Carbon 41 (2003) 823831

Gas adsorption on activated carbons from PET mixtures with a metal salt
Kyuya Nakagawa*, Shin R. Mukai, Tetsuo Suzuki, Hajime Tamon
Department of Chemical Engineering, Kyoto University, Kyoto 606 -8501, Japan Received 4 October 2002; accepted 16 November 2002

Abstract Activated carbons were prepared from carbonized PET by steam activation via pretreatment by mixing PET with a metal salt [Ca(NO 3 ) 2 ?4H 2 O, Ca(OH) 2 , CaCO 3 , ZnO, and AlNH 4 (SO 4 ) 2 ?12H 2 O], and with acid treatment after carbonization. The porous properties of the activated carbons were determined by the nitrogen adsorption method. The adsorption isotherms of CO 2 , C 2 H 6 , nC 4 H 10 and iC 4 H 10 at 298 K on the prepared activated carbons were measured to determine practical applications and to obtain a better understanding of the porous structure of the prepared carbons. Steam-activated carbons via pretreatment have a larger mesoporosity than carbons with no pretreatment. The metal salt used in the pretreatment for steam activation has no inuence on the microporous structure, but it does inuence the mesoporous structure of the prepared carbons. Activated carbons prepared via pretreatment show a large adsorption capacity for nC 4 H 10 and iC 4 H 10 . These carbons are suitable as adsorbents for canisters, etc. Application of the potential theory to adsorption data for the prepared carbons suggests that the pretreatment contributes to the formation of pores larger than 0.50 nm at high burnoff. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: A. Activated carbon; B. Activation; C. Adsorption; D. Porosity

1. Introduction Activated carbons are widely used in gas purication, solvent recovery, waste water treatment, etc. It is recognized that the pore structure is the most important property of activated carbons for their application in adsorption processes [1]. Activated carbons have a very wide range of pore sizes, from the Angstrom scale of micropores to the micrometer scale of macropores. They are used in various applications depending on their porous properties. For example, activated carbons with many micropores are used for gas adsorption, mesopores are necessary for the adsorption of large molecules, etc. Woods, coconut shell, coal, lignite, peat, etc. are usually chosen as raw materials for activated carbons. Various carbons differing in porous properties can be obtained by changing the raw materials and / or the preparation conditions, i.e. the carbonization and activation conditions. Many investigations have been performed to explore novel
*Corresponding author. Tel.: 181-75-753-5594; fax: 181-75753-3346. E-mail address: qya@cheme.kyoto-u.ac.jp (K. Nakagawa).

raw materials (such as waste materials) and to optimize the preparation conditions to obtain activated carbons with the desired porous properties. Optimization of the activation process has been extensively investigated [26]. As reported in the literature, pore development by activation reactions is governed by the diffusivity and reactivity of the activation agents. Mesopores develop under the conditions where micropore development is restricted, and vice versa. These conditions are determined by complex combinations of the activation temperature, activation agents, concentrations of activation agents, and the pore structures of the activated materials, which inuence the diffusivity and / or reactivity of the activation agents. This knowledge is very important not only to decide on the activation conditions, but also to deduce methods for developing many pores in activated carbons. The application of catalytic activation is one method for developing many pores. This is the way to produce reactive sites on the surface of carbons and to accelerate pore development. It has been reported that the formation of micropores is restricted in the presence of catalysis and many mesopores are obtained [79]. Siemieniewska et al. reported that the application of a graphite intercalation process during the

0008-6223 / 02 / $ see front matter 2002 Elsevier Science Ltd. All rights reserved. doi:10.1016 / S0008-6223(02)00404-9

