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Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Energy Sources, Part A: Recovery, Utilization, and Environmental Effects Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/ueso20 Pyrolysis Mechanisms of Biomass Materials A. Demirbas a a Sila Science , Trabzon, Turkey Published online: 13 May 2009. To cite this article: A. Demirbas (2009) Pyrolysis Mechanisms of Biomass Materials, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 31:13, 1186-1193, DOI: 10.1080/15567030801952268 To link to this article: http://dx.doi.org/10.1080/15567030801952268 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained in the publications on our platform. 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Terms & Conditions of access and use can be found at http://www.tandfonline.com/page/terms- and-conditions Energy Sources, Part A, 31:11861193, 2009 Copyright Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230 online DOI: 10.1080/15567030801952268 Pyrolysis Mechanisms of Biomass Materials A. DEMIRBAS 1 1 Sila Science, Trabzon, Turkey Abstract Pyrolysis is degradation of biomass by heat in the absence of oxygen which results in the production of liquid, gaseous, and solid products. Conversion of biomass materials composed predominantly of holocellulose and lignin using pyrolysis type reactions represents a promising option for the production of fuels and chemicals. The hemicelluloses degrade rst at temperatures of 470 to 530 K and cellulose follows in the temperature range of 510 to 620 K, with lignin being the last component to pyrolyse at temperatures of 550 to 770 K. If the purpose is to maximize the yield of liquid products resulting from biomass pyrolysis, a low temperature, high heating rate, short gas residence time process would be required. If the purpose were to maximize the yield of fuel gas resulting from pyrolysis, a high temperature, low heating rate, long gas residence time process would be preferred. For a high char production, a low temperature, low heating rate process would be chosen. Pyrolysis of lignocellulosic biomass materials has been found to be a promising method for producing pyrolytic oils also known as bio-oil. Keywords biomass, pyrolysis, pyrolysis mechanism, thermal degradation Introduction The term biomass (Greek, bio, life C maza or mass) refers to wood, short-rotation woody crops, agricultural wastes, short-rotation herbaceous species, wood wastes, bagasse, industrial residues, waste paper, municipal solid waste, sawdust, bio-solids, grass, waste from food processing, aquatic plants and algae animal wastes, and a host of other materials. Biomass is the name given to all of the earths living matter. Biomass, as the solar energy stored in chemical form in plant and animal materials, is among the most precious and versatile resources on earth. It is a rather simple term for all organic materials that originates from plants, trees, crops, and algae. The components of biomass include cellulose, hemicelluloses, lignin, extractives, lipids, proteins, simple sugars, starches, water, hydrocarbons, ash, and other compounds. Two larger carbohydrate categories that have signicant value are cellulose and hemicelluloses (holocellulose). The lignin fraction consists of non-sugar type molecules. Wood, woody, and other forms of biomass are some of the main renewable solid energy resources available, and they provide the only source of liquid, gaseous, and solid fuels (Bridgwater et al., 1999). Biomass is the only combustible renewable energy source that yields liquid, gaseous, and solid fuels (Bridgwater and Peacocke, 2000) and has been described as the renewable energy source with the highest potential to contribute to the energy needs of modern society (Bridgwater, 2003). One technique used to convert biomass into valuable liquid derivatives, also known as bio-oil, is pyrolysis. The resulting Address correspondence to Professor Ayhan Demirbas, P. K. 216, TR-61035 Trabzon, Turkey. E-mail: ayhandemirbas@hotmail.com 1186 D o w n l o a d e d
