PERGAMON

Carbon 38 (2000) 18731878

Preparation of activated carbon from lignin by chemical activation

Junichi Hayashi a , *, Atsuo Kazehaya a , Katsuhiko Muroyama a , A.Paul Watkinson b
b a Department of Chemical Engineering, Kansai University, 3 -3 -35 Yamate-cho, Suita, Osaka, 564 -8680 Japan Pulp and Paper Centre, Department of Chemical and Bio-Resource Engineering, The University of British Columbia, Vancouver, BC, Canada V6 T 1 Z4

Received 30 September 1999; accepted 25 January 2000

Abstract Activated carbons were prepared from lignin by chemical activation with ZnCl 2 , H 3 PO 4 and some alkali metal compounds. The inuence of carbonization and activating reagent on the pore structure of the activated carbon was investigated. It was found that the maximum surface areas were obtained at the carbonization temperature of 6008C in both ZnCl 2 and H 3 PO 4 activation, and that the surface areas were as large as those of the commercial activated carbons. On the other hand, in alkali metal activation it was found that the maximum surface areas were obtained at the carbonization temperature of 8008C. Except for Na 2 CO 3 maximum surface areas were much larger than those of the commercial activated carbons. The activated carbon prepared by K 2 CO 3 activation showed a surface area of nearly 2000 m 2 / g. It was shown that ZnCl 2 works effectively as dehydration reagent below 6008C. On the other hand, K 2 CO 3 works effectively in two temperature ranges, below 5008C and above 6008C. Below 5008C, the carbonization behavior was modied by impregnation with K 2 CO 3 , but the pore structure changes little. Above 6008C, carbon was consumed by K 2 CO 3 reduction and then the surface area was increased. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: A. Activated carbon; B. Activation; C. BET surface area; D. Surface areas

1. Introduction Activated carbon is a high-porosity material which is useful in adsorption of both gases and solutes from aqueous solution. Therefore it has been widely used for the separation of gases, the recovery of solvents, the removal of organic pollutants from drinking water and as a catalyst support. As environmental pollution is becoming a more serious problem, the need for activated carbon is growing. Coals and ligno-cellulosic materials are commonly used as the starting material for preparing activated carbon. Recently, numerous attempts to prepare activated carbon from solid wastes have also been made [110]. The development of methods to re-use waste materials is

*Corresponding author. Tel.: 181-6-6368-0913; fax: 181-66388-8869. E-mail address: hayashi7@kansai-u.ac.jp (J. Hayashi)

greatly desired and the production of activated carbons from wastes is an interesting possibility. Lignin is a waste which is generally used only for its fuel value. Therefore, it was of interest to prepare a higher value product such as an activated carbon from lignin. There are basically two methods for preparing activated carbon: physical and chemical activation. Physical activation consists of two steps: the carbonization of the starting material, and the activation of the char by using carbon dioxide or steam. In chemical activation both the carbonization and the activation step proceed simultaneously. Many studies for preparing activated carbon by chemical activation [1,4,5,916] have been done. Recently, activated carbons with very high surface area have been prepared by chemical activation [1114]. Gas storage is a potential application for such high surface area materials. However, the purpose of most of these studies was to prepare the activated carbon, and little attention has been given to the inuence of the activating reagent on the pore

0008-6223 / 00 / $ see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S0008-6223( 00 )00027-0

1874

J. Hayashi et al. / Carbon 38 (2000) 1873 1878 Table 2 Specic surface areas and pore volumes of commercial activated carbons Specic surface area (m 2 / g) Coconut shell AC Coal AC 1267 1089 Micropore volume (ml / g) 0.492 0.428 Mesopore volume (ml / g) 0.061 0.179

structure and to the mechanism of activation. Therefore it is of interest to investigate these matters. The purposes of the present work were to prepare activated carbons from lignin by chemical activation and to examine the inuence of preparation conditions (carbonization temperature and chemical reagent) on the pore structure of the activated carbon and to clarify the temperature range where the chemical reagents work effectively.

