon produced with nitrogen compound.
Especially, there was almost no peak in the pattern of the activated carbon produced
with melamine. This peak is contributed to the height of the crystallite which consists
of a few defective micro-graphen layers. These crystallites are connected to each others
by the crosslinking bond and the pore is the space between the crystallites (Franlin
1950). The broad peak means that the prepared activated carbons are predominantly the
amorphous structure (Wang 1997).
Therefore, the height size of crystallite is
small and the crystallites are allocated
disorderly. Because of the disorder
allocation, the space between the
crystallites is large, and consequently,
both the specific surface area and the
pore volume are large (Zhu 2007). It
was deduced that the disordered carbon
layer structure was formed by the
interaction between the sawdust, nitrogen
compound and K
2
CO
3
and that
consequently, the specific surface area
and the pore volume were large.
Fig. 8 XRD pattern of produced activate carbon at 1073 K
I
n
t
e
n
s
i
t
y
80 60 40 20 0
2 [deg]
Sawdust-Urea-K
2
CO
3
(1:1:2)
Sawdust-K
2
CO
3
(1:2)
Sawdust-Melamine-K
2
CO
3
(1:1:2)
C H N O(diff.)
Sawdust-K
2
CO
3
83.43 0.9 0.27 15.4
Sawdust-urea-K
2
CO
3
87.65 0.78 0.74 10.83
Sawdust-melamine-K
2
CO
3
85.78 0.97 1.34 11.91
Elemental analysis [wt%(d.b.)]
J.Hayashi, O. Okuma, T. Horikawa

CONCLUSION
We tried to produce the activated carbon with large surface area from the sawdust with
nitrogen additives (urea or melamine) by chemical activation with K
2
CO
3
. At the
carbonization temperature of 1073 K, the specific surface area reached the maximum
value (>2000 m
2
/g). Especially, when a melamine was used as nitrogen compound, the
activated carbons with large mesopore volume were produced. It was concluded that
the carbonization behaviour at less than 573 K was affected by addition of nitrogen
compound and that the disordered carbon layer structure was formed and that
consequently, the specific surface area and the pore volume became large.
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BRIEF BIOGRAPHY OF PRESENTER
1993 PhD (Chemical Engineering), Kyoto University
1992-1996 Research Associate, Kansai University
1996-2002 Lecturer, Kansai University
2001-2002 Visiting Scholars, the University of Sydney
2002-2011 Associate professor, Kansai University
2011-now Professor, Kansai University