A sawdust mixture was used as the starting material. Urea or a melamine was added to sawdust as the nitrogen compound. K 2 CO 3 was added to this mixture as an activation reagent. It was concluded that the activated carbon with large specific surface area can be produced even from the starting material with low nitrogen content.
A sawdust mixture was used as the starting material. Urea or a melamine was added to sawdust as the nitrogen compound. K 2 CO 3 was added to this mixture as an activation reagent. It was concluded that the activated carbon with large specific surface area can be produced even from the starting material with low nitrogen content.
A sawdust mixture was used as the starting material. Urea or a melamine was added to sawdust as the nitrogen compound. K 2 CO 3 was added to this mixture as an activation reagent. It was concluded that the activated carbon with large specific surface area can be produced even from the starting material with low nitrogen content.
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. REFERENCES Bacaoui, A., Yaacoubi, A., Dahbi, A., Bennouna, C., Phan Tan Luu, R., Maldonado- Hodar, F.J., Rivera-Utrilla, J. and Moreno-Castilla, C. 2001 Optimization of conditions for the preparation of activated carbons from olive-waste cakes, Carbon, vol.39, pp425-432
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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