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Energy & Fuels 2006, 20, 432-438

Hydrogen Production by Gasification of Cellulose over Ni Catalysts Supported on Zeolites


Megumu Inaba,* Kazuhisa Murata, Masahiro Saito, and Isao Takahara
National Institute of AdVanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan ReceiVed September 2, 2005. ReVised Manuscript ReceiVed NoVember 25, 2005

Hydrogen production by cellulose gasification over Ni catalysts was investigated. The catalytic activity and the species of products were affected by the type of supports. The use of simple metal oxides as supports resulted in the formation of large quantities of dark-colored tar but avoided carbon deposition, whereas the use of zeolites as supports inhibited tar formation but promoted carbon deposition. The loading of Ce on zeolite enhanced the rate of gasification and partially inhibited carbon deposition. On the other hand, in most cases, higher reaction temperatures led to a greater quantity of hydrogen being formed, a higher rate of gasification, and less tar formation or carbon deposition. In this reaction, metallic Ni is likely to be an active site and there is a structure sensitivity of Ni and NiO crystallite: larger Ni crystallite favored hydrogen formation and inhibited tar formation, while larger NiO crystallite inhibited hydrogen formation and tar decomposition. Our results indicate that Ni/Ce/H-ZSM-5 catalyst is a promising candidate for this reaction, despite being slightly less effective than Rh/Ce/SiO2 catalyst, since Ni catalysts are cheaper.

Introduction As part of the search for alternatives to fossil fuels, which raise atmospheric CO2 levels when burned, attention is increasingly focusing on the potential of biomass for use as a renewable energy resource. Hydrogen, too, is an ideal clean energy source, since its combustion releases only water and no carbon dioxide. For this purpose, gasification of biomass is a promising method. In biomass gasification, the formation of tar is likely to be unfavorable. Although gasification at high temperatures decreases tar formation, the process requires high energy input that leads to high costs. Moreover, high temperatures may damage the gasification furnace. For these reasons, the process should be operated at low temperature. One of the most promising methods for eliminating tar from the product gas is the catalytic gasification of biomass. Many reports describe the use of catalysts (for example, dolomite); however, carbon deposition on catalysts may cause deactivation.1,2 Tomishige et al. studied the catalytic gasification of cellulose as a model of the conversion of biomass to synthesis gas.3-5 In his study, which used a fluidized bed reactor, they found that Rh catalysts supported on CeO2 or Ce/SiO2 showed high activity for this reaction. Rh/Ce/SiO2 catalysts, in particular, showed catalytic activity for a long period without the formation of tar or char.4,5 Moreover, they reported catalysts to be effective for the gasification of real biomass.6,7
* Corresponding author. Phone and fax: +81-29-861-4776. E-mail: mg.inaba@aist.go.jp. (1) Bridgwater, A. V. Appl. Catal., A: Gen. 1994, 116, 5-47. (2) Sutton, D.; Kelleher, B.; Ross, J. R. H. Fuel Process. Technol. 2001, 73, 155-173. (3) Asadullah, M.; Fujimoto, K.; Tomishige, K. Ind. Eng. Chem. Res. 2001, 40, 5894-5900. (4) Asadullah, M.; Ito, S.; Kunimori, K.; Tomishige, K. Ind. Eng. Chem. Res. 2002, 41, 4567-4575. (5) Asadullah, M.; Ito, S.; Kunimori, K.; Yamada, M.; Tomishige, K. J. Catal. 2002, 208, 255-259. (6) Asadullah, M.; Miyazawa, T.; Ito, S.; Kunimori, K.; Tomishige, K. Appl. Catal., A: Gen. 2003, 246, 103-116.

