Energy Sources, Part A, 30:2737, 2008 Copyright Taylor & Francis Group, LLC ISSN: 1556-7036 print/1556-7230 online

e DOI: 10.1080/00908310600626705

Products from Lignocellulosic Materials via Degradation Processes

A. DEMIRBAS1
1

Sila Science, Trabzon, Turkey

Abstract Products from lignicellulosic materials by degradation processes are reviewed based on the results of some investigations. Biomass provides a potential source of added value chemicals, such as reducing sugars, furfural, ethanol and other products by using biochemical or chemical and thermochemical. The initial degradation reactions include depolymerization, hydrolysis, oxidation, dehydration, and decarboxylation. The gas phase of pyrolitic degradation products contain mostly carbon monoxide and carbon dioxide, and minor proportions of hydrogen, methane, ethane, and propane. The liquid fraction consists mainly of water, with small proportions of acetaldehyde, propion aldehyde, butiraldehyde, acrolein, croton-aldehyde, furan, acetone, butanedione, and methanol. There are many studies on biomass conversion methods because of energy problems and environmental pollution. Ethanol is an alcohol and is fermented from sugars, starches or from lignocellulosic biomass. In order to produce bioethanol from lignocellulosic biomass, a pretreatment process is used to reduce the sample size, degrade the hemicelluloses to sugars, and open up the structure of the cellulose component. The cellulose portion is hydrolyzed by acids or enzymes into glucose sugar that is fermented to bioethanol. The sugars from the hemicelluloses are also fermented to bioethanol. Keywords biomass, biomass conversion processes, degradation

Introduction
Lignocellulosic materials include wood, grass, forestry waste, agricultural residues, and municipal solid wastes. Wood is mainly composed of cellulose, hemicellulose and lignin. Cellulose is a high molecular weight linear polymer of -1,4-linked D-glucose units which can appear as a highly crystalline material (Fan et al., 1982). Hemicelluloses are branched polysaccharides consisting of pentoses, hexoses and uronic acids (Saka, 1991). Softwood hemicelluloses have a higher proportion of mannose and glucose units than hardwood hemicelluloses, which usually contain a higher proportion of xylose units. Furthermore, hemicelluloses are more highly acetylated in hardwoods than in softwoods (Fengel and Wenger, 1989). The relative abundance of individual sugars in carbohydrate fraction of wood is shown in Table 1. Lignin is an aromatic polymer synthesised from phenylpropanoid precursors (Adler, 1977). Lignins are divided into two classes, namely guaiacyl lignins and guaiacyl-syringyl lignins, differing in the substituents of the phenylpropanoid skeleton. Guaiacyl-lignins have a methoxy-group in
Address correspondence to Professor Ayhan Demirbas, P.K. 216, TR-61035 Trabzon, Turkey. E-mail: ayhandemirbas@hotmail.com

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A. Demirbas Table 1 Relative abundance of individual sugars in carbohydrate fraction of wood (% by weight) Sugar Glucose Xylose Mannose Galactose Arabinose Rhamnose Uronic acids Softwoods 6165 913 716 617 <3.5 <1 47 Softwood bark 5763 1115 616 15 411 <1 Hardwoods 5573 2039 0.44 14 <1 <1 47 Hardwood bark 5365 1836 0.33 16 28 <1

Source: Goldstein, 1981.

