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Combustion Science and Technology

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CATALYTIC GASIFICATION OF WOOD BIOMASS IN SUBCRITICAL AND SUPERCRITICAL WATER

MITSUMASA OSADA , TAKAFUMI SATO , MASARU WATANABE , MASAYUKI SHIRAI & KUNIO ARAI
a c d d a b

Department of Chemical Engineering , Tohoku University , Aramaki, Aoba, Sendai, Japan

b

Department of Applied Chemistry , Utsunomiya University , Utsunomiya, Japan

c

Research Center of Supercritical Fluid Technology , Tohoku University , Aramaki, Aoba, Sendai, Japan
d

Supercritical Fluid Research Center, National Institute of Advanced Industrial Science and Technology , Sendai, Japan Published online: 25 Jan 2007.

To cite this article: MITSUMASA OSADA , TAKAFUMI SATO , MASARU WATANABE , MASAYUKI SHIRAI & KUNIO ARAI (2006) CATALYTIC GASIFICATION OF WOOD BIOMASS IN SUBCRITICAL AND SUPERCRITICAL WATER, Combustion Science and Technology, 178:1-3, 537-552, DOI: 10.1080/00102200500290807 To link to this article: http://dx.doi.org/10.1080/00102200500290807

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Combust. Sci. and Tech., 178: 537552, 2006 Copyright Q Taylor & Francis LLC ISSN: 0010-2202 print/1563-521X online DOI: 10.1080/00102200500290807

CATALYTIC GASIFICATION OF WOOD BIOMASS IN SUBCRITICAL AND SUPERCRITICAL WATER

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MITSUMASA OSADA Department of Chemical Engineering, Tohoku University, Aramaki, Aoba, Sendai, Japan TAKAFUMI SATO Department of Applied Chemistry, Utsunomiya University, Utsunomiya, Japan MASARU WATANABE Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki, Aoba, Sendai, Japan MASAYUKI SHIRAI KUNIO ARAI Supercritical Fluid Research Center, National Institute of Advanced Industrial Science and Technology, Sendai, Japan

Research in biomass gasification with subcritical and supercritical water is reviewed. Catalytic conversion of biomass in sub- and supercritical water is a low-temperature gasification technique that can be carried out from 473 to 973 K. Research is categorized according to temperature and water density, since reaction mechanisms greatly depend on these variables.
Received 4 August 2004; accepted 17 April 2005. This research was partially supported by the Ministry of Education, Culture, Sports, Science and Technology, a Grant-in-Aid for the COE project, Giant Molecules and Complex Systems. Address correspondence to karai@arai.che.tohoku.ac.jp 537

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Keywords: supercritical water, gasification, biomass, cellulose, lignin

INTRODUCTION Need for Subcritical and Supercritical Water Gasification Wood biomass has great potential as an energy or chemical resource. As an energy resource, wood biomass is renewable and an organism-derived organic material. In this review, discussion of wood biomass focuses on its chemical constituents such as cellulose and lignin, as well as chemical units such as glucose and phenol, along with various crop residues and sewage sludge. Gasification processes for wood biomass have received attention as an efficient conversion technology. Applications of the obtained gas are very wide, for example, use in gas turbines, in fuel cells and for the synthesis of chemicals (Yoshida et al., 2003). In gasification processes, methane fermentation and thermal gasification at ambient pressures are used in industry. Methane fermentation is a technology in which biomass is decomposed by microorganisms under the anaerobic conditions to methane and carbon dioxide. This technology can be applied for wet biomass; however, the decomposition rate is slow and the fermentation of lignin is difficult. Thermal gasification at ambient pressure is a technology that produces gases by thermal decomposition and chemical reaction in the high-temperature region over 973 K. For gasification at ambient pressure, oxygen (or air) is needed for partial combustion and to maintain the high reaction temperatures ( > 973 K). Furthermore, for using wet biomass, a drying process is required. Subcritical and supercritical water gasification of wood biomass has many advantages compared with methane fermentation process from the viewpoint of energy, environmental and economy (Matsumura, 2002). Most organics include lignin can be gasified completely in supercritical water and the reaction rate is faster than that of methane fermentation. Subcritical and supercritical water gasification has some advantages compared with thermal gasification at ambient pressures. Gasification occurs at temperatures below 973 K and this makes it possible to use waste heat from other processes such as that from iron production or cement production to supply necessary energy. Further, a drying process is not required for subcritical and supercritical water

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gasification processes, since the reaction proceeds in water. Yoshida et al. (2003) reported that supercritical water gasification process is highly efficient for handling wet biomass from the view of carbon dioxide emissions. Characteristics of Subcritical and Supercritical Water Gasification