2. Experimental
Chemical recovery 5

2.1. Preparation of activated carbon

Strong black liquor from Kraft pulping of a mainly spruce wood furnish from New Brunswick, Canada was acidulated with pure CO 2 to precipitate the lignin, which was then washed in acid several times and dried. Ultimate analysis of the lignin on a dry basis is given in Table 1. Six chemicals (K 2 CO 3 , Na 2 CO 3 , KOH, NaOH, ZnCl 2 , H 3 PO 4 ) were used as activating reagents. Lignin was mixed with the activating reagent and water, and kneaded. This mixture was then dried at 1108C to prepare the impregnated sample. The impregnation ratio was estimated from the following equation: Impregnation ratio 5 (weight of sample after impregnation) 2 (weight of lignin) ]]]]]]]]]]]]]]. (weight of lignin) In this study the impregnation ratios were 1.0 for all samples. The impregnated sample was set on a ceramic boat which was then inserted in a stainless tube (i.d.535 mm). The impregnated sample was heated up to the carbonization temperature under N 2 ow at the rate of 108C / min and was held for 1 h at the carbonization temperature. The carbonization temperature was varied over the temperature range of 500 to 9008C. After carbonization, the sample was cooled down under N 2 ow, and the carbonized sample was washed sequentially several times with hot water, and nally with cold distilled water to remove residual chemical. The washed sample was dried at 1108C to prepare the activated carbon. The yield was calculated based on the weight of lignin and the chemical recovery was estimated using the following equation:

(weight of sample before washing) 2 (weight of sample after washing) ]]]]]]]]]]]]]]. (weight of impregnated chemical)

2.2. Characterization of pore structure

The adsorption isotherm of N 2 was measured on the activated carbon at 77 K by use of a constant volume adsorption apparatus (BELSORP 28, BEL Japan Inc.). Before measuring the isotherm, the activated carbon was heated at 2008C for 2 h in vacuo to clean its surface. The surface area of the activated carbon was calculated by the BET method using the adsorption isotherm of N 2 . The micropore volume was calculated from the amount adsorbed at relative pressure of 0.1 in the N 2 isotherm, and the mesopore volume was calculated by subtracting the amount adsorbed at relative pressure of 0.1 from that at 0.95 [17].

2.3. Thermogravimetric analysis

The weight loss behavior of the lignin impregnated with chemical during the carbonization was measured using a thermobalance (TGA-50, Shimadzu). Samples were heated to 10008C at a heating rate of 108C / min under N 2 ow. In order to compare the prepared activated carbon with commercial products, the surface areas and the pore volumes of two commercial activated carbons prepared from coconut shell and coal were measured. Results are summarized in Table 2.

3. Results and discussion

3.1. The inuence of chemical reagent and carbonization temperature on the surface area
The surface areas of activated carbons prepared at different temperatures using various activating reagents are shown in Fig. 1. The lignin chars prepared at the carbonization temperature of 500 to 9008C without chemical activation had surface areas of 1050 m 2 / g, and are not shown in this gure. Using ZnCl 2 and H 3 PO 4 as the activating reagent, it is observed that the surface areas were around 1000 m 2 / g

Table 1 Elemental analysis of lignin [wt.% (d.a.f)] C 59.8 H 5.3 N 0.1 O(diff.) 34.8 [wt.% (d.b.)] Ash 4.0

J. Hayashi et al. / Carbon 38 (2000) 1873 1878

1875

commercial activated carbons. Thus activated carbons with very high specic surface areas can be prepared from lignin by chemical activation with K 2 CO 3 . The surface area is a maximum value at the temperature of 8008C in alkali metal compound activation, and at the temperature of 6008C with ZnCl 2 and H 3 PO 4 activation. These results indicate that at temperatures greater than 6008C, alkali metal compounds work effectively as activating reagents, but ZnCl 2 and H 3 PO 4 do not. This suggests that there is a difference in the activation mechanism between the alkali metal compounds and the ZnCl 2 and H 3 PO 4 .