the 3-carbon position, whereas syringyl-lignins have a methoxy-group in both the 3carbon and 5-carbon positions. Softwood and hardwood lignins belong to the rst and second category, respectively. Softwoods generally contain more lignin than hardwoods (Saka, 1991). Biomass provides a potential source of added value chemicals, such as reducing sugars, furfural, ethanol and other products, by using biochemical or chemical and thermochemical. There are many studies on biomass conversion methods because of energy problems and environmental pollution (Kucuk and Demirbas, 1997). Lignocellulosic materials represent an important source of energy and chemicals. Before the area of petrochemicals, various chemicals were produced from biomass by techniques such as extraction, fermentation, and carbonization (Pakdel et al., 1997). Of the biomass conversion processes, interest in pyrolysis has been growing (Bridgwater and Kuester, 1998; Grassi et al., 1990). Pyrolysis is a thermochemical process that converts biomass into liquid, charcoal, and noncondensable gases by heating the biomass in the absence of air (Demirbas, 2001a). Many biomass pyrolysis processes have been investigated (Demirbas, 2000; Caballero et al., 2000; Demirbas, 2001b; Demirbas, 2005). The liquid fraction of the pyrolysis products consists of 2 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 oils are composed of a range of oxygenated compounds, including cyclopentanone, methoxybenzene, acetic acid, furfural, acetophenone, phenol, benzoic acid and their alkylated derivatives (Demirbas, 2002; Gullu, 2003). Limited work has been conducted on the application of phenolic fraction separated from pyrolysis liquid products. Phenolics are valuable compounds and have been used as food aromas, pharmaceuticals and as intermediates for chemical synthesis. Signicant amounts of phenolic compounds frequently occur in foods such as fruits and vegetables and are routinely consumed in our diet. Phenolics, including simple phenols (mostly phenolic acids), avonoids and anthocyanins, are hydrophilic compounds with antioxidant activity in vitro (Ju and Bramlage, 1999; Santos-Gomes et al., 2002). Flavonoids represent a large group of phenolic compounds found in plants (Vvedenskaya and Vorsa, 2004). Flavonoids and phenolic acids are two large and heterogeneous groups of biologically active non-nutrients

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(Hakkinen et al., 1999). Phenolic phytochemicals are important aromatic secondary metabolites in plants, many of which are commonly substituted by sugar moieties such as glucose, arabinose, xylose, rhamnose, and galactose (Kim et al., 2003). Flavonols and phenolic acids have been proposed to have benecial effects on health as antioxidants (Rice-Evans et al., 1996; Natella et al., 1999) and anticarcinogens (Hakkinen and Trrnen, 2000). The phenolic compounds can be obtained from pyrolysis of lignin. The cleavage of the lignin aromatic CO bond led to the formation of one oxygen atom products, i.e., 3-propylphenol, 4-propylphenol and methyl-4-propylphenols. The selectivity of the formation of 3-propylphenol was higher than that of 4-propylphenol at all reaction temperature and all reaction temperatures and all reaction times. The extent of conversion of 1-ethyl-4-hydroxybenzene (4-ethylphenol), as a model compound was relatively small under both sets of reaction conditions. The main reaction products were diethyl phenol, p-cresol, and phenol. The nature of these products shows that CC cleavage occurred between the aromatic ring and a-carbon atom. There was no indication of signicant formation of polymerized reaction products. The cleavage of the propyl side chain CC bonds gave minor products, i.e., 3-methylpyrocatechol, 4-methylpyrocatechol, 4methylguaiacol, guaiacol, cresols, and phenol. The nature of the products show that cleavage occurred between the a- and b-carbon atoms, as well as between the ring and alpha carbon atoms (Demirbas, 2002).

Degradation of Lignocellulosic Materials by Hydrolysis

Biomass provides a potential source of added-value chemicals, such as reducing sugars, furfural, ethanol and other products, by using enzyme- or acid-catalyzed hydrolysis. Enzyme-catalyzed hydrolysis of biomass is a much slower reaction than acid hydrolysis. The recovery of the enzymes is difcult. Concentrated acid hydrolysis of biomass is limited by corrosion and expensive acid recovery problems. Various methods for the hydrolysis of lignocellulosic materials have recently been described (Olsson and Hahn-Hagerdal, 1996). The dilute acid process is conducted under high temperature and pressure, and has a reaction time in the range of seconds or minutes, which facilitates continuous processing. As an example, using a dilute acid process with 1% sulfuric acid in a continuous ow reactor at a residence time of 0.22 minutes and a temperature of 510 K with pure cellulose provided a yield over 50% sugars. In this case, 1,000 kg of dry wood would yield about 164 kg of pure ethanol. Dilute acids lead to a limited hydrolysis called prehydrolysis. Dilute-acid hydrolysis is carried out using mineral acids such as H2 SO4 or HCl, at temperatures between 395 K and 475 K (Grethlein and Converse, 1991; Torget and Hsu, 1994). The chief advantages to using hydrochloric acid over sulfuric acid are that HCI permeates the wood more easily than H2 SO4 and is a volatile compound, which assists in the crucial acid recovery steps. The Udic-Rheinau process was an attempt to make the Bergius-Rheinau process economically advantageous. In the improved process, the wood was rst prehydrolyzed in 1% HCI at 403 K to remove the hemicelluloses. The wood was then dried and subsequently hydrolyzed with 40% HC1 at 295 K for 10 h. After washing the lignin residue with dilute HC1, the HCI was recovered by vacuum distillation. This process was more economical than the Bergius-Rheinau process (Kucuk and Demirbas, 1997). The biggest advantage of dilute acid processes is their fast rate of reaction, which facilitates continuous processing. Since 5-carbon sugars degrade more rapidly than 6-carbon sugars, one way to decrease sugar degradation is to have a two-stage process. The rst stage is conducted under mild