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preparation of carbon adsorbents is applicable for controlling the porous properties [10]. The present authors proposed a new method to prepare activated carbons with different pore size distributions from PET in a previous report [11]. In that article, we used two preparation methods. One was a conventional steamactivation method. The other was steam activation via pretreatment, that is, mixing the raw material (PET) with a calcium compound and then acid treatment after carbonization to wash out the mixed calcium compound. The activated carbons prepared by the latter method have many mesopores and micropores. In contrast, activated carbons prepared by the conventional method have mainly micropores. These results suggest that the pretreatment method is useful for preparing mesoporous activated carbons. This article reports the preparation of activated carbons from carbonized PET by steam activation via pretreatment, that is, mixing the raw materials (PET) with a metal salt [Ca(NO 3 ) 2 ?4H 2 O, Ca(OH) 2 , CaCO 3 , ZnO, or AlNH 4 (SO 4 ) 2 ?12H 2 O] and acid treatment after carbonization. The inuence of the metal salt on the porous properties of the prepared activated carbons was investigated. The porous properties of the prepared carbons were determined by the nitrogen adsorption method. Adsorption isotherms of CO 2 , C 2 H 6 , nC 4 H 10 and iC 4 H 10 at 298 K on the prepared activated carbons were also measured to conrm the micropore structures and to determine the practical application of the prepared activated carbons as adsorbents.

after acid treatment contained no ash, which was conrmed by thermogravimetric analysis (Rigaku, TG-8120).

2.3. Steam activation

Activated carbons were prepared from chars by steam activation. 0.4 g of the char was placed in a quartz reactor, and heated in an electric furnace from room temperature to 1123 K at 20 K / min. The gas ow rate was 200 cm 3 / min and the steam concentration was 0.0025 g / cm 3 . The activation time (i.e., the holding time at 1123 K) was changed from 0 to 240 min in order to prepare carbons of different burnoff. Four series of carbons were prepared. The HT series of carbons were heat treated at 1123 K for a few minutes without steam ow. The 0A series of carbons were held at 1123 K for 5 min under steam ow. The 1A series of carbons were held at 1123 K for 90120 min under steam ow. The 2A series of carbons were held at 1123 K for 180240 min under steam ow.

2.4. Characterization of activated carbons

Adsorption and desorption isotherms of N 2 on the activated carbons were measured at 77 K using a volumetric adsorption apparatus (BEL Japan, BELSORP28). The BET method was used to evaluate the specic surface area of the activated carbons from the adsorption isotherms. The pore size distribution (range of pore radii 1.020 nm) was estimated by applying the Dollimore Heal method [12] to the desorption isotherms, and the mesopore volume was determined. The micropore volume was evaluated by the t-plot method [13]. The adsorption isotherm of N 2 on Spheron 6 was adopted, which was measured by BEL Japan as the standard isotherm. Adsorption isotherms of CO 2 , C 2 H 6 , nC 4 H 10 and iC 4 H 10 were also measured on the activated carbons at 298 K using the same apparatus.

2. Experiment

2.1. Carbonization
Pellets (diameter |2 mm, length |2 mm) of PET (polyethylene terephthalate) were used for the raw material of the activated carbons. Ten grams of PET pellets were mixed with 5 wt% of metal salts, and the samples were then set in a quartz reactor and heated by an electric furnace. The reactor was kept under an inert atmosphere with a N 2 ow of 80 cm 3 / min. The reactor was heated from room temperature to 773 K at 0.4 K / min, and kept at 773 K for 1 h. The obtained chars were powdered by a mortar. Six groups of chars were prepared, i.e. from PET pellets (P1), and from PET pellets mixed with Ca(NO 3 ) 2 ? 4H 2 O (P2), Ca(OH) 2 (P3), CaCO 3 (P4), ZnO (P5), and AlNH 4 (SO 4 ) 2 ?12H 2 O (P6).

3. Results and discussion

3.1. Burnoff and activation time

The activation time and the burnoff of the prepared carbons are shown in Table 1. The weight loss of the HT series carbons varies from 12 to 25%. This means that a relatively large weight loss occurs before reaching 1123 K (i.e., before starting the activation reaction with steam). The weight loss is due to the vaporization of volatile matter. One can see that P2P6 group carbons have more volatile matter and disorganized carbon than group P1. It is suggested that the different carbon structure is produced by carbonization under inuence of the mixture. One can see that the burnoff of 0A series carbons varies from 13 to 29%. Burnoff then increases linearly to the holding time for all groups of 1A and 2A series