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Pyrolysis Mechanisms of Biomass Materials 1187 bio-oil can then be used as fuel or for the production of chemicals and other bio-based products (Maher and Bressler, 2007). Pyrolysis of lignocellulosic biomass materials has been found to be a promising method for producing pyrolytic oils also known as bio-oil (Demirbas, 2000a). Biomass is the only organic petroleum substitute which is renewable (Garg and Datta, 1998; Demirbas, 2004). Depending on the operation conditions, pyrolysis processes can be divided into three subclasses: conventional pyrolysis, fast pyrolysis, and ash pyrolysis. Yields of products obtained from biomass pyrolysis depend mainly on the chemical composition of the feedstock and the operating temperature (Ceylan and B-son Bredenberg, 1982). In the absence of oxygen, the thermal stability is in the order: lignin, cellulose, and hemicelluloses (Demirbas, 2000a). Pyrolysis of Biomass Materials Pyrolysis is the thermal decomposition of materials in the absence of oxygen or when signicantly less oxygen is present than required for complete combustion. Pyrolysis is the basic thermochemical process for converting biomass to a more useful fuel. Biomass is heated in the absence of oxygen, or partially combusted in a limited oxygen supply, to produce a hydrocarbon-rich gas mixture, an oil-like liquid, and a carbon-rich solid residue. Pyrolysis dates back to at least ancient Egyptian times, when tar for caulking boats and certain embalming agents were made by pyrolysis. In the 1980s, researchers found that the pyrolysis liquid yield could be increased using fast pyrolysis where a biomass feedstock is heated at a rapid rate and the vapors produced are also condensed rapidly (Mohan et al., 2006). In wood derived pyrolysis oil, specic oxygenated compounds are present in relatively large amounts (Rowell and Hokanson, 1979; Phillips et al., 1990; Mohan et al., 2006). A current comprehensive review focuses on the recent developments in the wood/biomass pyrolysis and reports the characteristics of the resulting bio-oils, which are the main products of fast wood pyrolysis (Mohan et al., 2006). Sufcient hydrogen added to the synthesis gas to convert all of the biomass carbon into methanol carbon would more than double the methanol produced from the same biomass base (Phillips et al., 1990). Rapid heating and rapid quenching produced the intermediate pyrolysis liquid prod- ucts, which condense before further reactions break down higher molecular-weight species into gaseous products. High reaction rates minimize char formation. Under some con- ditions, no char is formed (Demirbas, 2005). At higher fast pyrolysis temperatures, the major product is gas. Many researchers have attempted to exploit the complex degradation mechanisms by conducting pyrolysis in unusual environments (Mohan et al., 2006). The main pyrolysis variants are listed in Table 1. Pyrolysis is the simplest and almost certainly the oldest method of processing one fuel in order to produce a better one. Pyrolysis can also be carried out in the presence of a small quantity of oxygen (gasication), water (steam gasication), or hydrogen (hydrogenation). One of the most useful products is methane, which is a suitable fuel for electricity generation using high-efciency gas turbines. Cellulose and hemicelluloses form mainly volatile products on heating due to the thermal cleavage of the sugar units. The lignin forms mainly char since it is not readily cleaved to lower molecular weight fragments. The progressive increase in the pyrolysis temperature of the wood led to the release of the volatiles thus forming a solid residue that D o w n l o a d e d
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1188 A. Demirbas Table 1 Pyrolysis methods and their variants Method Residence time Temperature, K Heating rate Products Carbonation Days 675 Very low Charcoal Conventional 530 min 875 Low Oil, gas, char Fast 0.55 s 925 Very high Bio-oil Flash-liquid a <1 s <925 High Bio-oil Flash-gas b <1 s <925 High Chemicals, gas Hydro-pyrolysis c <10 s <775 High Bio-oil Methano-pyrolysis d <10 s >975 High Chemicals Ultra pyrolysis e <0.5 s 1,275 Very high Chemicals, gas Vacuum pyrolysis 230 s 675 Medium Bio-oil a Flash-liquid: Liquid obtained from ash pyrolysis accomplished in a time of <1 s. b Flash-gas: Gaseous material obtained from ash pyrolysis within a time of <1 s. c Hydropyrolysis: Pyrolysis with water. d Methanopyrolysis: Pyrolysis with methanol. e Ultra pyrolysis: Pyrolyses with very high degradation rate. is different chemically from the original starting material (Demirbas, 2000b). Cellulose and hemicelluloses initially break into compounds of lower molecular weight. This forms an activated cellulose which decomposes by two competitive reactions: one forming volatiles (anhydrosugars) and the other char and gases. The thermal degradation of the activated cellulose and hemicelluloses to form volatiles and char can be divided into categories depending on the reaction temperature. Within a re all of these reactions take place concurrently and consecutively. Gaseous emissions are predominantly a product of pyrolitic cracking of the fuel. If ames are present, re temperatures are high, and more oxygen is available from thermally induced convection. The biomass pyrolysis is attractive because solid biomass and wastes can be readily converted into liquid products. These liquids, as crude bio-oil or slurry of charcoal of water or oil, have advantages in transport, storage, combustion, retrotting, and exibility in production and marketing. The pyrolysis of biomass is a thermal treatment that results in the production of charcoal, liquid, and gaseous products. Among the liquid products, methanol is one of the most valuable products. The liquid fraction of the pyrolysis products consists of two phases: an aqueous phase containing a wide variety of organo-oxygen compounds of low molecular weight and a non-aqueous phase containing insoluble organics of high molecular weight. This phase is called tar and is the product of greatest interest. The ratios of acetic acid, methanol, and acetone of the aqueous phase were higher than those of the non-aqueous phase. The point where the cost of producing energy from fossil fuels exceeds the cost of biomass fuels has been reached. With a few exceptions, energy from fossil fuels will cost more money than the same amount of energy supplied through biomass conversion (Demirbas, 2007). The kinematic viscosity of bio-oil varies from as low as 11 mm 2 /s to as high as 115 mm 2 /s at 313 K depending on the nature of the feedstock, temperature of pyrolysis process, thermal degradation degree and catalytic cracking, the water content of the D o w n l o a d e d
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Pyrolysis Mechanisms of Biomass Materials 1189 bio-oil, the amount of light ends that have collected, and the pyrolysis process used. The bio-oils have water contents of typically 1530 wt% of the oil mass, which cannot be removed by conventional methods like distillation. Phase separation may partially occur above certain water contents. The water content of bio-oils contributes to their low energy density, lowers the ame temperature of the oils, leads to ignition difculties, and, when preheating the oil, can lead to premature evaporation of the oil and resultant injection difculties. The higher heating value (HHV) of pyrolysis oils is below 26 MJ/kg (compared to 4245 MJ/kg for conventional petroleum fuel oils). In contrast to petroleum oils, which are nonpolar and in which water is insoluble, bio-oils are highly polar and can readily absorb over 35% water (Demirbas, 2007). The bio-oil from wood is typically a liquid, almost black through dark red brown. The density of the liquid is about 1,200 kg/m 3 , which is higher than that of fuel oil and signicantly higher than that of the original biomass. The bio-oils have water contents of typically 1433 wt%, which cannot be removed by conventional methods like distillation. Phase separation may occur above certain water contents. The HHV is below 27 MJ/kg (compared to 4346 MJ/kg for conventional fuel oils). The bio-oil formed at 725 K contained high concentrations of compounds such as acetic acid, 1-hydroxy-2-butanone, 1-hydroxy-2-propanone, methanol, 2,6- dimethoxyphenol, 4-methyl-2,6-dimetoxyphenol, and 2-cyclopenten-1-one, etc. A sig- nicant characteristic of the bio-oils was the high percentage of alkylated compounds especially methyl derivatives. As the temperature increased, some of these compounds were transformed via hydrolysis (Kuhlmann et al., 1994). The formation of unsaturated compounds from biomass materials generally involves a variety of reaction pathways such as dehydration, cyclization, Diels-Alder cycloaddition