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process conditions to recover the 5-carbon sugars while the second stage is conducted under harsher conditions to recover the 6-carbon sugars. Hydrolysis of lignocellulosic materials by concentrated sulfuric or hydrochloric acids is a relatively old process. The concentrated acid process uses relatively mild temperatures, and the only pressures involved are those created by pumping materials from vessel to vessel. Reaction times are typically much longer than for dilute acid. This method generally uses concentrated sulfuric acid followed by a dilution with water to dissolve and hydrolyze or convert the substrate into sugar. This process provides a complete and rapid conversion of cellulose to glucose and hemicelluloses to 5-carbon sugars with little degradation. The critical factors needed to make this process economically viable are to optimize sugar recovery and cost effectively recovers the acid for recycling. Another basic method of hydrolysis is enzymatic hydrolysis. The chemical pretreatment of the lignocellulosic biomass is necessary before enzymatic hydrolysis. The rst application of enzymatic hydrolysis was used in separate hydrolysis and fermentation steps. Enzymatic hydrolysis is accomplished by cellulolytic enzymes. Different kinds of cellulases may be used to cleave the cellulose and hemicelluloses. A mixture of endoglucanases, exoglucanases, -glucosidases and cellobiohydrolases is commonly used (Ingram and Doran, 1995; Laymon et al., 1996). Figure 1 shows the main degradation products occurring during hydrolysis of lignocellulosic material. When hemicelluloses are hydrolysed to xylose, mannose, acetic acid, galactose, and glucose are liberated. Xylose is a hemicellulosic sugar mainly used for its bioconversion to xylitol (Herrera et al., 2003). Hemicellulosic hydrolysis can be generalized as Hemicelluloses ! Xylan ! Xylose ! Furfural Acetyl groups ! Acetic acid (1) (2)

Degradation of xylan yields eight main products: water, methanol, formic, acetic, and propionic acids, hydroxy-1-propanone, hydroxy-1-butanone and 2-furfuraldeyde (Gullu, 2003). At high temperature and pressure, xylose is further degraded to furfural (Dunlop, 1948). Levulinic acid is formed by hydroxymethyl furfural degradation (Ulbricht

Figure 1. Main degradation products occurring during hydrolysis of lignocellulosic material.

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et al., 1984). Cellulose is hydrolysed to glucose. The following reaction is proposed for hydrolysis of cellulose: Cellulose ! Glucan ! Glucose ! Decomposition products (3)

The residual lignin after acid hydrolysis can be a raw material for producing phenol, benzene, toluene, xylene, and other aromatics through hydrocracking and related processes. The rational upgrading of this fraction plays an important role in the economic utilization of two-stage biomass hydrolysis (Kucuk and Demirbas, 1997). Phenolic compounds are generated from partial breakdown of lignin (Bardet et al., 1985; Lapierre et al., 1983; Sears et al., 1971), and have also been reported to be formed during carbohydrate degradation (Popoff and Theander, 1976; Suortti, 1983). The furan derivatives such as furfural and low molecular phenolic compounds will react further to form some polymeric material.

