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Pretreatment of agroindustry waste by ozonolysis for synthesis of biorefinery products  319


           Many pretreatment methods have been applied for lignocellulosic biomass, but these
           methods may not be suitable for biohydrogen production since it targeted the bioetha-
           nol as the final products (Wu et al., 2013b). The main objective of other pretreatment
           methods is to separate lignin and hemicellulose within the lignocellulose composite,
           which is practically suitable for bioethanol production, since it utilizes just the cellu-
           lose, but possibly not for biohydrogen production that utilizes both cellulose and
           hemicellulose (Monlau et al., 2013).
              Wu et al. (2013b) have investigated the ozone pretreatment to enhance the pro-
           duction of biohydrogen from wheat straw. They reported that the wheat straw was
           effectively degraded with ozone and increased the delignification with increased
           dose of ozone that significantly increased reducing sugar yields. The biohydrogen
           was produced by conducting the reaction in a simultaneous enzyme hydrolysis and
           dark fermentation, and the results showed that the ozone pretreatment significantly
           increased biohydrogen production by a maximum of 158% for ozonated sample at
           45 min. Thus it was proven that the biohydrogen production from lignocellulosic
           biomass using ozonolysis is technically feasible (Wu et al., 2013b).
              Another study from Wu et al (2013b) used barley straw to study the effect of
           ozone pretreatment for hydrogen production. The straw lignin was effectively
           degraded, and the reducing sugar yield was increased with ozone pretreatment com-
           pared to untreated biomass. The hydrogen production increased significantly by a
           maximum of 166% at 45 min of straw ozonation (Wu et al., 2013b). In the fermen-
           tation experiment the 90 min ozonated samples produced less hydrogen, while the
           highest sugar release was found in this group, indicating that the delignification
           using ozone does not produce enzyme inhibitor indicating the microorganisms that
           were inhibited in the simultaneous dark fermentation with saccharification process.
              Besides the ozonolysis process, Hu et al. (2018) worked on the production of
           biohydrogen production via dilute acid pretreated sugarcane bagasse through the
           detoxification and fermentation strategy. The laccase and NaBH 4 were used to
           detoxify the sugarcane bagasse and were washed before the anaerobic degradation
           process. The biohydrogen production was found to be increased 10 times higher
           when detoxification by washing, compared to the nondetoxified samples.
           Meanwhile, the detoxified samples by laccase and NaBH 4 obtained low (below
           7 mM) biohydrogen yield. This shows that washing by water proved to be effective
           as a detoxification method compared to acid pretreated sugarcane bagasse by lac-
           case NaBH 4 for biohydrogen production (Hu et al., 2018).


           14.3.3 Levulinic acid
           In biomass structure, complex carbohydrate network that linked monosaccharide,
           disaccharide, and polysaccharide is presented. Thus the depolymerization of ligno-
           cellulosic biomass is required for conversion into chemicals and fuels. The reac-
           tions comprise hydrolysis, dehydration, and rehydration, involving a series of
           complex reactions and drastic reaction conditions (Tiong et al., 2018). However, in
           biomass utilization, the variability of conversion and yield obtained from the bio-
           mass materials is depending on the reaction system applied. LA becomes a platform
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