We have investigated hydrogen production by gasification of cellulose over Ni-based catalysts, since Ni has reforming ability and is cheap, and found that Ni/Ce/zeolite catalysts are effective for this reaction.8 We also studied the active site of the Ni catalyst. Experimental Section
Preparation of Catalysts. Scheme 1 shows the catalyst preparation procedure. Ni catalysts were prepared using an impregnation method. Simple metal oxides and zeolites were used as supports. As simple metal oxide supports, CeO2, SiO2, and ZrO2 were used. SiO2 was commercially obtained from Fuji Silicia. ZrO2 was obtained from Nikki. CeO2 was obtained from Wako Pure Chemicals. As zeolite supports, H- (27), H-mordenite (18.3), Namordenite (18.3), H-ZSM-5 (29), Na-ZSM-5 (29), USY (14), and Na-Y (5.7) were used (the numbers in parentheses denote Si/Al2 ratios). These were obtained from Tosoh. Before impregnation, supports were calcined at 500 C in a muffle furnace for 6 h. NaZSM-5 was prepared by ion exchange of H-ZSM-5: it was stirred in NaNO3 solution with heating, followed by filtration, drying at 120 C in an oven, and calcining at 500 C in a muffle furnace for 6 h. Ce-loaded zeolites were also prepared as supports to prevent carbon deposition during the reaction. Carbon deposition may lead to catalyst deactivation. The loading of Ce was varied from 5 to 30 wt %. Ce(NO3)36H2O (Wako Pure Chemicals) was used as the source of Ce, and an aqueous solution was used for impregnation. After impregnation with Ce, the wet supports were dried at 120 C in an oven, followed by calcining at 500 C in flowing air for 6 h. Nickel was loaded on these supports. Ni(NO3)26H2O (Wako Pure Chemicals) was used as the source of Ni and an aqueous solution was used for impregnation. The loading of Ni was 10 wt %.
(7) Asadullah, M.; Miyazawa, T.; Ito, S.; Kunimori, K.; Tomishige, K. Energy Fuels 2003, 17, 842-849. (8) Inaba, M.; Murata, K.; Saito, M.; Takahara, I. Hydrogen Production by Decomposition of Cellulose over Metal Catalysts. Presented at the Fifteenth World Hydrogen Energy Conference, Yokohama, Japan, June 27July 1, 2004.

10.1021/ef050283m CCC: $33.50 2006 American Chemical Society Published on Web 01/12/2006

H2 production by Cellulose Gasification on Ni


Scheme 1. Procedure for Catalyst Preparation

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For comparison, Rh/Ce/SiO2 and Rh/SiO2 catalysts were prepared as described by Tomishige.4-7 Rh(acac)3 (Soekawa Chemicals) was used as the source of Rh, and acetone solution was employed for impregnation. The loading of Rh was 2 wt %. Ce/SiO2 support was prepared using the same method as for Ce/zeolite support. Here, the loading of Ce was 30 wt %. In both the Ni and Rh catalysts, after impregnation, the wet supports were dried at 120 C in an oven, followed by calcining at 700 C in flowing air for 3 h. Before reaction, catalysts were pressed into pellets, crushed into particles, and sieved. Particles sized 0.5-2 mm were used. Measurement of Catalytic Activity. A schematic diagram of experimental equipment is shown in Figure 1. Catalytic activity was measured using a fixed-bed reactor. The gasification reactor was a quartz tube 35 cm in height and 9 mm in inner diameter. Reaction gas was obtained by mixing air (50%) and N2 (50%) containing N2 (ca. 90%) and O2 (ca. 10%) at a flow rate of 30 cm3 min-1. Catalyst (1 g) was placed within the reactor. W/F ) 13.3 gh mol-1, where W ) weight of the catalyst in grams and F ) flow rate of the inlet gas in moles per hour. After the reactor was heated to reaction temperature, the cap was briefly removed and the cellulose was dropped into the reactor from above. Reaction temperatures were 500 and 600 C. Commercially available cellulose (Aldrich) was used. Before the reaction, cellulose was also pressed into pellets, crushed into particles, and sieved. Particles sized 0.5-2 mm were used. The cellulose weight per experiment was 0.3 g, which contains 11 100 mol of C-atoms and 18 500 mol of H-atoms. Typically, to analyze the total gas, the effluent gas was collected using a gas bag for 30 min, and then analyzed using gas chromatography (GC) on Molecular Sieve 5A and Porapak Q columns. Tar obtained during the reaction was trapped in a glass tube cooled to 0 C in ice water. To investigate tar formation, the weight of the glass tube used to trap the tar was measured before and after seven reactions. The color of the tar was also observed. Semisolid (char) or viscous tar, which could not reach the glass tube, was obtained at the lower part of the reactor. The amounts of these products could not be measured accurately, since it was not possible to collect them individually. Therefore, to calculate the amount of tar (including char) as accurately as possible, the number of C-atoms in the tar was calculated from the amount of added cellulose, the gaseous products, and deposited carbon, as described below. Characterization of Catalysts. In most cases, carbon deposition occurred on catalysts during the reaction, and to measure the amount of deposited carbon, thermogravimetric (TG) analyses (Mac Science, TG-DTA2000) of catalysts after seven reactions were carried out. The weight of carbon was calculated from the weight loss due to combustion of deposited carbon, and from this value, the mol number of C-atoms (moles) was calculated. The mol number of C-atoms included in the tar was calculated as follows: (total mol number of C-atoms in cellulose added seven times) - (total mol number of C-atoms in gaseous products in seven reactions) - (mol number of C-atoms in deposited carbon). The mol number of

Figure 1. Schematic diagram of equipment.