Biochemical Degradation of Lignocellulosic Materials

Biochemical degradation is the process by which biomass is converted to gas (methane/ carbon dioxide), waste (compost or fertilizer) and water by using microorganisms. The biochemical processes refer mainly to (1) aerobic fermentation, which produces compost, carbon dioxide, and water; (2) anaerobic fermentation which produces fertilizer and gas (methane/carbon dioxide), and (3) alcoholic fermentation which produces ethanol, carbon dioxide, and waste. Anaerobic decomposition is a complex process. The process by which anaerobic bacteria decompose organic matter into methane, carbon dioxide, and a nutrient-rich sludge involves a step-wise series of reactions requiring the cooperative action of several organisms. A variety of factors affect the rate of digestion and biogas production. The most important is temperature. In a process of manure and straw mixture digestion, for the rst 3 days, methane yield was almost 0% and carbon dioxide generation was almost 100%. In this period, digestion occurred as aerobic fermentation to carbon dioxide. The yields of methane and carbon dioxide gases were fty-fty at the 11th day. At the end of the 20th day, the digestion reached the stationary phase. The methane content of the biogas was in the range of 7379% for the runs, the remainder being principally carbon dioxide. During a 30-day digestion period, 8085% of the biogas was produced in the rst 1518 days. This implies that the digester retention time can be designed to 1518 days instead of 30 days (Demirbas and Ozturk, 2004). Another anaerobic method is to produce landll gas (a mixture of methane and other gases). The degradation of the organic component of refuse in landlls is a process carried out by a succession of microbial populations.

Thermochemical Degradation of Lignocellulosic Materials

Thermochemical degradation can be subdivided into direct liquefaction, gasication, and pyrolysis. In the case of liquefaction, feedstock macro-molecule compounds are decomposed into fragments of light molecules in the presence of a suitable catalyst. With pyrolysis, on the other hand, a catalyst is usually unnecessary, and the light decomposed fragments are converted to oily compounds through homogeneous reactions in the gas phase.

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A. Demirbas

The degradation of biomass into smaller products mainly proceeds by depolymerization and deoxygenation. During these reactions, however, some condensation and repolymerization of intermediate products also do proceed. To prevent these undesirable reactions of intermediates, various methods have been attempted. The use of hydrogen is believed to be one of the highly effective methods. When hydrogen is not used, another stabilizer is needed. Concerning the catalytic effect of alkali metal salts, there has been little description about the roles that a catalyst plays in the liquefaction with some exceptions. Appell (1967) proposed the mechanism for sodium carbonate-catalyzed liquefaction of carbohydrate in the presence of carbon monoxide. According to this mechanism, deoxygenation occurs through decarboxylation from esterm formed by the hydroxyl group and formate ion derived from the carbonate. Alkali salts, such as sodium carbonate and potassium carbonate, can act as catalysts for hydrolysis of macromolecules, such as cellulose and hemicellulose, into smaller fragments (Chornet and Overend, 1985). The micellar-like broken down fragments produced by hydrolysis are then degraded to smaller compounds by dehydration, dehydrogenation, deoxygenation and decarboxylation. These compounds, once produced, rearrange through condensation, cyclization, and polymerization, leading to new compounds (Chornet and Overend, 1985). Lignin is a macromolecule, which consists of alkylphenols and has a complex threedimensional structure. It is generally accepted that free phenoxyl radicals are formed by thermal decomposition of lignin above 525 K and that the radicals have a random tendency to form a solid residue through condensation or repolymerization. The yield of heavy oil decreased as the holding time was prolonged, owing to the formation of solid residue by repolymerization of heavy oils, once produced. In the case of barks containing larger amounts of lignin than woods, the yields of heavy oil could be lower, attributed to repolymerization of the primary heavy oils (Demirbas, 2000). The heavy oil obtained from the liquefaction process was a viscous tarry lump, which sometimes caused troubles in handling. For this purpose, some organic solvents were added to the reaction system. When only glycerol was used as a reaction solvent, in the presence of alkaline, the polymers, polyglyceride, are formed on under heating, and the glycerol is spent entirely (Demirbas, 1985).

