Oxidative pretreatment of lignocellulosic biomass for enzymatic hydrolysis: Progress and challenges.

Deconstruction of cell wall structure is important for biorefining of lignocellulose to produce various biofuels and chemicals. Oxidative delignification is an effective way to increase the enzymatic digestibility of cellulose. In this work, the current research progress on conventional oxidative pretreatment including wet oxidation, alkaline hydrogen peroxide, organic peracids, Fenton oxidation, and ozone oxidation were reviewed. Some recently developed novel technologies for coupling pretreatment and direct biomass-to-electricity conversion with recyclable oxidants were also introduced. The primary mechanism of oxidative pretreatment to enhance cellulose digestibility is delignification, especially in alkaline medium, thus eliminating the physical blocking and non-productive adsorption of enzymes by lignin. However, the cost of oxidative delignification as a pretreatment is still too expensive to be applied at large scale at present. Efforts should be made particularly to reduce the cost of oxidants, or explore valuable products to obtain more revenue.

Model-based process intensification of dilute acid pre-hydrolysis of oil palm empty fruit bunch biomass for pretreatment and furfural production.

A novel process for simultaneous production of furfural and pretreatment of oil palm empty fruit bunch (EFB) by dilute acid pre-hydrolysis was developed based on non-isothermal kinetic modeling. Mass transfer analysis suggested that the internal diffusion could be neglected as diffusion time of sulfuric acid in EFB particles was significantly shorter than the pre-hydrolysis period, whereas the heating stage could not be neglected due to a significant part of xylan was solubilized at the stage. A strategy for increasing furfural yield was developed by intermittent discharging of steam, resulting in 71.4 % furfural yield. The pretreated solids showed good enzymatic digestibility. 136.3 g/L glucose corresponding to 81.6 % yield was obtained by high-solid loading hydrolysis. 95.4 g furfural and 212 g glucose could be obtained from 1 kg dry EFB. Therefore, non-isothermal effects on polysaccharide hydrolysis and pentose decomposition should be considered carefully for an efficient process design of EFB biorefining.

Multifactorial effects of gluconic acid pretreatment of waste straws on enzymatic hydrolysis performance.

The chemical compositions of lignin, hemicellulose and cellulose are so far unascertained to various lignocellulose in respect to effect of cellulose enzymatic hydrolysis. The novel and environment-friendly gluconic acid (GA) pretreatment technology showed impressive results on the enzymatic hydrolysis of cellulose in various agricultural straws. However, only few of the main reasons or critical issues pertaining to this reaction are known. Therefore, the novel GA pretreatment was carried out to remove hemicellulose from the three representative waste straws under different conditions. Next, for the enzymatic hydrolysis of the residual cellulose fraction in the pretreated straws, some mathematical correlations have been investigated between enzyme accessibility, hemicellulose removal rate, and cellulose crystallinity index. Both linear and nonlinear models were compared using five-parameter logic curve, four-parameter logic curve, and Deming regression. Hemicellulose removal was logically ascribed to be the trigger for cellulose saccharification efficiency during GA pretreatment of these waste straws.

Comprehensive investigation of multiples factors in sulfuric acid pretreatment on the enzymatic hydrolysis of waste straw cellulose.

The prerequisite for cellulosic biochemical production from lignocellulosic materials is efficient enzymatic hydrolysis that is a complicated heterogeneous catalytic process and affected by the complex lignin-cellulose-hemicellulose network. Understanding the main influencing factors for enzymatic hydrolysis is of substantial significance to guide the design of a biorefinery process. An experimental study of the pretreatment indicated that acid pretreatment is preferable for herbaceous feedstocks. Therefore, the classic dilute sulfuric acid pretreatment was utilized to hydrolyze and remove hemicellulose from three representative types of agricultural straws at various intensities. From the enzymatic hydrolysis of residual cellulose perspective, the crystallinity index and enzyme accessibility of the pretreated materials were also mathematically correlated to hemicellulose removals, respectively. For the better insight and understanding of the mathematical logics, the linear and nonlinear kinetic models were therefore compared, and the relationship was established by the five-parameter logistic equations and Allosteric sigmoidal models with well fittings.

Enzymatic hydrolysis of cellulose using extracts from insects.

The use of Zophobas morio extracts in the aspect of cellulose hydrolysis is presented for the first time. The aim of this study was to investigate the action of enzymes obtained from Z. morio on cellulose hydrolysis and to determine their influence on the structural properties of cellulose with use the Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Cellulose hydrolysis products were analyzed by high performance liquid chromatography (HPLC). This analysis indicated that microcrystalline cellulose with smaller particle size was more susceptible to enzymatically treatment. Moreover, our investigation of cellulase activity showed a different profile of the used enzyme during particular developmental stages of Z. morio. Midgut extracts obtained from adult insects are more effective in degrading cellulose than extracts from larvae. The analysis of cellulose hydrolysis confirms that the efficiency of this reaction also depends on the structure of cellulosic materials and internal conditions of enzymatic reaction. In this study the cellulolytic activity of Z. morio midgut extracts showed that these insects could be valuable sources of cellulases.

Enzymatic hydrolysis of cellulosic materials using synthetic mixtures of purified cellulases bioengineered at N-glycosylation sites.

Mutant forms of recombinant endoglucanase II (EG II, N194A), cellobiohydrolase I (CBH I, N45A) and cellobiohydrolase II (CBH II, N219A) from Penicillium verruculosum with enhanced cellulase activities, achieved by engineering of enzyme N-glycosylation sites in our previous studies, were used as components of the binary and ternary mixtures of cellulases in hydrolysis of Avicel and milled aspen wood. Using the engineered forms of the enzymes at a dosage of 10 mg/g substrate resulted in significant boosting of the glucose release from cellulose in the presence of excess ß-glucosidase relative to the performance of the corresponding wild-type mixtures at the same loading. The boosting effects reached 11-40% depending on the reaction time and substrate type. In hydrolysis of both cellulosic substrates by the binary mixtures of cellulases, all the enzyme pairs exhibited synergism. The magnitude of the synergistic effects (Ks) did not depend notably upon the induced mutations in the enzymes, and they were in the range of 1.3-1.8 for the combinations of EG II with CBH I (or CBH II), and 2.3-2.9 for the CBH I-CBH II pair. The results of this study should provide a basis for the development of a more effective fungal strain capable of producing cellulase cocktails with enhanced hydrolytic performance against lignocellulosic materials.