2.2. Acid treatment

Two grams of the char was impregnated in 100 cm 3 1.0 N HCl solution at room temperature for 24 h and stirred using a magnetic stirrer. After acid treatment, the samples were washed with distilled water until the pH of the ltrate was |5.0, and then dried in an oven at 383 K. Carbons

K. Nakagawa et al. / Carbon 41 (2003) 823831 Table 1 Preparation conditions and porous properties of the prepared activated carbons Group P1 Mixture None Series HT 0A 1A 2A HT 0A 1A 2A HT 0A 1A 2A HT 0A 1A 2A HT 0A 1A 2A HT 0A 1A 2A Activation time (min) 0 5 120 240 0 5 150 180 0 5 150 180 0 5 150 240 0 5 1150 240 0 5 150 240 Burnoff (wt%) 12.5 12.7 68.7 77.8 13.2 18.0 63.7 85.7 25.0 29.4 60.6 81.0 14.4 20.7 57.1 87.5 13.9 20.5 61.6 85.9 15.6 23.3 63.5 85.1 SBET a (cm 2 / g) 394 456 1450 1740 396 521 1460 2190 419 495 1200 1960 421 446 1170 2180 416 459 1240 2240 370 493 1220 2080 Vmic b (cm 3 / g) 0.21 0.24 0.72 0.93 0.20 0.25 0.66 0.81 0.21 0.23 0.55 0.86 0.22 0.23 0.59 0.93 0.20 0.25 0.66 1.10 0.17 0.27 0.66 0.82

825

Vmes c (cm 3 / g) 0.04 0.06 0.13 0.15 0.04 0.08 0.27 0.90 0.07 0.08 0.19 0.50 0.09 0.05 0.14 0.78 0.09 0.05 0.16 0.87 0.03 0.04 0.11 0.61

P2

Ca(NO 3 ) 2 ?4H 2 O

P3

Ca(OH) 2

P4

CaCO 3

P5

ZnO

P6

AlNH 4 (SO 4 ) 2 ?12H 2 O

SBET , BET surface area. Vmic , micropore volume. c Vmes , mesopore volume.
b

carbons, and the overall reaction rates of P2P6 group carbons are a little higher than group P1 carbons. It is suggested that the activation reactions of all groups of carbons are typical steam-activation reactions, and their activation processes are similar.

3.2. Porous properties of the prepared activated carbons 3.2.1. N2 adsorption isotherms Fig. 1 shows examples of N 2 adsorption isotherms at 77 K on the prepared activated carbons. The amount of N 2 adsorbed on each group of carbons increases with burnoff, as expected. All groups of HT and 0A series carbons have type I adsorption isotherms according to the BDDT classication. The P1 group of carbons exhibited type I isotherms with increasing burnoff (Fig. 1a). On the other hand, the shape of the isotherms changed for the P2 group of carbons as burnoff increased (Fig. 1b). These isotherms become type IV, and suggest the formation of mesopores. 3.2.2. Effect of burnoff on porous properties As shown in Table 1, the porous properties of the prepared activated carbons vary from 370 to 2200 m 2 / g

for the BET surface area, from 0.2 to 1.1 cm 3 / g for the micropore volume, and from 0.04 to 0.9 cm 3 / g for the mesopore volume. The porous properties of P1 group carbons are fairly similar to those reported in the literature [14]. These activated carbons have a BET surface area .1000 m 2 / g and mainly contain micropores. It is noteworthy that the mesopore volume of 2A series carbons of groups P2P6 are quite large. Although the porous properties of HT series carbons of all groups are quite similar, the properties of the carbons become different with an increase in burnoff. Micropore volume and mesopore volume are plotted as a function of burnoff in Fig. 2. It is conrmed that all groups of carbons have similar micropore volumes (Fig. 2a). On the contrary, it can be seen that the development of mesopores of P2P6 group carbons is much larger than that of group P1 with a burnoff of more than 60% (Fig. 1b).