Pyrolysis Liquid, solid, and gaseous products were obtained from lignocellulosic materials by pyrolysis. 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 (mainly aromatics) of high molecular weight. This phase is called bio-oil or tar, and is the product of greatest interest. The ratios of acetic acid, methanol, and acetone of aqueous phase were higher than those of the non-aqueous phase. It has been reported that the rst runs in the pyrolysis of the pyroligneous acid consists of about 50% methanol, 18% acetone, 7% esters, 6% aldehydes, 0.5% ethyl alcohol, 18.5% water, and small amounts of furfural (Wenzl et al., 1970). Table 2 shows the gas chromatographic analysis of the liquid fraction of pyrolysis products from beech wood (Demirbas, 2006). 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

Products from Lignocellulosics Table 2 Gas chromatographic analysis of the liquid fraction of pyrolysis products from beech wood (wt% dry basis) Reaction temperature (K) Compound Acetic acid Methyl acetate 1-hydroxy-2-propanone Methanol 1-hydroxy-2-butanone 1-hydroxy-2-propane acetate Levoglucosan 1-hydroxy-2-butanone acetate Formic acid Guaiacol Crotonic acid Butyrolactone Propionic acid Acetone Valeric acid Isovaleric acid Furfural 5-methyl-furfural Butyric acid Valerolactone Propanone 2-butanone Crotonolactone Acrylic acid 2-cyclopenten-1-one 2-methyl-2-cyclopenten-1-one Cyclopentenone Methyl-2-furancarboxaldehyde Phenol 2,6-dimethoxyphenol Methyl phenol 4-methyl-2,6-dimetoxyphenol
Source: Demirbas, 2006.

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625 16.8 0.47 6.32 4.16 3.40 1.06 2.59 0.97 1.18 0.74 0.96 0.74 0.96 0.62 0.72 0.68 2.52 0.65 0.56 0.51 0.41 0.18 0.12 0.44 1.48 0.40 0.10 0.73 0.24 2.28 0.32 2.24

675 16.5 0.35 6.84 4.63 3.62 0.97 2.10 0.78 1.04 0.78 0.74 0.68 0.81 0.78 0.62 0.59 2.26 0.51 0.50 0.45 0.35 0.17 0.19 0.39 1.65 0.31 0.14 0.65 0.30 2.09 0.38 2.05

725 15.9 0.21 7.26 5.08 3.82 0.88 1.62 0.62 0.84 0.82 0.62 0.66 0.60 0.93 0.55 0.51 2.09 0.42 0.46 0.38 0.28 0.32 0.29 0.33 1.86 0.24 0.16 0.58 0.36 1.98 0.44 1.84

775 12.6 0.16 7.66 5.34 3.88 0.83 1.30 0.54 0.72 0.86 0.41 0.67 0.49 1.08 0.46 0.42 1.84 0.44 0.39 0.32 0.25 0.38 0.36 0.25 1.96 0.17 0.23 0.50 0.43 1.88 0.50 1.74

825 8.42 0.14 8.21 5.63 3.96 0.78 1.09 0.48 0.60 0.89 0.30 0.62 0.41 1.22 0.38 0.35 1.72 0.40 0.31 0.34 0.26 0.45 0.40 0.19 2.05 0.13 0.27 0.44 0.54 1.81 0.66 1.69

875 5.30 0.11 8.46 5.82 4.11 0.75 0.38 0.45 0.48 0.93 0.18 0.63 0.34 1.28 0.30 0.26 1.58 0.36 0.23 0.35 0.21 0.43 0.44 0.15 2.13 0.14 0.31 0.38 0.66 1.76 0.87 1.58

and 2-cyclopenten-1-one, etc. A signicant characteristic of the bio-oils was the high percentage of alkylated compounds especially methyl derivatives. The destructive reaction of cellulose is started at temperatures lower than 325 K and is characterized by a decreasing polymerization degree. 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. The isothermal pyrolysis of cellulose in air and milder