H-atoms in the tar could not be calculated because some of the H-atoms in cellulose were oxidized to water. The NiO species of Ni catalysts may be partially reduced to metallic Ni during the reaction, since this reaction proceeds in a reducing atmosphere caused by the presence of cellulose. X-ray diffraction (XRD) (Mac Science, M18XHF22-SRA) measurements of catalysts after seven reactions were carried out to investigate the state of supported Ni after reactions; for example, the Ni/NiO ratio was calculated from the intensity of diffraction peaks of Ni and NiO. The size of the Ni or NiO crystallite was also calculated by Sherrers formula. Transmission electron microscopic (TEM) observations (Hitachi H9000) of catalyst before and after reaction were carried out at 300 kV to investigate the state of loaded Ni and Ce. Here, Ni/Ce/ H-ZSM-5 (Si/Al2 ) 29) (Ce ) 30 wt %) catalysts before and after seven reactions at 500 C were used as samples. Samples for TEM observation were dispersed in distilled water using an ultrasonic wave, placed on Cu grids, and dried in an air atmosphere.

Results and Discussion Catalytic Performance at 500 C. The yields of gaseous products, the yield rate of hydrogen, and the rates of gasification as both C-atoms and H-atoms over several catalysts at 500 C are shown in Table 1. As gaseous products, hydrogen, carbon monoxide, carbon dioxide, and methane were the main products, and negligible amounts of C2+ hydrocarbons, aldehydes, and alcohols were obtained. The gasification rates in terms of C-atoms and H-atoms were respectively calculated from the mol numbers of C-atoms and H-atoms contained in gaseous products among C-atoms and H-atoms included in the initially added cellulose. C-atoms of nongaseous products were included in tar or deposited carbon, and H-atoms of nongaseous products were included in tar and water. During a total of seven reactions, the yield of hydrogen increased with the number of reactions. It appears that the ratio of Ni/NiO increased during the reactions. Therefore, in general, the data for the fifth reaction was adopted as representative of the catalytic activity. After the fifth reaction, the yield of gaseous products was virtually constant. Hydrogen yields were affected by the kind of support: in the case of Ni/simple metal oxide catalysts, the yields of hydrogen were Ni/SiO2 (2850 mol) > Ni/ZrO2 (2093 mol) > Ni/CeO2 (1650 mol). In the case of zeolite supports, more than 2500 mol of hydrogen was obtained, except for Ni/H- (1627 mol) and Ni/USY (1726 mol). The yield rate of hydrogen was from 17% to 44%. Generally, in both cases, in terms of C-atoms and in terms of H-atoms, the gasification rate was closely related to the hydrogen yield: the higher the yield of hydrogen, the higher the resultant gasification rate.

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Table 1. Results of Reaction at 500 C catalysta 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 yield s of gaseous products (mol) H2 CO CO2 CH4 others 2850 2093 1650 1627 3410 2863 2885 2696 1726 2823 2774 2880 2780 2382 3997 1957 853 1220 834 2153 1125 1031 1301 1534 1963 813 1384 1576 1071 791 1833 1944 4688 3446 3166 2642 4636 3805 4147 4142 3003 4422 4280 4446 4676 4329 4747 2991 1258 199 140 110 996 252 795 641 87 919 743 854 1520 824 1063 144 3 22 20 123 3 23 30 121 110 2 70 77 18 22 38 84 rate of gasification (%) C-atom H-atom 61.3 44.3 37.7 47.1 60.9 46.4 56.9 59.8 48.2 55.5 59.4 63.6 65.9 54.0 69.7 47.8 58.1 27.6 21.5 23.7 58.5 37.1 49.2 46.7 24.0 50.5 48.3 51.9 63.4 44.2 67.4 26.9 yield rate of H2 (%) 30.8 22.6 17.8 17.6 36.9 31.0 31.2 29.1 18.7 30.5 30.0 31.1 30.1 25.8 43.2 21.2 C-atom in deposited carbon (mol) 11350 536 0 12820 12420 2451 7240 6238 8325 12350 7675 5788 1285 797 790 2518 color of tar yellow brown brown yellow yellow brown colorless yellow yellow brown colorless colorless colorless brown yellow brown yield of tar (g) 0.44 0.59 0.68 0.64 0.33 0.48 0.43 0.45 0.58 0.41 0.37 0.41 0.31 0.36 0.30 0.58

Inaba et al.