reactions, and ring rearrangement. For example, 2,5-hexandione can undergo cyclization under hydrothermal conditions to produce 3-methyl-2-cyclopenten-1-one with very high selectivity of up to 81% (An et al., 1997). Reaction Mechanisms of Biomass Prolysis Pyrolysis mechanisms of biomass have been studied by many investigators (Domburg et al., 1974; Adjaye et al., 1992; Demirbas, 2000a). According to the proposed mecha- nism, the heat variations associated with the thermal degradation reactions may affect the pyrolysis route. Experimental runs indicate several endothermic and/or exothermic peaks for biomass pyrolysis (Stamm and Harris, 1953; Shazadeh et al., 1976). According to several researchers, cellulose pyrolysis is endothermic (Brown et al., 1952; Roberts and Clough, 1963; Demirbas and Kucuk, 1994), but lignin pyrolysis is exothermic (Demirbas et al., 1996). The general changes that occur during pyrolysis are enumerated below (Babu and Chaurasia, 2003; Mohan et al., 2006): 1. Heat transfer from a heat source increases the temperature inside the fuel. 2. The initiation of primary pyrolysis reactions at this higher temperature releases volatiles and forms char. 3. The ow of hot volatiles toward cooler solids results in heat transfer between hot volatiles and cooler unpyrolyzed fuel. 4. Condensation of some of the volatiles in the cooler parts of the fuel, followed by secondary reactions, can produce tar. D o w n l o a d e d
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1190 A. Demirbas 5. Autocatalytic secondary pyrolysis reactions proceed while primary pyrolytic re- actions simultaneously occur in competition. 6. Further thermal decomposition, reforming, water gas shift reactions, radicals recombination, and dehydrations can also occur, which are a function of the processs residence time/temperature/pressure prole. The mechanism of pyrolysis reactions of structural components of biomass (hemi- celluloses, cellulose, and lignin) was extensively discussed in an earlier study (Demirbas, 2000a). A process has been investigated for the saccharication of wood, involving prehy- drolysis, lignocellulose pyrolysis, and tar hydrolysis. In this process, ground wood was rst prehydrolyzed to remove the more readily hydrolyzable hemicelluloses. The residual lignocellulose was then pyrolyzed rapidly to provide a tar containing levoglucosan and its condensation products. The destructive reaction of cellulose is started at temperatures lower than 325 K and is characterized by a decreasing polymerization degree. Thermal degradation of cellulose proceeds through two types of reaction: a gradual degradation, decomposition, and charring on heating at lower temperatures, and a rapid volatilization accompanied by the formation of levoglucosan on pyrolysis at higher temperatures. The glucose chains in cellulose are rst cleaved to glucose and from this, in a second stage, glucosan is formed by the splitting off of one molecule of water. Since cellulose and levoglucosan have the same elementary formula, C 6 H 10 O 5 , a yield of 100% of the latter might be expected. The initial degradation reactions include depolymerization, hydrolysis, oxidation, dehydration, and decarboxylation (Shazadeh and Stevenson, 1982). The hemicelluloses reacted more readily than cellulose during heating (Roni et al., 2002). The thermal degradation of hemicelluloses begins above 373 K during heating for 48 h; hemicelluloses and lignin are depolymerized by steaming at a high temperature for a short time (Shazadeh et al., 1976). Lignin is broken down by extensive cleavage of b-aryl ether linkages during steaming of wood under 488 K (March, 1977). It has been found that on analysis of the methoxyl groups after isothermal heating of dry distilled wood, lignin decomposition begins at about 550 K with a maximum rate occurring between 625 K and 725 K and the completion of the reaction occurs at 725 K and 775 K (Sandermann and Augustin, 1963). The formation of char from lignin under mild reaction conditions is a result of the breaking of the relatively weak bonds, like the alkyl-aryl ether bond(s), and the consequent formation of more resistant condensed structures, as has already been noted (Domburg et al., 1974). One additional parameter, which may also have an effect on the char