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conditions, in the temperature range 625645 K, was investigated (Fengel and Wegener, 1983). The decreased formation of char at the higher rate of heating was accompanied by an increased formation of tar. The liquid fraction consisted mainly of water, with small proportions of acetaldehyde, propion aldehyde, butiraldehyde, acrolein, crotonaldehyde, furan, acetone, butanedione, and methanol. The net effect is a decrease in the volatile fuel production and an increased yield of char cellulose converted to levoglucosan at above 535 K temperatures (Freudenberg and Neish, 1968). Rapid depolymerization of the cellulose by pyrolysis can lead to the recovery of free sugars from both levoglucosan and its condensation products in the tar. The hemicelluloses, which are present in deciduous woods chiey as pentosans and in coniferous woods almost entirely as hexosanes, undergo thermal decomposition very readily. It was therefore to be expected that furan derivatives would readily be found among the decomposition products. The thermal degradation of hemicelluloses begins above 373 K during heating for 48 h; hemicelluloses and lignin are depolymerized by steaming at high temperature for a short time. The metoxyl content of wet meals decreased at 493 K. Therefore, the decrease of metoxyl contents below 473 K is mainly attributed to the loss of metoxyl groups from the hemicelluloses (Demirbas, 2000). 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 to wood itself (Wenzl et al., 1970). This can be explained by the fact that the main source of acetic acid is the acetyl groups which are split of during the isolation of the single components. Undoubtedly, most of the acetyl groups are attached to the pentosans. The acetyl derivatives of xylose and arabinose are found in the products of a mild acid hydrolysis. The pyrolysis of lignin has been studied widely (Adler, 1977; Pakdel et al., 1997; Demirbas, 2000). Pyrolysis seems to produce the most substituted phenols on a selective basis. Lignin is broken down by extensive cleavage of -aryl ether linkages during steaming of wood under 488 K (March, 1977). The cleavage of the aromatic CO bond led to the formation of one oxygen atom products, i.e., 3-propylphenol, 4-propylphenol, and methyl-4-propylphenols. The extent of conversion of 1-ethyl-4-hydroxybenzene (4ethylphenol), as a model compound, was relatively small under both sets of reaction conditions. The nature of these products shows that CC cleavage occurred between the aromatic ring and -carbon atom. There was no indication of signicant formation of polymerized reaction products. The cleavage of the propyl side chain CC bonds gave minor products, i.e., 3-methylpyrocatechol, 4-methylpyrocatechol, 4-methylguaiacol, guaiacol, cresols, and phenol (Demirbas, 2000). The phenol content increased to 52% and the yield of neutral oils increased from 18 to 33% with increasing temperature, while the methoxyl content decreased. The methoxyl content at 675 K amounted to 11.8%, at 875 K to only 5%. The coke formed could be briqueted without the addition of a binder (Demirbas, 1999). Gasication Some solids, liquids, and gases are produced in every thermal degradation process, including gasication. However, pyrolysis differs from gasication in that the products of interest are the char and liquids. Gasication is the process by which lignocellulosic matter is converted to gas through thermal decomposition in an oxygen decient environment, followed by secondary reactions of the resulting volatiles. The gas phase of

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Figure 2. Main themochemical degradation products from lignocellulosic material.

thermal degradation products contains mostly carbon monoxide and carbon dioxide, and minor proportions of hydrogen, methane, ethane, and propane. The yield of produced gas increased linearly with an increase in the temperature, and the concentrations of H2 , CH4 , and C2 H4 increased linearly with an increase in the temperature. Hydro-gasication conversion of biomass to liquids has been demonstrated with the use of a number of processing congurations. Generally, wood or biomass is injected as slurry into a high pressure reactor, using a water or synthetic oil carrier. The reaction occurs in reducing hydrogen phase. The reaction temperature varies from 625 to 695 K and the pressure from 5 to 28 MPa. Sodium carbonate or nickel carbonate catalysts are used in some cases. Figure 2 shows main themochemical degradation products from lignocellulosic material.

