Milling of lignocellulosic biomass

Ethanol is being considered as an attractive alternative transportation fuel for the future. One method of producing ethanol from lignocellulose involves reducing the size of biomass to smaller particles, and using acid or enzyme treatments to hydrolyze the biomass to sugars. The size-reduction step is necessary to eliminate mass- and heat-transfer limitations during the hydrolysis reactions. However, milling to small size consumes large amounts of energy, and reducing the energy usage is critical to the overall process economics. In this study, the energy requirements and size distribution for milling wood were measured for various pilot-scale size-reduction equipment. Hammer milling used less energy than disk milling, but produced particles with a larger-size distribution. Additionally, energy requirements were measured for shredding paper and switchgrass.     

Co-pyrolysis of macroalgae and lignocellulosic biomass

Synergistic effect of co-pyrolysis of macroalgae [Enteromorpha prolifera (EP)] and lignocellulosic biomass [rice husk (RH)] in a fixed bed reactor for maximum and enhanced biofuels yield has been investigated. The main and interaction effects of three effective co-pyrolysis parameters (pyrolysis temperature, feedstock blending ratio, and heating rate) were also modeled and simulated to determine the yield rates of bio-oil and bio-char, respectively. Optimization studies were, then, performed to predict the optimal conditions for maximum yields using the central composite circumscribed experimental design in Design Expert^® software 8.0.6. Analysis of variance was carried out to determine whether the fit of the multiple regressions is significant for the second-order model. Normal pyrolysis oils from EP, RH, and co-pyrolysis oils obtained from different feedstock blending ratios were examined using the gas chromatography-mass spectrometry to identify their compositions. Some vital properties of oils and bio-chars such as the heating value, water content, elemental compositions, and specific gravity were also determined, which unveiled that synergistic effect exists between EP and RH during co-pyrolysis, and this led to increase in products’ yields and improved co-pyrolysis products’ quality.

     

Ionic liquids: Promising green solvents for lignocellulosic biomass utilization

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Anaerobic digestion of lignocellulosic biomass and wastes

Anaerobic digestion represents one of several commercially viable processes to convert woody biomass, agricultural wastes, and municipal solid wastes to methane gas, a useful energy source. This process occurs in the absence of oxygen, and is substantially less energy intensive than aerobic biological processes designed for disposal purposes. The anaerobic conversion process is a result of the synergistic effects of various microorganisms, which serve as a consortium. The rate-limiting step of this conversion process has been identified as the hydrolysis of cellulose, the major polymeric component of most biomass and waste feedstocks. Improvements in process economics therefore rely on improving the kinetic and physicochemical characteristics of cellulose degrading enzymes. The most thoroughly studied cellulase enzymes are produced by aerobic fungi, namely Trichoderma reesei. However, the pH and temperature optima of fungal cellulases make them incompatible for use in anaerobic digestion systems, and the major populations of microorganisms involved in cellulase enzyme production under anaerobic digestion conditions are various bacterial producers. The current state of understanding of the major groups of bacterial cellulase producers is reviewed in this paper. Also addressed in this review are recently developed methods for the assessment of actual cellulase activity levels, reflective of the digester "hydrolytic potential," using a series of detergent extractive procedures.     

Pretreatment processes for lignocellulosic biomass conversion to biofuels and bioproducts

Lignocellulosic materials, such as forestry, agricultural and agroindustrial residues, are among the most important sources of biomass for the production of fuels, chemicals and materials. However there are physical and chemical barriers in the lignin–carbohydrate supramolecular structure that render most plant cell wall components almost completely unavailable for conversion into commercial products. Thus successful conversion strategies must lead to the disruption of this structure and result in partial or total separation of the lignocellulosic components, increasing the accessibility of cellulose, hemicelluloses and lignins. It must also minimize the formation of by-products. Each pretreatment technology has its own characteristics and is usually applied to a specific source of carbohydrates and lignins. A general overview of the most important pretreatment methods for the production of platform chemicals and fermentable sugars are given in this paper.     

Integrated catalytic process for obtaining liquid fuels from renewable lignocellulosic biomass

An integrated process for obtaining liquid biofuels is reported. The process is based on the separation of a lignocellulosic feedstock into cellulose and low-molecular-weight lignin (LMWL) followed by their conversion into two types of liquid biofuels, namely, hydrocarbon mixtures and bioalcohols. Different methods of wood fractionation into cellulose and LMWL—mechanical, steam explosion, and selective oxidation methods and their combinations—are compared. The amount of cellulose derived from wood and the amount of hydrolysate obtained from this cellulose for ethanol biosynthesis are determined by the efficiency of the method used for the fractionation of the lignocellulosic material. The best results are achieved by combining mechanical activation and subsequent catalytic oxidation of wood. Use of the resulting high-quality glucose solution, which are free of pentoses—sugars inhibiting ethanol biosynthesis—allows the alcohol yield to be increased by 30–35%. Liquid hydrocarbon mixtures enriched with phenols and products of their alkylation with ethanol have been obtained by thermal processing of LMWL in ethanol at an elevated pressure.     