formation, is the moisture content of the kraft lignin used. Water is formed by dehydration. In the pyrolysis reactions, methanol arises from the breakdown of methyl esters and/or ethers from decomposition of pectin-like plant materials (Goldstein, 1981). Methanol also arises from methoxyl groups of uronic acid (Demirbas and Gll, 1998). Acetic acid is formed in the thermal decomposition of all three main components of wood. When the yield of acetic acid originating from the cellulose, hemicelluloses, and lignin is taken into account, the total is considerably less than the yield from the wood itself (Wenzl et al., 1970). Acetic acid comes from the elimination of acetyl groups originally linked to the xylose unit. If wood is completely pyrolyzed, resulting products are about what would be expected by pyrolyzing the three major components separately. The hemicelluloses would break down rst, at temperatures of 470 K to 530 K. Cellulose follows in the temperature range 510 K to 620 K, with lignin being the last component to pyrolyze at temper- D o w n l o a d e d
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Pyrolysis Mechanisms of Biomass Materials 1191 atures of 550 K to 770 K. A wide spectrum of organic substances was contained in the pyrolytic liquid fractions given in the literature (Beaumont, 1985). Degradation of xylan yields eight main products: water, methanol, formic, acetic and propionic acids, 1-hydroxy-2-propanone, 1-hydroxy-2-butanone, and 2-furfuraldeyde. The methoxy phenol concentration decreased with increasing temperature, while phenols and alkylated phenols increased. The formation of both methoxy phenol and acetic acid was possible as a result of the Diels-Alder cycloaddition of a conjugated diene and unsaturated furanone or butyrolactone. Timell (1967) described the chemical structure of the xylan as the 4-methyl-3- acetylglucoronoxylan. It has been reported that the rst runs in the pyrolysis of the pyroligneous acid consist of about 50% methanol, 18% acetone, 7% esters, 6% aldehydes, 0.5% ethyl alcohol, 18.5% water, and small amounts of furfural (Demirbas, 2000a). Pyroligneous acids disappear in high-temperature pyrolysis. The composition of the water soluble products was not ascertained but it has been reported to be composed of hydrolysis and oxidation products of glucose such as acetic acid, acetone, simple alcohols, aldehydes, sugars, etc. (Sasaki et al., 1998). Conclusion Bio-oil from biomass pyrolysis mainly consisted of aromatic, aliphatic, and naphthenic hydrocarbons and oxygenated compounds such as phenols, furans, alcohols, acids, ethers, aldehydes, and ketones. The organic compounds from biomass pyrolysis are the following main groups: 1. A gas fraction containing: CO, CO 2 , some hydrocarbons, and H 2 . 2. A condensable fraction containing: H 2 O and low molecular weight organic com- pounds (aldehydes, acids, ketones, and alcohols). 3. A tar fraction containing: higher molecular weight sugar residues, furan deriva- tives, phenolic compounds and airborne particles of tar, and charred material which form the smoke. The kinematic viscosity of bio-oil varies from as low as 11 mm 2 /s to as high as 115 mm 2 /s at 313 K depending on nature of the feedstock, temperature of pyrolysis process, thermal degradation degree and catalytic cracking, the water content of the bio- oil, the amount of light ends that have collected, and the pyrolysis process used. The bio-oil viscosity and chemical composition were found to change substantially over time probably due to polymerization of some components. Upon storage, the concentration of aromatic hydrocarbons and phenols decreased while the concentration of aldehydes and ketones increased (Adjaye et al., 1992). References Adjaye, J. D., Sharma, R. K., and Bakhshi, N. N. 1992. Characterization and stability analysis of wood-derived bio-oil. Fuel Proc. Technol. 31:241256. An, J., Bagnell, L., Cablewski, T., Strauss, C. R., and Trainor, R. W. 1997. Applications of high- temperature aqueous media for synthetic organic reactions. J. Org. Chem. 62:25052511. Babu, B. V., and Chaurasia, A. S. 2003. Modeling for pyrolysis of solid particle: Kinetics and heat transfer effects. Energy Convers. Mgmt. 44:22512275. Balat, M. 2009. New biofuel production technologies. Energy Edu. Sci. Technol. A 22:147161. D o w n l o a d e d