Conclusion
Lignicellulosic materials provides a potential source of added value chemicals, such as reducing sugars, furfural, ethanol and other products, by using biochemical or chemical and thermochemical. The initial degradation reactions include depolymerization, hydrolysis, oxidation, dehydration, and decarboxylation. There are many studies on biomass conversion methods because of energy problems and environmental pollution. In the pyrolysis reactions of biomass: water is formed by dehydration; acetic acid comes from the elimination of acetyl groups originally linked to the xylose unit; furfural is formed by dehydration of the xylose unit; formic acid proceeds from carboxylic groups of uronic acid; and methanol arises from methoxyl groups ofuronic acid. Pyroligneous acids disappear in high-temperature pyrolysis. Levoglucosan is also sensitive to heat and decomposes to acetic acid, acetone, phenols, and water. Methanol arises from the methoxyl groups of aronic acid.

References
Adler, E. 1977. Lignin chemistrypast, present and future. Wood Sci. Technol. 11:169218. Appell, H. R. 1967. In: Fuels from Waste, Anderson, L., Tilman, D. A., (Eds.). New York: Academic Press.

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Bardet, M., Robert, D. R., and Lundqvist, K. 1985. On the reactions and degradation of the lignin during steam hydrolysis of aspen wood. Sven. Papperstidn. 6:6167. Bridgwater, A. V., and Kuester, J. L. (Eds.). 1998. Research in Thermochemical Biomass Conversion. London: Elsevier Applied Science. Caballero, M. A., Corella, J., Aznar, M. P., and Gil, J. 2000. Biomass gasication with air in uidized bed. Hot gas cleanup with selected commercial and full-size nickel-based catalysts. Ind. Eng. Chem. Res. 39:11431154. Chornet, E., and Overend, R. P. 1985. Fundamentals of Thermochemical Biomass Conversion. Amsterdam: Elsevier. Demirbas, A. 1985. A new method on wood liquefaction. Chim. Acta Turc. 13:363368. Demirbas, A. 1999. Fuel properties of charcoal derived from hazelnut shell and the production of briquets using pyrolytic oil. Energy 24:141150. Demirbas, A. 2000. Mechanisms of liquefaction and pyrolysis reactions of biomass. Energy Convers. Mgmt. 41:633646. Demirbas, A. 2001a. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Convers. Mgmt. 42:13571378. Demirbas, A. 2001b. Biomass to charcoal, liquid, and gaseous products via carbonization process. Energy Sources 23:579587. Demirbas, A. 2002. Analysis of liquid products from biomass via ash pyrolysis. Energy Sources 24:337345. Demirbas, A. 2005. Pyrolysis of ground beech wood in irregular heating rate conditions. J. Anal. Appl. Pyrolysis 73:3943. Demirbas, A. 2006. Unpublished data. Demirbas, A., and Ozturk, T. 2004. Anaerobic digestion of agricultural solid residues. Int. J. Green Energy. 1:483494. Dunlop, A. P. 1948. Furfural formation and behaviour. Ind. Eng. Chem. 40:204209. Fan, L. T., Lee, Y. H., and Gharpuray, M. M. 1982. The nature of lignocellulosics and their pretreatments for enzymatic hydrolysis. Adv. Biochem. Eng. 23:158187. Fengel, D., and Wegener, G. 1989. Wood: Chemistry, Ultrastructure, Reactions. Berlin, New York: Walter De Gruyter. Freudenberg, K., and Neish, A. C. 1968. Constitution and Biosynthesis of Lignin. New York: Springer. Goldstein, I. S. 1981. Organics Chemicals from Biomass. Boca Raton, Florida: CRC Press, Inc. Grethlein, H. E., and Converse, A. O. 1991. Common aspects of acid prehydrolysis and steam explosion for pretreating wood. Biores. Technol. 36:7782. Grassi, G., Gosse, G., and dos Santos, G. (Eds.). 1990. Biomass for Energy and Industry. London: Elsevier Applied Science. Gullu, D. 2003. Effect of catalyst on yield of liquid products from biomass via pyrolysis. Energy Sources 25:753765. Hakkinen, S. H., and Trrnen, A. R. 2000. Content of avonols and selected phenolic acids in strawberries and Vaccinium species: Inuence of cultivar, cultivation site and technique. Food Res. Int. 33:517524. Hakkinen, S., Heinonen, M., Karenlampi, S., Mykkanen, H., Ruuskanen, J., and Trrnen, R. 1999. Screening of selected avonoids and phenolic acids in 19 berries. Food Res. Int. 32: 345353. Herrera, A., Tellez-Luis, S. J., Ramyrez, J. A., and Vazquez, M. 2003. Production of xylose from sorghum straw using hydrochloric acid. J. Cereal Sci. 37:267274. Ingram, L. O., and Doran, J. B. 1995. Conversion of cellulosic materials to ethanol. FEMS Microbiol. Rev. 16:235241. Ju, Z., and Bramlage, W. J. 1999. Phenolics and lipid-soluble antioxidants in fruit cuticle of apples and their antioxidant activities in model systems. Postharvest Biol. Technol. 16:107118. Kim, D-O., Jeong, S. W., and Lee, C. Y. 2003. Antioxidant capacity of phenolic phytochemicals from various cultivars of plums. Food Chemistry 81:321326.