3.2.3. Pore size distributions Mesopore size distributions calculated by the DollimoreHeal method are shown in Fig. 3. It is clear that the distributions of group P1 differ greatly from those of groups P2P6. In group P1, mesopores are formed in the

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Fig. 1. Adsorption and desorption isotherms for N 2 at 77 K. (a) Group P1, (b) group P2. Closed symbols, adsorption; open symbols, desorption.

region narrower than pore radii of 2 nm and the region wider than pore radii of 9 nm as burnoff increases (Fig. 3a). In groups P2P6, the development of mesopores is remarkable in the region 29 nm, and mesopores are also formed in the region narrower than pore radii of 2 nm and the region wider than pore radii of 9 nm (Fig. 3bf).

Great differences are not observed in pore size distributions of HT, 0A and 1A series carbons of groups P2P6. On the other hand, differences in the development of pore radii of 29 nm are observed in 2A series carbons. The shapes of the pore size distributions of groups P2, P4 and P5 are similar (Fig. 3b, d and e), that is, the

Fig. 2. Pore volumes of the prepared activated carbons as a function of burnoff. (a) Burnoff vs. micropore volume; (b) burnoff vs. mesopore volume.

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Fig. 3. Pore size distributions. (a) Group P1, (b) group P2, (c) group P3, (d) group P4, (e) group P5, (f) group P6.

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peaks in the region 29 nm are sharper and larger than those of groups P3 and P6 (Fig. 3c and f). Hence, the mixture of metal salts inuences the porous structure of carbons when burnoff is high.

3.3. Gas adsorption characteristics 3.3.1. Adsorption isotherms It was demonstrated in the previous section that activated carbons prepared via pretreatment have unique mesopore size distributions. It is also expected that these activated carbons will have different adsorption characteristics from commercial activated carbons. The adsorption isotherms of gases are useful for conrming the applications of the prepared activated carbons as adsorbents, and for a better understanding of the pore structure of the prepared carbons. The adsorption isotherms of CO 2 , C 2 H 6 , nC 4 H 10 and iC 4 H 10 at 298 K on the prepared activated carbons were measured. The adsorption isotherms of CO 2 , C 2 H 6 and nC 4 H 10 on a commercial activated carbon [15] were used as the reference isotherms. Adsorption isotherms for CO 2 are shown in Fig. 4. The amount of CO 2 adsorbed on all groups of carbons did not change much as burnoff increased and the amount of CO 2 adsorbed on 2A series carbons was smaller than on carbons of the other series. This trend is also found for P3P6 group carbons, and is the most remarkable for group P1 carbons. One can see that the amount of CO 2 adsorbed on the 2A series carbon of group P1 is much smaller than that of commercial activated carbon (Fig. 4a). This is because the adsorption potential becomes weak as the pore size increases by activation. One can see that the amount of CO 2 adsorbed on all series of carbons is larger than that of the commercial activated carbon, except for the 2A series carbon of group P1. Adsorption isotherms for C 2 H 6 are shown in Fig. 5. The

amounts of C 2 H 6 adsorbed on HT and 0A series carbons of all groups are similar. The amount of C 2 H 6 adsorbed on all groups of carbons increases with burnoff, and a large increase of the amount adsorbed is observed between 0A and 1A series carbons. However, the amount adsorbed on 2A carbon greatly decreases in group P1 (Fig. 5a), as observed in the CO 2 adsorption isotherms. The amounts adsorbed on 1A and 2A carbons of group P2 are almost the same, and much larger than the commercial activated carbon (Fig. 5b). Similar results were also observed on P3P6 group carbons. Adsorption isotherms for nC 4 H 10 are shown in Fig. 6. The amounts of nC 4 H 10 adsorbed on all groups of carbons increase with burnoff. This result is different from CO 2 or C 2 H 6 adsorption. The amounts adsorbed on 1A series carbons are much larger than those on 0A series carbons. Fig. 6a shows that the amounts of nC 4 H 10 adsorbed on 1A and 2A series carbons are almost the same as those on the commercial carbon. On the other hand, Fig. 6b shows that the adsorption capacity of nC 4 H 10 of 1A and 2A series carbons are much larger than that of the commercial carbon. These results are also observed for P3P6 group carbons. Adsorption isotherms for iC 4 H 10 are shown in Fig. 7. Figs. 6 and 7 show that the amounts of iC 4 H 10 adsorbed are much smaller than those of nC 4 H 10 on HT series carbons of groups P1 and P2. Hence, HT series carbons would show a molecular sieving effect for the adsorption of nC 4 H 10 and iC 4 H 10 . 0A series carbons adsorb iC 4 H 10 more than HT series carbons because of steam activation. It can be seen that the amounts of iC 4 H 10 adsorbed on 1A series carbons are much larger than those on 0A series carbons. The differences in the amounts adsorbed on 1A and 2A series carbons of group P2 are much larger than those of group P1. This is the same trend as for the nC 4 H 10 adsorption isotherms, and also observed for P3P6