C-atom in tar (mol) 21 450 46 910 48 930 34 770 18 750 44 160 27 170 25 740 36 530 29 720 27 250 23 050 29 010 37 900 24 820 41 050

a (1) Ni/SiO ; (2) Ni/ZrO ; (3) Ni/CeO ; (4) Ni/H-; (5) Ni/H-mordenite; (6) Ni/Na-mordenite; (7) Ni/H-ZSM-5; (8) Ni/Na-ZSM-5; (9) Ni/USY; (10) 2 2 2 Ni/Na-Y; (11) Ni/Ce/H-ZSM-5 (Ce ) 5 wt %); (12) Ni/Ce/H-ZSM-5 (Ce ) 10 wt %); (13) Ni/Ce/H-ZSM-5 (Ce ) 30 wt %); (14) Ni/Ce/H-mordenite (Ce ) 30 wt %); (15) Rh/Ce/SiO2; (16) Rh/SiO2.

As mentioned below, Ni/H-ZSM-5 catalyst yielded colorless tar, suggesting that H-ZSM-5 zeolite is a promising support for decomposing tar. Therefore, Ce-loaded H-ZSM-5 zeolite was tried as a support to inhibit carbon deposition. In the case of Ni/Ce/H-ZSM-5 catalysts, the amount of Ce-loading did not much affect the yield of hydrogen. However, increased Celoading favored the formation of CO2 and methane, and as a result, the rate of gasification increased, in terms of both C-atoms and H-atoms. On the other hand, Ni/H-mordenite catalyst yielded 3410 mol of hydrogen, the highest among the Ni catalysts, suggesting that this catalyst is better than Ni/H-ZSM-5 catalyst with respect to hydrogen yield. However, Ni/Ce/H-mordenite catalyst (Ce ) 30 wt %) yielded only 2382 mol of hydrogen, suggesting that hydrogen yield is noticeably decreased by Celoading, unlike with Ce/H-ZSM-5 supports. Moreover, in this case, gasification rates in terms of C-atoms and H-atoms were reduced to 54.0% and 44.2%, respectively. We tried other kinds of metals, for example, Mg, Ca, Zn, Zr, and La, loaded with Ni on H-ZSM-5 zeolite supports; however, lower hydrogen yields were obtained than for Ce-loading. On the other hand, Rh/Ce/SiO2 catalyst, which we prepared for comparison, showed an especially high hydrogen yield of 3997 mol, higher than any Ni catalysts, while Rh/SiO2 catalyst showed a somewhat low hydrogen yield of 1957 mol. The rate of gasification in terms of C-atoms over Rh/Ce/ SiO2 and Ni/Ce/H-ZSM-5 (Ce ) 30 wt %) catalyst was 69.7% and 65.9%, respectively, and the gasification rate in terms of H-atoms over Rh/Ce/SiO2 and Ni/Ce/H-ZSM-5 was 67.4% and 63.4%, respectively. The differences in catalytic activity between them were not very noticeable. From this result, Ni/Ce/H-ZSM-5 (Ce ) 30 wt %) catalyst appears to be a promising candidate as a non-noble metal catalyst. The color and amount of tar, and the mol number of C-atoms in tar obtained during a total of seven reactions, are also shown in Table 1. In the case of Ni/metal oxide catalysts, 0.44 g (Catom ) 21450 mol) of yellow tar was obtained for Ni/SiO2 catalyst; however, 0.59 (C-atom ) 46910 mol) and 0.68 g (C-atom ) 48930 mol) of brown tars were obtained for Ni/ ZrO2 and Ni/CeO2 catalysts, respectively. On the other hand, in the case of Ni/zeolite catalysts, colorless or yellow tar was obtained, and the amount of tar formed was within 0.6 g (Catom ) 35000 mol) in most cases, except for the case of Ni/ Na-mordenite catalyst, which yielded 0.48 g (C-atom ) 44160