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1192 A. Demirbas Beaumont, O. 1985. Flash pyrolysis products from beech wood. Wood Fiber Sci. 17:228239. Bridgwater, A. V. 2003. Renewable fuels and chemicals by thermal processing of biomass. Chem. Eng. J. 91:87102. Bridgwater, A. V., and Peacocke, G. V. C. 2000. Fast pyrolysis processes for biomass. Renew. Sust. Energy Rev. 4:173. Bridgwater, A. V., Meier, D., and Radlein, D. 1999. An overview of fast pyrolysis of biomass. Organic Geochem. 30:14791493. Brown, H. P., Panshin, A. J., and Forsaith, C. C. 1952. Textbook of Wood Technology, vol. II. New York: McGraw-Hill. Ceylan, R., and B-son Bredenberg, J. 1982. Hydrogenolysis and hydrocracking of the carbon- oxygen bond. 2. Thermal cleavage of the carbon-oxygen bond in guaiacol. Fuel 61:377382. Demirbas, A. 2000a. Biomass resources for energy and chemical industry. Energy Educ. Sci. Technol. 5:2145. Demirbas, A. 2000b. Mechanisms of liquefaction and pyrolysis reactions of biomass. Energy Convers. Mgmt. 41:633646. Demirbas, A. 2004a. Combustion characteristics of different biomass fuels. Prog. Energy Combus. Sci. 30:219230. Demirbas, A. 2005. Potential applications of renewable energy sources, biomass combustion prob- lems in boiler power systems and combustion related environmental issues. Progress Energy Combus. Sci. 31:171192. Demirbas, A. 2007. The inuence of temperature on the yields of compounds existing in bio-oils obtained from biomass samples via pyrolysis. Fuel Proc. Technol. 88:591597. Demirbas, A. 2008. Economic and environmental impacts of the liquid biofuels. Energy Edu. Sci. Technol. 22:3758. Demirbas, A., and Gll, D. 1998. Acetic acid, methanol, and acetone from lignocellulosics by pyrolysis. Energy Edu. Sci. Technol. 1:111115. Demirbas, A., Akdeniz, F., Erdogan, Y., and Pamuk, V. 1996. Kinetic for fast pyrolysis of hazelnut shell. Fuel Sci. Technol. Int. 14:405417. Demirbas, A., and Kucuk, M. M. 1994. Kinetic study on the pyrolysis of hazelnut shell. Cellulose Chem. Technol. 28: 8594. Goldstein, I. S. 1981. Organic Chemical from Biomass. Boca Raton, FL: CRC Press, p. 13. Kuhlmann, B., Arnett, E. M., and Siskin, M. 1994. Classical organic reactions in pure superheated water. J. Organic Chem. 59:30983101. Maher, K. D., and Bressler, D. C. 2007. Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals. Biores. Technol. 98:23512368. March, J. 1977. Advanced Organic Chemistry: Reactions, Mechanisms and Structure. New York: McGraw-Hill, p. 620. Mohan, D., Pittman, C. U., Jr., and Steele, P. H. 2006. Pyrolysis of wood/biomass for bio-oil: A critical review. Energy Fuels 20:848889. Phillips, V. D., Kinoshita, C. M., Neill, D. R., and Takahashi, P. K. 1990. Thermochemical production of methanol from biomass in Hawaii. Appl. Energy 35:167175. Roni Cohen, R., Jensen, K. A., Jr., Houtman, C. J., and Hamel, K. E. 2002. Signicant levels of extracellular reactive oxygen species produced by brown rot basidiomycetes on cellulose. FEBS Lett. 531:483488. Rowell, R. M., and Hokanson, A. E. 1979. Methanol from Wood: A Critical Assessment in Progress in Biomass Conversion, vol. 1. Sarkanen, K. V., and Tillman, D. A. (Eds.). New York: Academic Press. Sandermann, W., and Augustin, H. 1963. Chemical investigations on the thermal decomposition of wood. Holz. Roh-Werkst 12:256265. Sasaki, M., Kabyemela, B. M., Malaluan, R. M., Hirose, S., Takeda, N., Adschiri, T., and Arai, K. 1998. Cellulose hydrolysis in subcritical and supercritical water. J. Supercrit. Fluids 13:261 268. D o w n l o a d e d
b y
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Pyrolysis Mechanisms of Biomass Materials 1193 Shazadeh, V., Sarkanen, K. V., and Tillman, D. A. 1976. Thermal Uses and Properties of Carbohydrates and Lignins. New York: Academic Press. Shazadeh, F., and Stevenson, T. T. 1982. Saccharication of Douglas-r wood by a combination of prehydrolysis and pyrolysis. J. Appl. Polym. Sci. 27:45774585. Stamm, A. J., and Harris, E. 1953. Chemical Processing of Wood. New York: Chem. Publ. Timell, T. E. 1967. Recent progress in the chemistry of wood hemicelluloses. Wood Sci. Technol. 1:4570. Wenzl, H. F. J., Brauns, F. E., and Brauns, D. A. 1970. The Chemical Technology of Wood. New York: Academic Press. D o w n l o a d e d