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Subcritical and supercritical water is a solvent in which both chemical formation and decomposition reactions occur (Akiya and Savage, 2002). Subcritical water below 647 K has several properties that differ from those of water at room temperature. For example, the dielectric constant decreases from about 78 at 298 K to 27 at 523 K. This decrease in dielectric constant gives rise to increased solubility of small organic compounds. Supercritical water above the critical temperature of 647 K is miscible with light gases and small organic compounds, and its dielectric constant is 2 at 673 K, 25 MPa. Supercritical water offers the unique possibility of shifting dominant reaction mechanisms from those of free-radical to those of ionic through manipulating the water density (Watanabe et al., 2004). The water density greatly changes with temperature and pressure as shown in Figure 1.

Figure 1. Temperature and pressure dependence of water density.

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The composition of gasified biomass depends on reaction temperature. Three main reactions of wood biomass occur in supercritical water: C H2 O ! CO H2 CO H2 O ! CO2 H2 CO 3H2 ! CH4 H2 O endothermic thermoneutral exothermic 1 2 3

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Eq. (1) is the water gas reaction, Eq. (2) is the water-gas shift reaction, and Eq. (3) is the methanation reaction. Figure 2 shows the temperature dependence of the composition of gas produced from lignin under subcritical and supercritical water at 30 MPa. Hydrogen and carbon dioxide are the main products at temperatures greater than 800 K, whereas methane and carbon dioxide are the main products at temperatures below 800 K. Subcritical and supercritical water gasification have been examined over a wide range condition of 473973 K and 4.350 MPa. In this paper, wood biomass gasification under subcritical and supercritical water is reviewed for three temperature regions ((I). 773973 K, (II) 647773 K, (III) below 647 K) as shown in Figure 1. The free-radical mechanism

Figure 2. Equilibrium gas composition of lignin under subcritical and supercritical water at 30 MPa. (1) Estimated with CHEMKIN III (Kee et al., 2001). (2) Molecular formula of lignin is C43.39H45.46O12.15. Initial lignin and water ratio was 1=10 (w=w).

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dominates at high-temperature and low-density conditions, namely region I in Figure 1. The ionic mechanism dominates at low-temperature and high-density conditions, namely region III. In region II, both freeradical and ionic mechanisms proceed. The characteristics of each region for biomass gasification are summarized next. HIGH-TEMPERATURE SUPERCRITICAL WATER GASIFICATION AT 773973 K Supercritical water gasification from 773 to 973 K is (region I) shown in Table 1. For this temperature region, free-radical mechanisms such as pyrolysis reactions dominate at low-density conditions and the reaction is second order. For these type gasifications, low-cost activated carbon and alkali catalysts can be used as catalysts. However, the conditions require high-energy input. On the other hand, Feng et al. (2004) reported that the efficiency of supercritical water gasification process increases with decreasing temperature and increasing pressure. Activated carbon catalysts are effective for the inhibition of formation of char. Xu et al. (1996) conducted glucose gasification in supercritical water with a flow-type apparatus at temperatures from 873 to 973 K and at pressures from 25 to 30 MPa. They gasified glucose to form carbon dioxide, hydrogen, methane, and carbon monoxide over an activated carbon catalyst. They reported that the amount of carbon monoxide produced varied according to the type of activated carbon used. Antal et al. (2000) reported on the gasification of potato-starch and wood sawdust with a flow-type reactor at 973 K and 28 MPa. Carbon dioxide, hydrogen, and methane were the main products. Alkali catalysts such as potassium carbonate and potassium hydroxide promote the water-gas shift reaction and the increase of the hydrogen yield (Kruse et al., 2000). The hydrogen produced seems to promote decomposition of organics through hydrogenation. Schmieder et al. (2000) conducted the gasification of glucose and vanillin, which are model compounds of wood biomass, with a flow-type apparatus at temperatures from 873 to 973 K and pressures from 25 to 30 MPa with potassium carbonate or potassium hydroxide, which are contained in real biomass as an ash. Glucose and vanillin completely gasified to hydrogen and carbon dioxide within 140 s. Schmieder et al. (2000) conducted the gasification of straw. They reported that complete gasification was achieved using alkali catalysts with a batch-type reactor at 773 K,

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Table 1. Subcritical and supercritical water gasification