mol) of brown tar, suggesting that zeolite supports have a higher activity for decomposition of tar components than simple metal oxide supports. Of the Ni/zeolite catalysts, Ni/H-ZSM-5 catalyst formed colorless tar, suggesting that this has especially high activity for tar decomposition. In the case of Ni/Ce/HZSM-5 catalysts, the yield of tar changed little by Ce-loading, with the tar remaining colorless. On the other hand, Rh/Ce/SiO2 catalyst yielded only small amounts of yellow tar, 0.30 g (C-atom ) 24820 mol), suggesting that this catalyst has especially high activity for the decomposition of tar, while Rh/SiO2 catalyst yielded 0.58 g of brown tar (C-atom ) 41050 mol). In general, there seems to be an inverse correlation between the hydrogen yield and the amount of C-atoms in the tar: the greater the amount of tar, the lower the resultant yield of hydrogen. The amount of C-atoms in carbon deposited on the catalysts during a total of seven reactions is also shown in Table 1. The quantity of C-atoms for each metal oxide support was Ni/SiO2 (11 350 mol) > Ni/ZrO2 (536 mol) > Ni/CeO2 (0 mol). Thus, carbon deposition and tar formation are inversely proportional. On the other hand, Ni/zeolite catalysts showed large amounts of deposited carbon, suggesting that they possess high activity for tar decomposition, while decomposed tar could be deposited as carbon on the catalysts. Ni/Na-mordenite catalyst showed 2451 mol of deposited carbon, lower than that of Ni/ H-mordenite catalyst (12 420 mol). However, this catalyst formed 0.48 g (C-atom ) 44 160 mol) of brown tar, while Ni/H-mordenite catalyst yielded 0.33 g (C-atom ) 18 750 mol) of yellow tar, suggesting that the presence of Na+ cations can inhibit carbon deposition to some degree but inhibit tar decomposition. In fact, Ni/Na-ZSM-5 catalyst showed 6238 mol of deposited carbon, lower than that of Ni/H-ZSM-5 catalyst with the same Si/Al2 ratio, which showed 7240 mol. However, Ni/Na-Y catalyst showed as much as 12 350 mol of deposited carbon, and brown tar was formed. In this point, further investigation is required. The amount of carbon deposition could be affected by the pore size of zeolites as well as the Ce-loading. In fact, in the case of Ni/Ce/H-ZSM-5 catalysts, the amount of carbon deposition decreased with increased Ce-loading, suggesting that Ce-loading can inhibit carbon deposition.8 On the other hand, Ni/Ce/H-mordenite catalyst showed decreased amounts of

H2 production by Cellulose Gasification on Ni


Table 2. Results of Reaction at 600 C catalysta 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 yield s of gaseous products (mol) H2 CO CO2 CH4 others 4624 3429 2250 4361 4455 4453 4438 4217 4602 4345 4423 4068 3861 3432 3817 3758 3286 2589 1843 2889 3015 3582 3040 3095 3270 3097 3159 3236 3195 2997 2969 3676 4076 3630 2879 3991 4152 3428 4024 4118 3529 3676 4217 4327 4225 4298 4302 3124 862 355 141 841 934 226 901 897 394 453 932 1123 1382 1209 1747 368 2 15 27 4 2 22 3 2 4 2 3 4 2 2 2 53 rate of gasification (%) C-atom H-atom 74.1 59.6 44.4 69.7 73.0 65.7 71.8 73.1 64.9 65.1 74.9 78.4 79.4 76.7 81.3 65.9 68.7 45.2 28.2 65.5 68.4 53.7 67.6 65.1 58.4 56.8 68.1 68.4 71.7 63.3 79.1 50.4 yield rate of H2 (%) 50.0 37.1 24.3 47.1 48.2 48.1 48.0 45.6 49.8 47.0 47.8 44.0 41.7 37.1 41.3 40.6

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C-atom in deposited carbon (mol) 1414 100 0 1803 2646 528 3002 1934 2770 1509 3226 756 125 200 108 368

color of tar colorless yellow brown colorless colorless yellow colorless colorless colorless yellow colorless colorless colorless colorless colorless yellow

yield of tar (g) 0.34 0.32 0.65 0.39 0.33 0.35 0.32 0.34 0.32 0.33 0.30 0.33 0.30 0.24 0.21 0.22