Fig. 4. Adsorption isotherms for CO 2 at 298 K. (a) Group P1, (b) group P2.

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Fig. 5. Adsorption isotherms for C 2 H 6 at 298 K. (a) Group P1, (b) group P2.

group carbons. Hence, it is suggested that these activated carbons can be applied as adsorbents for canisters, etc.

3.3.2. Application of adsorption potential theory to gas adsorption isotherms The modication of the PolanyiDubinin adsorption theory proposed by Lewis et al. [16] is given by
[(RT /V 9) ln( fs /f )] I 5 [(RT /V 9) ln( fs /f )] II when NIV 9 5 NIIV 9 I II (2) (1)

where f is the fugacity of the gas at the adsorption pressure and temperature, fs is the fugacity of the saturated liquid at the adsorption temperature, N is the moles adsorbed per

unit weight adsorbent, R is the gas law constant, T is the adsorption temperature, and V 9 is the molal volume of saturated liquid at the vapor pressure equal to the adsorption pressure. If the adsorption potential theory can be applied to adsorption equilibrium, plots of NV 9 versus (T /V 9) ln( fs /f ) for all the adsorbates would fall on one curve. When the potential theory is applied to the adsorption isotherms of several adsorbates of different molecular sizes (CO 2 , 0.33 nm; C 2 H 6 , 0.40 nm; nC 4 H 10 , 0.43 nm; iC 4 H 10 , 0.50 nm), the formation of pores in the activated carbons during activation can be postulated. Fig. 8 shows plots of the adsorption capacities versus the adsorption potential. The amount of CO 2 and C 2 H 6 adsorbed on HT series carbons can be correlated with the potential, as shown in Fig. 8a. Hence, it was found that HT series carbons of all groups have the same micropore

Fig. 6. Adsorption isotherms for nC 4 H 10 at 298 K. (a) Group P1, (b) group P2.

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Fig. 7. Adsorption isotherms for nC 4 H 10 at 298 K. (a) Group P1, (b) group P2.

Fig. 8. Correlation of adsorption isotherms. (a) HT series, (b) 1A series, (c) 2A series.

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structure in the region ,0.40 nm. On the other hand, the adsorption data for nC 4 H 10 do not t the correlation curve and the data for iC 4 H 10 greatly deviate from the curve. Since the amount of iC 4 H 10 adsorbed is extremely small compared with nC 4 H 10 , it can be seen that the carbons show the molecular sieving effect and that all their pores are smaller than 0.50 nm. As steam activation proceeds, the micropore structure of the carbon prepared via pretreatment for steam activation (groups P2P6) becomes different from that of the carbons prepared by conventional steam activation (group P1). Fig. 8b suggests that the adsorption data for CO 2 , C 2 H 6 , and nC 4 H 10 on 1A series carbons of groups P1P6 can be correlated by the potential theory. However, data for the carbons of group P1 deviate in the low potential region. Hence, it can be seen that all carbons prepared via pretreatment (groups P2P6) have the same micropore structure. For the adsorption of CO 2 , C 2 H 6 , nC 4 H 10 , and iC 4 H 10 on 2A series carbons, correlation of the adsorption data is shown in Fig. 8c. The deviation of the data for group P1 from the correlation curve is larger than that for the 1A carbons shown in Fig. 8b. Hence, it can be seen that steam activation pretreatment contributes to the formation of pores larger than 0.50 nm.