542 Main gaseous product Reaction condition Reactor 100 873 K; 34.5 MPa 973 K; 28 MPa 823873 K; 2031 MPa 773 K; 35 MPa; 120 min Flow Batch; 1000 cm3 Flow Flow 79 100 90 CO2, H2, CH4 H2, CO2 Xu et al. (1996) Antal et al. (2000) CO2, H2, CH4, CO CO2, H2, CH4 Schmieder et al. (2000) Schmieder et al. (2000) 18 9 97 100 CO2, CH4, H2 CO, CO2, H2 CO2, H2, CH4 CO2, CH4, H2 647 K; 22 MPa; 30 min 673 K; 25 MPa; 20 min 723 K; 44 MPa; 120 min 673 K; 40 MPa; 180 min Batch; 1000 cm3 Batch; 6 cm3 Batch; 10.8 cm3 Batch; 6 cm3 Modell (1985) Yoshida et al. (2004) Park and Tomiyasu (2003) Osada et al. (2004) 100 84 84 H2, CO2 CH4, CO2 CO2, CH4, H2 Flow Batch; 100 cm3 Batch; 130 cm3 623 K; 20 Mpa 623 K; 19 MPa; 60 min 538 K; 5.6 MPa; 24 h Elliott et al. (2004) Minowa et al. (1998) Cortright et al. (2002)

Biomass feed

Catalyst

Yield of gas on carbon basis [%]

(a) Region I: High-temperature supercritical water (773973 K)

Glucose

Potato starch wood sawdust Glucose vanillin Straw

Activated carbon Activated carbon KOH

K2CO3

(b) Region II: Low-temperature supercritical water (647773 K)

Cellulose Lignin Cellulose

Nickel Nickel RuO2

Lignin

Ruthenium

(c) Region III: Subcritical water (below 647 K)

Manure grain Cellulose

Ruthenium Nickel

Glucose

Platinum

Refer to Fig.1 definition of regions I, II, and III.

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35 MPa, and at a reaction time of 120 min with the products hydrogen and carbon dioxide being obtained. LOW-TEMPERATURE SUPERCRITICAL WATER GASIFICATION AT 647773 K In supercritical water, from 647 to 773 K, the reaction mechanism shifts with increasing water density from one that supports free-radical mechanisms to that supports ionic reaction mechanisms. Hydrolysis is an important ionic reaction that promotes decomposition of cellulose and lignin. There have been many studies that have reported on the decomposition of cellulose and lignin without catalyst in supercritical water as described next. The mechanism of cellulose decomposition in supercritical water around 673 K is summarized in Figure 3 (Kruse et al., 2003; Mok and Antal, 1992; Sasaki et al., 1998, 2000, 2003a, 2003b, 2004; Sinag et al., 2003, 2004). Cellulose decomposition proceeds mainly through hydrolysis, dehydration, and retro-aldol condensation. Hydrolysis can take place at the glycosidic bond of cellulose to form cello oligosaccharides and glucose. Dehydration and retro-aldol condensation can occur at the reducing end of cellulose to form levoglucosan, glycolaldehyde, and erythrose. Watanabe et al. (2002) reported the formation of char during the decomposition of cellulose. Char is formed by dehydration reaction from low molecular weight compounds, which were produced from cellulose, in the subcritical region at elevated temperatures (Fang et al., 2004). There are some reports that lignin decomposes to alkylphenols through hydrolysis in supercritical water around 673 K (Bobleter and Consin, 1979; Ehara et al., 2002; Funazukuri et al., 1990; Yokoyama et al., 1998). The mechanism of char formation from lignin seems to be as follows: formation of phenolic compounds and formaldehyde takes place through hydrolysis, and then condensation reaction occurs between the phenolic compounds and formaldehyde to produce char as shown in Figure 4 (Okuda et al., 2004a, 2004b; Saisu et al., 2003). The inhibition of char formation is important since gasification of the char is difficult. To prevent char formation and promote gasification, nickel and ruthenium catalysts have been mainly used in supercritical water from 647 to 773 K (region II) as summarized in Table 1. Modell (1985) reported the gasification of cellulose over a nickel catalyst with a batch type reactor at 647 K and 22 MPa and obtained carbon monoxide, carbon dioxide and

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Figure 3. Reaction pathway of cellulose in supercritical water around 673 K.

hydrogen as the main gaseous products. One advantage that they mentioned was that rapid heating prevented char formation. Yoshida and Matsumura, (2001) conducted gasification of cellulose and lignin mixtures over a nickel catalyst in supercritical water at 673 K and obtained methane and carbon dioxide as the main gaseous products. They reported that the lignin fraction inhibited gasification. Park and Tomiyasu (2003) reported cellulose gasification over the ruthenium oxide and obtained methane, carbon dioxide and hydrogen at 523 K and 44 MPa. They found that all hydrogen atoms in the gaseous products seemed to originate from water molecules, and that the catalytic

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Figure 4. Reaction pathway of lignin in supercritical water around 673 K.