C-atom in tar (mol) 21 370 31 780 44 920 28 640 28 530 33 640 24 390 20 660 31 000 30 830 19 180 18 890 19 070 25 320 15 990 35 540

a (1) Ni/SiO ; (2) Ni/ZrO ; (3) Ni/CeO ; (4) Ni/H-; (5) Ni/H-mordenite; (6) Ni/Na-mordenite; (7) Ni/H-ZSM-5; (8) Ni/Na-ZSM-5; (9) Ni/USY; (10) 2 2 2 Ni/Na-Y; (11) Ni/Ce/H-ZSM-5 (Ce ) 5 wt %); (12) Ni/Ce/H-ZSM-5 (Ce ) 10 wt %); (13) Ni/Ce/H-ZSM-5 (Ce ) 30 wt %); (14) Ni/Ce/H-mordenite (Ce ) 30 wt %); (15) Rh/Ce/SiO2; (16) Rh/SiO2.

deposited carbon, while the tar yield (brown tar) was increased by Ce-loading. Rh/Ce/SiO2 showed little carbon deposition (790 mol), suggesting that this catalyst has high activity for inhibiting carbon deposition during the reaction. On the other hand, Rh/ SiO2 catalyst showed 2518 mol of deposited carbon, more than Rh/Ce/SiO2. From these results, in the case of Rh catalysts as well as Ni catalysts, the loading of Ce plays an important role in hydrogen production and inhibition of tar formation and carbon deposition. However, there seems to be no correlation in any catalyst between the hydrogen yield and the amount of carbon deposition. Catalytic Performance at 600 C. The results of reactions over several catalysts at 600 C are shown in Table 2. Conditions of the measurement other than reaction temperature were the same as those inTable 1. In most cases, the yield of gaseous products, especially hydrogen, was much higher than that at 500 C. The yield rate of hydrogen was 24-50%. At 600 C, unlike at 500 C, the effect of the kind of supports on the hydrogen yield was not very pronounced, except for the case of Ni/CeO2 catalyst, which yielded 2250 mol of hydrogen, much smaller than other catalysts. The gasification rate was not affected by the kind of support, except for Ni/CeO2 catalyst, which showed especially low gasification rates of 44.4% and 28.2%, respectively, in terms of C-atoms and H-atoms. On the other hand, loading of Ce on H-ZSM-5 zeolite supports decreased the yield of hydrogen, but raised the yield of methane, while the yields of CO and CO2 remained almost constant; as a result, the gasification rates both in terms of C-atoms and in terms of H-atoms were improved. These results suggest that Ce-loading enhances the conversion of cellulose to methane, and as a result, carbon deposition is inhibited. However, at higher temperatures, Ce-loading also promotes the oxidation of hydrogen to water, rather than the oxidation of cellulose to CO or CO2. In general, at 600 C, the tar yield during the total of seven reactions was less than at 500 C, and the color of tar was light (yellow or colorless), except for the case of Ni/CeO2 catalyst, suggesting that higher reaction temperatures favor the gasification of cellulose. Moreover, the amount of deposited carbon after reaction at 600 C was less than after reaction at 500 C, suggesting that reaction at higher temperatures can inhibit carbon deposition. The amount of deposited carbon was less affected by the kind

Figure 2. XRD patterns of Ni/Ce/H-ZSM-5 (Si/Al2 ) 29) (Ce ) 30 wt %) catalysts: (a) before reaction; (b) after 7 reactions.

of support than at 500 C; however, Ni/metal oxide catalysts, such as Ni/ZrO2 and Ni/CeO2 catalysts, and Ni/Na-zeolite catalysts such as Ni/Na-mordenite, showed especially small amounts of deposited carbon. In the cases of Rh/Ce/SiO2 and Rh/SiO2 catalysts, moderate yields of hydrogen (3817 and 3758 mol, respectively), slightly lower than yields for Ni/zeolite and Ni/Ce/H-ZSM-5 catalysts, were observed, with low amounts of C-atoms in tar, suggesting that Rh catalysts also have high activity for decomposition of tars. Rh/Ce/SiO2 catalyst inhibited carbon deposition, and Rh/SiO2 catalyst also inhibited carbon deposition to some degree. Results of XRD. XRD patterns of Ni/Ce/H-ZSM-5 (Ce ) 30 wt %) catalysts before and after a total of seven reactions at 500 C are shown in Figure 2a and Figure 2b, respectively. Figure 2 shows that, before reaction (Figure 2a), loaded Ni is present as oxidized NiO, while after reaction (Figure 2b), a proportion of NiO is reduced to metallic Ni; as a result, the loaded Ni is present as both metallic Ni and oxidized NiO. A similar tendency was observed on all the other kinds of Ni catalysts. Conversely, loaded Ce persists as CeO2, maintaining this state during reactions without being reduced. Figure 3 shows a plot of the Ni/NiO ratio after reaction, calculated from the intensity of the diffraction peak, vs the yield of hydrogen at 500 C. Except for the case of Ni/CeO2 catalyst, which yielded small amounts of hydrogen but showed a high Ni/NiO ratio, the catalysts showing higher Ni/NiO ratios yielded

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Figure 3. Plot of Ni/NiO ratio of Ni catalysts after seven reactions vs H2 yield at 500 C. Numbers in parentheses indicate Ce loading (wt %).