References
[1] Wigmans T. Industrial aspects of production and use of activated carbons. Carbon 1989;27:1322. [2] Pastor-Villegas J, Duran-Valle CJ. Pore structure of activated carbons prepared by carbon dioxide and steam activation at different temperatures from extracted rockrose. Carbon 2002;40:397402. [3] Molina-Sabio M, Gonzalez MT, Rodrguez-Reinoso F, Sep ulveda-Escribano A. Effect of steam and carbon dioxide activation on the micropore size distribution of activated carbon. Carbon 1996;34:5059. [4] Gergova K, Eser S. Effect of activation method on the pore structure of activated carbons from apricot stones. Carbon 1996;34:87988. [5] Gonzalez MT, Molina-Sabio M, Rodrguez-Reinoso F. Steam activation of olive stone chars, development of porosity. Carbon 1994;32:140713. [6] Rodrguez-Reinoso F, Molina-Sabio M, Gonzalez MT. The use of steam and CO 2 as activating agents in the preparation of activated carbons. Carbon 1995;33:1523. [7] Yoshizawa N, Yamada Y, Furuta T, Shiraishi M, Kojima S, Tamai H et al. Coal-based activated carbons prepared with organometallics and their mesoporous structure. Energy Fuels 1997;11:32730. [8] Oya A, Yoshida S, Alcaniz-Monge J, Linares-Solano A. Formation of mesopores in phenolic resin-derived carbon ber by catalytic activation using cobalt. Carbon 1995;33:108590. [9] Cazorla-Amoros D, Ribes-Perez D, Roman-Martnez MC, Linares-Solano A. Selective porosity development by calcium-catalyzed carbon gasication. Carbon 1996;34:86978. [10] Siemieniewska T, Albiniak A, Broniek E, Kaczmarczyk J, Jankowska A, McEnaney B et al. Porosity development in steam activated chars from mixtures of coal tar pitch with graphiteFeCl 3 intercalation compounds. Fuel 1998;77:509 17. [11] Tamon H, Nakagawa K, Suzuki T, Nagano S. Improvement of mesoporosity of activated carbons from PET by novel pre-treatment for steam activation. Carbon 1999;37:16435. [12] Dollimore D, Heal GR. An improved method for the calculation of pore-size distribution from adsorption data. J Appl Chem 1964;14:10914. [13] Lippens BC, Boer JH. Pore system in catalysts, v. the t-method. J Catal 1965;4:31923. [14] Laszlo K, Bota A, Nagy LG, Cabasso I. Porous carbon from polymer waste materials. Colloids Surfaces A 1999;151:31120. [15] Valenzuela DP, Myers AL, editors, Adsorption equilibrium data handbook, Englewood Cliffs, NJ: Prentice-Hall, 1989, p. 33, 51, 80. [16] Lewis WK, Gilliland ER, Chertow B, Cadogan WP. Adsorption equilibria. Pure gas isotherms. Ind Eng Chem 1950;42:132632.

4. Conclusion Activated carbons were prepared by steam activation from carbonized PET via a mixture of several metal salts and acid treatment. The effects of different mixtures on the porous properties of the prepared activated carbons are discussed. The adsorption isotherms for CO 2 , C 2 H 6 , nC 4 H 10 and iC 4 H 10 on the prepared activated carbons were measured to conrm practical applications and for a better understanding of the porous structure of the prepared carbons, and the following conclusions were obtained. 1. Activated carbons prepared from PET have a large porosity. Steam-activated carbons via a mixture of metal salts and acid treatment as the pretreatment for activation have a larger mesoporosity than carbons with no pretreatment. 2. The kind of metal salt used in the pretreatment for steam activation does not inuence the microporous structure, but does inuence the mesoporous structure of the prepared carbon. 3. Since the activated carbons prepared via pretreatment show a large adsorption capacity for nC 4 H 10 and iC 4 H 10 compared with commercial carbon, the prepared carbons are suitable as adsorbents for canisters, etc. 4. Application of the potential theory to adsorption data for the prepared carbons suggests that the pretreatment contributes to the formation of pores larger than 0.50 nm at high burnoff.