3.2. The inuence of chemical reagent and carbonization temperature on the pore volume
The inuences of chemical reagent and carbonization temperature on the pore volume are shown in Fig. 2. This gure indicates that the micropores are well developed in the activated carbons prepared in this study. The pore volumes (micropore volume1mesopore volume) of the activated carbons prepared by ZnCl 2 and H 3 PO 4 activation increase with an increase in temperature over the range 500 to 6008C, and decrease with an increase in temperature over the range of 600 to 9008C. At temperatures above 6008C, the carbon structure shrinks, and the surface areas decrease as shown in Fig. 1 and the pore volumes decrease as shown in Fig. 2. The pore volumes of the activated carbons prepared by alkali metal compound activation generally increases with carbonization temperatures up to about 8008C. This indicates that the pores enlarge up to this temperature. Above 8008C, the excess enlargement induces combination of pores, resulting in an increase in mesopores for all alkali metal salts, and a decrease of micropore volume, and of surface area.

Fig. 1. Inuences of carbonization temperature and activating reagent on the surface area of prepared activated carbon.

and 700 m 2 / g at 5008C, respectively. The surface areas of these activated carbons are much larger than that of the lignin char. This indicates that ZnCl 2 and H 3 PO 4 work effectively as activating reagents below 5008C. The surface areas increase between the temperature of 500 and 6008C and the maximum surface areas of more than 1000 m 2 / g are observed at 6008C. From comparison with Table 2, the activated carbons prepared from lignin by chemical activation with ZnCl 2 and H 3 PO 4 have surface areas as large as those of the commercial activated carbons. In contrast, using the alkali metal compounds as activating reagent the surface areas of activated carbons prepared at a temperature of 5008C are very small compared with those of activated carbons prepared by ZnCl 2 and H 3 PO 4 activation. This indicates that the activation mechanisms of alkali metal compounds are different from those of ZnCl 2 and H 3 PO 4 below 5008C. The surface areas increase between the temperatures of 500 and 8008C, and then decrease with a further increase of temperature from 800 to 9008C. This shows that alkali metal compounds work as activating reagents effectively above 6008C. The surface areas of the activated carbon prepared by alkali metal compound activation (except for Na 2 CO 3 ) at 8008C are well over 1000 m 2 / g, and are larger than those of the commercial activated carbons. In particular, the carbon prepared by K 2 CO 3 activation has a surface area of about 2000 m 2 / g, being much larger than that of the

3.3. The mechanism of chemical activation

The mechanism of chemical activation can best be illustrated from the properties of activated carbons prepared by K 2 CO 3 and ZnCl 2 , which showed different tendencies in pore structural change. The effect of activating chemical on the weight loss behavior during the carbonization is shown in Fig. 3a which indicates the experimental and the calculated weight loss rates for the lignin impregnated with ZnCl 2 , and in Fig. 3b which shows the weight loss rates of the lignin and ZnCl 2 measured independently. The calculated rate in Fig. 3a was obtained by assuming that the weight loss for the lignin impregnated with ZnCl 2 was a summation of the values for lignin and ZnCl 2. A difference between experimental and calculated rates was found in the temperature range of 200 to 6008C in Fig. 3a. This difference indicates that ZnCl 2 as an activating reagent modies the carbonization behavior of lignin in this temperature range.

1876

J. Hayashi et al. / Carbon 38 (2000) 1873 1878

Fig. 2. Inuences of carbonization temperature and activating reagent on the pore volume of prepared activated carbon.

In the temperature range of 200 to 3508C, the experimental rate was larger than the calculated rate. This shows the evolution of the volatile matter due to the impregnation of the ZnCl 2 . Ahmadpour et al. [18] carbonized bituminous coal impregnated with ZnCl 2 and found that hydrogen was evolved below 2008C. When lignin impregnated with ZnCl 2 was carbonized, it was deduced that hydrogen was evolved as reported by Ahmadpour et al. [18]. This evolution of hydrogen could contribute to the difference of weight loss rate. In the temperature range of 350 to 4508C, the experimental rate is somewhat smaller than the calculated rate, and this shows that the evolution of the volatile matter is restricted by the impregnation of ZnCl 2 . The volatile matter evolved in this temperature range is mainly tar [19]. It is generally claimed that ZnCl 2 works as dehydration reagent [19,20] and then it is deduced that the dehydration induces the charring and aromatization of the carbon and restricted the formation of tar in this temperature range.

