4.1.3. Chemical pretreatmentSome chemicals such as acids, alkali, organic solvents, and ionic liquids have been reported to have significant effect on the native structure of lignocellulosic biomass (Fengel and Wegener 1984;Swatloski et al. 2002). Pretreatment with alkali such as NaOH, KOH, Ca(OH)2, hydrazine and anhydrous ammonia cause swelling of biomass, which increases the internal surface area of the biomass, and decreases both the degree of polymerization, and cellulose crystallinity.Alkaline pretreatment disrupts the lignin structure and breaks the linkage between lignin and the other carbohydrate fractions in lignocellulosic biomass, thus making the carbohydrates in the heteromatrix more accessible. The reactivity of remaining polysaccharides increases as the lignin is removed. Acetyl and other uronic acid substitutions on hemicellulose that lessen the accessibility of enzymes to cellulose surface are also removed by alkali pretreatments(Chandra et al. 2007; Chang and Holtzapple 2000; Galbe and Zacchi 2007; Mosier et al. 2005b). However, most of the alkali is consumed. Alkali pretreatment is most effective with low lignin content biomass like agricultural residues but becomes less effective as lignin contentof the biomass increases. Solutions of dilute (b4 wt.%) sulfuric acid, hydrochloric acid, andphosphoric acid have been also used to hydrolyze biomass (Mcmillan 1994; Nguyen 2000; Torget et al. 1990). Concentrated acids are not preferred because they are corrosive and must be recovered to make the pretreatment economically feasible (Sivers and Zacchi 1995). Dilute acid pretreatment in hydrolysis of hemicellulose to its monomeric units, rendering the cellulose more available. Acid pretreatment may require the use of an alkali to neutralize the hydrolysate.
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