Enzyme display technology for lignocellulosic biomass valorization by yeast cell factories

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New methods of heterogeneous catalysis for lignocellulosic biomass conversion to chemicals

This review deals with the use of solid catalysts for the enhancement of the efficiency and the development of a new generation of environmentally friendly, energy and resource efficient processes for the deep processing of lignocellulosic biomass to desired chemicals. The oxidative delignification of wood with hydrogen peroxide in the presence of the suspended TiO₂ catalyst, the oxidation of wood with molecular oxygen in the presence of copper catalysts, the acidcatalyzed conversion of cellulose to glucose and levulinic acid, and the thermal conversion of lignin to fuel additives on solid acid catalysts are analyzed. New integrated processes based on the heterogeneous catalytic oxidation are suitable for the complex processing of lignocellulosic biomass to produce valuable chemicals and engine fuel components without the use of toxic and corrosion-active reagents.     

Development of new ethanologenic Escherichia coli strains for fermentation of lignocellulosic biomass

Two new ethanologenic strains (FBR4 and FBR5) of Escherichia coli were constructed and used to ferment corn fiber hydrolysate. The strains carry the plasmid pLO1297, which contains the genes from Zymomonas mobilis necessary for efficiently converting pyruvate into ethanol. Both strains selectively maintained the plasmid when grown anaerobically. Each culture was serially transferred 10 times in anaerobic culture with sugar-limited medium containing xylose, but noselective antibiotic. An average of 93 and 95% of the FBR4 and FBR5 cells, respectively, maintained pLO1297 in anaerobic culture. The fermentation performances of the repeatedly transferred cultures were compared with those of cultures freshly revived from stock in pH-controlled batch fermentations with 10% (w/v) xylose. Fermentation results were similar for all the cultures. Fermentations were completed within 60 h and ethanol yields were 86–92% of theoretical. Maximal ethanol concentrations were 3.9–4.2% (w/v). The strains were also tested for their ability to ferment corn fiber hydrolysate, which contained 8.5% (w/v) total sugars (2.0% arabinose, 2.8% glucose, and 3.7% xylose). E. coli FBR5 produced more ethanol than FBR4 from the corn fiber hydrolysate. E. coli FBR5 fermented all but 0.4% (w/v) of the available sugar, whereas strain FBR4 left 1.6% unconsumed. The fermentation with FBR5 was completed within 55 h and yielded 0.46 g of ethanol/g of available sugar, 90% of the maximum obtainable. Author to whom all correspondence and reprint requests should be addressed. Names are necessary to report factually on available data. However, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA im plies no approval of the product to the exclusion of others that may also be suitable.     

Nonisothermal simultaneous saccharification and fermentation for direct conversion of lignocellulosic biomass to ethanol

The enzymatic reaction in the simultaneous saccharification and fermentation (SSF) is operated at a temperature much lower than its optimum level. This forces the enzyme activity to be far below its potential, consequently raising the enzyme requirement. To alleviate this problem, a nonisothermal simultaneous saccharification and fermentation process (NSSF) was investigated. The NSSF is devised so that saccharification and fermentation occur simultaneously, yet in two separate reactors that are maintained at different temperatures. Lignocellulosic biomass is retained inside a column reactor and hydrolyzed at the optimum temperature for the enzymatic reaction (50°C). The effluent from the column reactor is recirculated through a fermenter, which runs at its optimum temperature (20-30°C). The cellulase enzyme activity is increased by a factor of 2-3 when the hydrolysis temperature is raised from 30 to 50°C. The NSSF process has improved the enzymatic reaction in the SSF to the extent that it reduces the overall enzyme requirement by 30-40%. The effect of temperature on β-glucosidase activity was the most significant among the individual cellulase compounds. Both ethanol yield and productivity in the NSSF are substantially higher than those in the SSF at the enzyme loading of 5 IFPU/g glucan. With 10 IFPU/g glucan, improvement in productivity was more discernible for the NSSF. The terminal yield attainable in 4 d with the SSF was reachable in 40 h with the NSSF.     