Therefore the experimental rate was somewhat smaller than the calculated rate. In the temperature range of 450 to 6008C, the experimental rate is very much smaller than the calculated rate. It appears that the restriction of ZnCl 2 evaporation contributes to this difference. Little difference between the experimental and the calculated rate is observed above the temperature of 6008C. ZnCl 2 works effectively only below a temperature of 6008C. Fig. 4a shows the experimental and calculated weight loss rates of the lignin impregnated with K 2 CO 3 and Fig. 4b shows the weight loss rates of the lignin and K 2 CO 3 measured independently. In Fig. 4a, around a temperature of 4008C, the experimental weight loss rate peak shifts to the lower temperature range compared with the calculated one. Beguin et al. [21], Mochida et al. [22,23] and Yamashita et al. [24] found that dehydrogenation started at a relatively low temperature with the addition of alkali metal compounds. Similarly, in this study the dehydroge-

J. Hayashi et al. / Carbon 38 (2000) 1873 1878

1877

Fig. 3. (a) Experimental and calculated weight loss rate behaviors of ligninZnCl 2 and (b) weight loss rate behaviors of lignin and ZnCl 2 separately.

Fig. 4. Experimental and calculated weight loss rate behaviors of ligninK 2 CO 3 and (b) weight loss rate behaviors of lignin and K 2 CO 3 separately.

nation started at a relatively low temperature with the addition of K 2 CO 3 and the weight loss rate peak shifted to the lower temperature range. As described above, the addition of K 2 CO 3 modied the carbonization behavior of the lignin below 5008C. However, the surface area of the activated carbon prepared by K 2 CO 3 activation at 5008C is very small, as shown in Fig. 1. It can be presumed that the micro- or mesopore structure was scarcely modied. A large difference in rates is observed around the temperature of 8008C. It is clear that this increase is not due to the independent evaporation of K 2 CO 3 , because K 2 CO 3 by itself evaporates above 9008C as shown in Fig. 4b. Therefore it is concluded that this increase of the rate is due to the evaporation of K 2 CO 3 and / or the volatile matter from lignin, which is induced by the reaction of the carbonized lignin and K 2 CO 3 . The results show that K 2 CO 3 modies the carbonization behavior of the lignin as a chemical reagent in two temperature ranges, below 5008C and above 6008C, while ZnCl 2 modies the behavior below 6008C. Fig. 5 shows the yields of the prepared activated carbons based on the weight of the lignin. It is observed that the yields of the chars impregnated with ZnCl 2 are larger than those of the chars with no impregnation in the temperature range of 500 to 9008C. This fact supports the premise that ZnCl 2 promotes the charring and aromatization of the carbon. It is observed that the yields of the chars im-

pregnated with ZnCl 2 scarcely change in the temperature range of 600 to 9008C. In this temperature range the surface area and the pore volume of the activated carbon prepared by ZnCl 2 decrease as shown in Fig. 1. This decrease appears to be due to heat shrinking. The yields of the chars impregnated with K 2 CO 3 decrease between the temperatures of 7008C and 9008C, while the yields of other chars scarcely change. It is clear that the char is gasied by K 2 CO 3 . McKee [25] studied the

Fig. 5. Yields of lignin, lignin impregnated with K 2 CO 3 and lignin impregnated with ZnCl 2 at different carbonization temperatures.

1878

J. Hayashi et al. / Carbon 38 (2000) 1873 1878

K 2 CO 3 worked as the dehydrogenation reagent in activation below 5008C. It was reduced by carbon above 6008C, consequently carbon was removed as CO and the surface area and the pore volume increased. However, with excess activation pores were combined, and mesopore volume increased and the surface area decreased.