effect of ruthenium oxide resulted from a redox couple of RuIV=RuII. Osada et al. (2003, 2004) gasified lignin to methane and carbon dioxide completely at 673 K, 30 MPa in the presence of a ruthenium catalyst. They mentioned that immediate decomposition of intermediate

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compounds such as formaldehyde and alkylphenols was important to obtain high yields of gaseous products. Furthermore, they reported that the gaseous product yields of lignin gasification increases with increasing water density over a ruthenium catalyst at 673 K. One reason for this trend is that the rate of formation of low-molecular-weight fragments (phenols and aldehydes) increases with increasing water density. Sato et al. (2003) conducted the gasification of alkylphenols as lignin model compounds in the presence of supported noble metal catalyst and reported ruthenium catalysts were effective for decomposition of aromatics. Cellulose and lignin can be completely gasified to methane and carbon dioxide over ruthenium catalysts in supercritical water. As shown in Figures 3 and 4, cellulose and lignin decomposes to low-molecular fragments in supercritical water. This decomposition rate increases with increasing the water-density. Gasification of these fragments occurs over metal catalysts and condensation between fragments can be suppressed, which means that char formation can be reduced or eliminated. SUBCRITICAL WATER GASIFICATION BELOW 647 K Below 647 K (region III), a vapor and a liquid phase can exist. Equilibrium composition of gases produced from biomass in this region is generally methane and carbon (Figure 2). Since the reaction rate of hydrolysis in subcritical water is slower than that in supercritical water (Sasaki et al., 2004), it is difficult to gasify high molecular weight constituents of biomass such as cellulose and lignin. However, it is advantageous to gasify biomass in this temperature region since the input thermal energy would be low even though the gasification rate would be slow. This means that the role of the catalyst in region III becomes important. Many catalysts such as nickel, ruthenium, palladium, platinum and rhodium have been examined as summarized in Table 1. Elliott et al. (1993, 1994a, 1994b, 2004) examined the activities of supported ruthenium and nickel catalysts for the gasification with a bench-scale flow type reactor at 623 K and 21 MPa. Various wastewaters such as manure grain and brewers spent grain were completely gasified to methane and carbon dioxide. They also reported that ruthenium was more stable catalyst than nickel at these conditions. Minowa et al. (1998, 1999) conducted the gasification of cellulose over nickel, palladium, and platinum catalysts with a batch-type reactor at reaction conditions 623 K of temperature, 25 MPa of pressure, and

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10 to 180 min reaction time. They reported that methane and carbon dioxide were mainly produced over supported nickel catalysts, whereas hydrogen and carbon dioxide were obtained over supported palladium and platinum catalysts. Fang et al. (2004) observed cellulose gasification with nickel catalyst by using a batch-type micro reactor (50 nL) and reported that the heating rate seemed to affect char formation. Davda et al. (2003) reported the gasification of ethylene glycol as glucose model compound over silica-supported nickel, ruthenium, palladium, platinum, and rhodium at temperatures from 483 to 498 K, and at 2.2 MPa. The gaseous product yield on a carbon basis was in the order of ruthenium > rhodium, platinum > nickel, palladium. The selectivity of hydrogen was in the order of palladium > platinum > nickel > ruthenium > rhodium, and the opposite trend was seen for the alkane selectivity. Ruthenium was very active for CC bond breaking. The selectivity of gaseous products is governed by the catalytic properties of metals for the water-gas shift and methanation reactions. Cortright et al. (2002) reported the gasification of glucose over a supported platinum catalyst with a batch-type reactor at 523 K and 5.6 MPa. They obtained 84% of gaseous product yield on carbon basis for 24 h reaction time. SUMMARY Characteristics of gasification reactions in subcritical and supercritical water have been summarized for three temperature regions (region I, 773973 K; region II, 647773 K; region III, below 647 K). The characteristics of biomass reactions in these regions are: Region I (773973 K of temperature and 00.2 g=cm3 water density): Biomass decomposes through pyrolysis, and activated carbon catalysts are effective for the inhibition of formation of char. Alkali catalysts promote the water-gas shift reaction. Region II (647773 K of temperature and 0.20.6 g=cm3 water density): Cellulose and lignin are hydrolyzed to low-molecular fragments (glucose and alkylphenols, etc.) that can be decomposed over supported metal catalysts. Region III (below 647 K of temperature and above 0.6 g=cm3 water density): Biomass reaction proceeds by hydrolysis that is slow.

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The composition of gaseous products depends on the type of metal catalysts used. Catalytic conversion of biomass in subcritical and supercritical water is an effective method for biomass gasification at low temperatures. For future work, practical consideration of feeding solids continuously to high-pressure reactors requires study as well as heat recovery and rapid heating methods and conditions where catalyst lifetime is greatest.

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