Figure 5. Plot of Ni crystallite size of Ni catalysts after seven reactions vs H2 yield at 500 C. Numbers in parentheses indicate Ce loading (wt %).

Figure 4. Plot of Ni/NiO ratio of Ni catalysts after seven reactions vs amount of C atoms in tar after seven reactions at 500 C. Numbers in parentheses indicate Ce loading (wt %).

Figure 6. Plot of Ni crystallite size of Ni catalysts after seven reactions vs amount of C atoms in tar after seven reactions at 500 C. Numbers in parentheses indicate Ce loading (wt %).

more hydrogen. In general, metallic Ni catalytically reforms hydrocarbons to yield hydrogen,9 and methanates CO and CO2,10 while NiO has catalytic activity for deep oxidation,9,11,12 such as CO f CO2 and H2 f H2O. The obtained results may therefore be consistent with the view that metallic Ni, not oxidized NiO, is an active site in this reaction. There also appears to be an interaction between Ni and the support, affecting the oxidized state of the loaded Ni. On the other hand, loading of Ce on H-ZSM-5 support did not affect the Ni/NiO ratio. However, it seems likely that the catalytic activity of metallic Ni for methanation is enhanced by the loading of Ce with weak basicity, since it is reported that the methanation activity of metallic Ni is improved by the coexistence of weakly alkaline metal oxides.13 Figure 4 shows a plot of the Ni/NiO ratio vs the mol number of C-atoms in tar formed during a total of seven reactions at 500 C. In this case, Ni/CeO2 also yielded large amounts of tar despite a high Ni/NiO ratio; moreover, Ni/Na-mordenite and Ni/ZrO2 catalysts also yielded large quantities of tar. However, except in these cases, the catalysts showing higher Ni/NiO ratio generally yielded less tar. On the other hand, loading of Ce inhibited tar formation to some degree, without changing the
(9) Dissanayake, D.; Rosynek, M. P.; Kharas, K. C. C.; Lunsford, J. H. J. Catal. 1991, 132, 117-127. (10) Vannice, M. A. J. Catal. 1975, 37, 449-461. (11) Morooka, Y.; Ozaki, A. J. Catal. 1966, 5, 116-124. (12) Morooka, Y.; Morikawa, Y.; Ozaki, A. J. Catal. 1967, 7, 23-32. (13) Inui, T.; Funabiki, M.; Takegami, Y. Ind. Eng. Chem. Prod. Res. DeV. 1980, 19, 385-388.

Ni/NiO ratio. It is suggested that metallic Ni enhances the reduction of tar by reforming or methanation. Figure 5 shows a plot of the diameter of Ni crystallite after seven reactions vs the yield of hydrogen at 500 C. Most catalysts showed a Ni crystallite size of about 25 nm, little affected by the type of support, and hydrogen yields were also almost the same, although Ni/H-mordenite catalyst yielded a slightly higher amount of hydrogen and Ni/ZrO2 catalyst showed a low hydrogen yield. Ni/CeO2 catalyst showed a large Ni crystallite size, while Ni/H- and Ni/USY catalysts showed a small Ni crystallite size, but all these catalysts exhibited a low yield of hydrogen. Figure 6 shows a plot of the diameter of Ni crystallite after seven reactions vs the mol number of C-atoms in tar formed during seven reactions at 500 C. In this case, Ni/CeO2, Ni/ Na-mordenite, and Ni/ZrO2 catalysts yielded especially large amounts of C-atoms in tar. However, except for these cases, there appears to be a minor correlation. From these results, there seems to be a structure sensitivity: a higher crystallinity of metallic Ni favors hydrogen formation and tar decomposition. On the other hand, loading of Ce did not affect the diameter of Ni crystallite. From the plots of the diameter of NiO crystallite after a total of seven reactions vs the hydrogen yield and the mol number of C-atoms in tar formed during a total of seven reactions at 500 C, there seems to be a weak correlation between the diameter of NiO crystallite and these two factors, where the