References
[1] Kumamoto S, Takahashi Y, Ishibashi K, Noda Y, Yamada K, Chida T. Trans Mater Res Soc Jpn 1994;18A(Ecomaterials):64750. [2] Simitzis J, Sfyrakis J. J Appl Polym Sci 1994;54(13):2091 9. [3] Simitzis J, Sfyrakis J, Faliagas A. J Appl Polym Sci 1995;58(3):54150. [4] Gonzalez-Serrano E, Cordero T, Rodriguez-Mirasol J, Rodriguez JJ. Ind Eng Chem Res 1997;36(11):48328. [5] Ahmadpour A, Do DD. Carbon 1997;35(12):172332. [6] Tsai WT, Chang CY, Lee SL. Carbon 1997;35(8):1198200. [7] Sun J, Brady TA, Rood MJ, Lehmann CM, Rostam-Abadi M, Lizzio AA. Energy Fuels 1997;11(2):31622. [8] Bacaoui A, Yaacoubi A, Bennouna C, Dahbi A, Ayele J, Mazet M. Aqua (Oxford) 1998;47(2):6875. [9] Xia J, Noda K, Kagawa S, Wakao N. J Chem Eng Jpn 1998;31(6):98790. [10] Tsai WT, Chang CY, Lee SL. Bioresour Technol 1998;64(3):2117. [11] Marsh H, Yan DS, Orady TM, Wennerberg A. Carbon 1984;22(6):60311. [12] Caturla F, Molina-Sabio M, Rodriguez-Reinoso F. Carbon 1991;29(7):9991007. [13] Hu Z, Srinivasan MP. Microporous Mesoporous Mater 1999;27(1):118. [14] Qiao W, Ling L, Zha Q, Liu L. J Mater Sci 1997;32(16):444753. [15] Teng H, Yeh T. Ind Eng Chem Res 1998;37(1):5865. [16] Illan-Gomez MJ, Garcia-Garcia A, Salinas-Martinez LC, Linares-Solano A. Energy Fuels 1996;10(5):110814. [17] Rodriguez-Reinoso F, Lopez-Gonzalez JD, Berenguer C. Carbon 1982;20(6):5138. [18] Ahmadpour A, Do DD. Carbon 1996;34(4):4719. [19] Rodriguez-Reinoso F, Molina-Sabio M. Carbon 1992;30(7):11118. [20] Balci S, Dogu T, Yucel H. J Chem Tech Biotechnol 1994;60(4):41926. [21] Beguin F, Settan R. Carbon 1972;10(5):53951. [22] Mochida I, Nakamura E, Maeda K, Takeshita K. Carbon 1975;13(6):48993. [23] Mochida I, Nakamura E, Maeda K, Takeshita K. Carbon 1976;14(2):1239. [24] Yamashita Y, Ouchi K. Carbon 1982;20(1):415. [25] McKee DW. Fuel 1983;62(2):1705.

Fig. 6. K 2 CO 3 recovery ratios at different carbonization temperatures.

gasication of graphite by alkali metal and found that K 2 CO 3 was reduced in inert atmosphere by carbon as follows: K 2 CO 3 1 2C 2K 1 3CO Fig. 6 shows the recovery ratios of K 2 CO 3 over the temperature range 500 to 9008C. The recovery ratio decreases with an increase of the temperature. This result supports previous ndings that K 2 CO 3 is reduced by carbon in inert atmospheres.

4. Conclusion Activated carbons have been prepared from lignin by chemical activation. The maximum surface areas of the activated carbons prepared by ZnCl 2 activation and by H 3 PO 4 activation observed at 6008C, were as large as values for commercial activated carbons. The micropores were well developed. In contrast, the maximum surface areas of activated carbons prepared with alkali metal compounds occurred at 8008C, and were generally larger than the surface areas of the commercial activated carbons. With K 2 CO 3 activation, the surface area reached about 2000 m 2 / g. The mesopore volumes were seen to increase with carbonization temperature. ZnCl 2 worked as dehydration reagent and restricted the formation of tar and promoted the charring of the carbon below the carbonization temperature of 6008C. Consequently the carbon structure was modied and the surface area increased. However, above 6008C ZnCl 2 does not work as an activation reagent, and the surface area and the pore volume decreased because of heat shrinkage.