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Kucuk, M. M., and Demirbas, A. 1997. Biomass conversion processes. Energy Convers. Mgmt. 38:151165. Lapierre, C., Rolando, C., and Monties, B. 1983. Characterization of poplar lignins acidolysis products: Capillary gas-liquid and liquid-liquid chromatography of monomeric compounds. Holzforschung 37:189198. Laymon, R. A., Adney, W. S., Mohagheghi, A., Himmel, M. E., and Thomas, S. R. 1996. Cloning and expression of fulllength Trichoderma reesei cellobiohydrolase I cDNAs in Escherichia coli. Appl. Biochem. Biotechnol. 57/58:389397. March, J. 1977. In: Advanced Organic Chemistry: Reactions, Mechanisms and Structure. New York: McGraw-Hill. Natella, F., Nardini, M., Di Felice, M., and Scaccini, C. 1999. Benzoic and cinnamic acid derivatives as antioxidants: Structure-activity relation. J. Agric. Food Chem. 47:14531459. Olsson, L., and Hahn-Hagerdal, B. 1996. Fermentation of lignocellulosic hydrolysates for ethanol production. Enzyme Microb. Technol. 18:312331. Pakdel, H., Amen-Chen, C., and Roy, C. 1997. Phenolic compounds from vacuum pyrolysis of wood wastes. Can. J. Chem. Eng. 75:121126. Popoff, T., and Theander, O. 1976. Formation of aromatic compounds from carbohydrates part III. Reaction of D-glucose and D-froctose in slightly acidic, aqueous solution. Acta Chem. Scand. B 30:397402. Rice-Evans, C. A., Miller, N. J., and Paganga, G. 1996. Structure-antioxidant activity relationships of avonoids and phenolic acids. Free Radical Biol. Med. 20:933956. Saka, S. 1991. Chemical Composition and Distribution. New York: Dekker, pp. 358. Santos-Gomes, P. C., Seabra, R. M., Andrade, P. B., and Fernandes-Ferreira, M. 2002. Phenolic antioxidant compounds produced by in vitro shoots of sage (Salvia ofcinalis L.). Plant Sci. 162:981987. Sears, K. D., Beelik, A., Casebier, R. L., Engen, R. J., Hamilton, J. K., and Hergert, H. L. 1971. Southern pine prehydrolyzates: Characterization of polysaccharides and lignin fragments. J. Polym. Sci. 36:425443. Suortti, T. 1983. Identication of antimicrobial compounds in heated neutral glucose and fructose solutions. Lebensm. Unters. Forsch. 177:9496. Torget, R., and Hsu, T. A. 1994. Two-temperature dilute acid prehydrolysis of hardwood xylan using a percolation process. Appl. Biochem. Biotechnol. 45/46:523. Ulbricht, R. J., Sharon, J., and Thomas, J. 1984. A review of 5-hydroxymethylfurfura HMF in parental solutions. Fundam. Appl. Toxicol. 4:843853. Vvedenskaya, I. O., and Vorsa, N. 2004. Flavonoid composition over fruit development and maturation in American cranberry, Vaccinium macrocarpon Ait. Plant Sci. 167:10431054. Wenzl, H. F. J., Brauns, F. E., and Brauns, D. A. 1970. The Chemical Technology of Wood. New York: Academic Press.