H2 production by Cellulose Gasification on Ni

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Scheme 2. Assumed Scheme of Cellulose Gasification

Scheme 3. Image of Cellulose Gasification over Ni Catalysts

Figure 7. TEM images of Ni/Ce/H-ZSM-5 (Si/Al2 ) 29) (Ce ) 30 wt %) catalysts: (a) before reaction; (b) after seven reactions.

distribution of the size of NiO crystallite (ca. 13-21 nm) was narrower than Ni crystallite (ca. 15-41 nm). These results suggest a weak structure sensitivity: the higher crystallinity of NiO inhibits hydrogen formation and tar decomposition. The loading of Ce did not affect the diameter of either NiO crystallite or Ni crystallite. In the case of the reaction at 600 C, no clear correlation could be found between the Ni/NiO ratio or the size of Ni or NiO crystallite and hydrogen production or tar formation, partly because the reduced Ni may be reoxidized to NiO due to the high temperature and exposure to an oxidative atmosphere. Moreover, the size of NiO crystallite before reaction was measured by XRD; however, we were unable to find a clear correlation between the size of NiO and the hydrogen yield or the tar yield. TEM Observations. TEM images of Ni/Ce/H-ZSM-5 (Ce ) 30 wt %) catalysts before and after a total of seven reactions at 500 C are shown in parts a and b, respectively, of Figure 7. Figure 7a shows that, before reaction, particles of NiO and CeO2 are present on H-ZSM-5 supports: dark-colored NiO particles, 10-20 nm in size, appear to flock together to form large particles of ca. 100 nm. On the other hand, semi-dark-colored

CeO2 particles, with a size of 5-10 nm, appear to be dispersed on the surface of the H-ZSM-5 support and NiO particles. On the other hand, Figure 7b shows that, after reaction, the diameters of the Ni and NiO particles sintered to form darkcolored, large (ca. 100 nm) particles; however, it was impossible to distinguish between the Ni and NiO particles. On the other hand, the diameter of CeO2 particles retained their size of 5-10 nm during reaction. These results suggest that the Ni particles readily sinter, but the Ce particles maintain their isolated state without sintering. Although deposited carbon covers the Ni (or NiO) particles, it appears that the concentration of carbon around the CeO2 particles is lower than that around the Ni particles. Scheme of Cellulose Gasification. We assume that this cellulose gasification consists of complex reactions, the most predominant of which are shown in Scheme 2.3,7 Cellulose may undergo pyrolysis (1) at the primary stage due to insufficient oxygen, and then undergo combustion (2) enhanced by NiO due to sufficient oxygen feed. The pyrolysis of cellulose leads to the formation of tar, char, water, and gaseous products, while the combustion of cellulose results in the formation of CO2 and water. Tar and char then undergo CO2 reforming (3) and steam reforming (4), enhanced by metallic Ni, to yield CO and hydrogen. However, Ni enhances not only reforming but also methanation (5), in which methane and water are formed from CO and hydrogen. The reverse reaction (6) (reforming from methane and water to CO and hydrogen) may also occur. Conclusions Hydrogen production by cellulose gasification over Ni catalysts was investigated. As shown in Scheme 3, the catalytic activity and the kinds of products were affected by the kind of support. Large quantities of dark-colored tar were obtained with most Ni/conventional metal oxide catalysts, while carbon deposition could be avoided. Most Ni/zeolite catalysts could inhibit the formation of tar to some degree; however, carbon

438 Energy & Fuels, Vol. 20, No. 2, 2006

Inaba et al.

deposition occurred. The Ce-loading on zeolite support was able to enhance the rate of gasification, and, as a result, could to some extent inhibit tar formation and carbon deposition. In most cases, the higher reaction temperature led to a greater amount of hydrogen formed, a higher rate of gasification, and less tar formation and carbon deposition. However, at 500 C, the hydrogen yield was not affected by Ce-loading, while at 600 C, the hydrogen yield was decreased by Ce-loading due to hydrogen combustion to H2O. In formation of hydrogen from cellulose, it appears that metallic Ni is the catalytically active

site and there is minor structure sensitivity of Ni. Ce-loading enhanced the combustion activity of tar and improved the methanation activity of metallic Ni, raising the overall gasification rate. Although Ni/Ce/H-ZSM-5 catalyst may be slightly less effective than Rh/Ce/SiO2 catalyst, the former is a promising candidate for this reaction due to its low cost of preparation. Further investigation is now in progress to find better catalysts and reaction systems to reduce the production of tar.
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