Hydrothermal conversion of lignocellulosic biomass into high-value energy storage materials

Preparation of hierarchically porous, heteroatom-rich nanostructured carbons through green and scalable routes plays a key role for practical energy storage applications. In this work, naturally abundant lignocellulosic agricultural waste with high initial oxygen content, hazelnut shells, were hydrothermally carbonized and converted into nanostructured ‘hydrochar'. Environmentally benign ceramic/magnesium oxide(Mg O) templating was used to introduce porosity into the hydrochar. Electrochemical performance of the resulting material(HM700) was investigated in aqueous solutions of 1 M H_2SO_4, 6 M KOH and1 M Na_2SO_4, using a three-electrode cell. HM700 achieved a high specific capacitance of 323.2 F/g in 1 M H_2SO_4(at 1 A/g,-0.3 to 0.9 V vs. Ag/Ag Cl) due to the contributions of oxygen heteroatoms(13.5 wt%)to the total capacitance by pseudo-capacitive effect. Moreover, a maximum energy density of 11.1 Wh/kg and a maximum power density of 3686.2 W/kg were attained for the symmetric supercapacitor employing HM700 as electrode material(1 M Na_2SO_4, E = 2 V), making the device promising for green supercapacitor applications.     

Combined sedimentation and filtration process for cellulase recovery during hydrolysis of lignocellulosic biomass

A combined sedimentation and ultrafiltration process was investigated for recovering cellulase enzymes during the hydrolysis of lignocellulosic biomass. Lignocellulosic particles larger than approx 50 μm in length were first removed via sedimentation using an inclined settler. Ultrafiltration was then used to retain the remaining lignocellulosic particles and the cellulose enzymes, while transmitting fermentable sugars and other small molecules. The permeate flux from the ultrafiltration step for a feed consisting of 0.22 w/v% cellulase is 64±5 L/m²-h, while that for a feed consisting of the settler overflow from a mixture 0.22 w/v% cellulase and 10 wt% lignocellulose fed to the settler is 130±20 L/m²-h. The higher permeate flux in the latter case is presumably due to binding of a portion of the cellulase enzymes to the lignocellulosic particles during hydrolysis and filtration, preventing the enzymes from fouling the membrane. A filter paper activity assay shows little loss in enzymatic activity throughout the combined sedimentation/ultrafiltration separation process.     

Kinetics of glucose decomposition during dilute-acid hydrolysis of lignocellulosic biomass

Recent research work in-house both at Auburn University and National Renewable Energy Laboratory has demonstrated that extremely low concentrations of acid (e.g., 0.05–0.2 wt% sulfuric acid) and high temperatures (e.g., 200–230°C) are reaction conditions that can be effectively applied for hydrolysis of the cellulosic component of biomass. These conditions are far from those of the conventional dilute-acid hydrolysis processes, and the kinetic data for glucose decomposition are not currently available. We investigated the kinetics of glucose decomposition covering pH values of 1.5–2.2 and temperatures of 180–230°C using glass ampoule reactors. The primary factors controlling glucose decomposition are the reaction medium, acid concentration, and temperature. Based on the experimental data, a kinetic model was developed and the best-fit kinetic parameters were determined. However, a consistent discrepancy in the rate of glucose disappearance was found between that of the model based on pure glucose data and that observed during the actual process of lignocellulosic biomass hydrolysis. This was taken as an indication that glucose recombines with acid-soluble lignin during the hydrolysis process, and this conclusion was incorporated accordingly into the overall model of glucose decomposition.     

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).     

Bioconversion potential of Trichoderma viride HN1 cellulase for a lignocellulosic biomass Saccharum spontaneum

The industrialisation of lignocellulose conversion is impeded by expensive cellulase enzymes required for saccharification in bioethanol production. Current research undertakes cellulase production from pretreated Saccharum spontaneum through Trichoderma viride HN1 under submerged fermentation conditions. Pretreatment of substrate with 2% NaOH resulted in 88% delignification. Maximum cellulase production (2603 ± 16.39 U/mL/min carboxymethyl cellulase and 1393 ± 25.55 U/mL/min FPase) was achieved at 6% substrate at pH 5.0, with 5% inoculum, incubated at 35°C for 120 h of fermentation period. Addition of surfactant, Tween 80 and metal ion Mn⁺², significantly enhanced cellulase yield. This study accounts proficient cellulase yield through process optimisation by exploiting cheaper substrate to escalate their commercial endeavour.     

Molecular-beam mass-spectrometric analysis of lignocellulosic materials : I. Herbaceous biomass

A rapid analytical technique has been developed to qualitatively screen and quantitatively analyze biomass feedstocks for conversion into hydrocarbon fuels and chemicals. In this rapid analytical pyrolysis approach, herbaceous biomass feedstocks stored in the open without cover for 6 to 9 months were characterized using the molecular-beam mass spectrometer (MBMS). The biomass materials were pyrolyzed at 600°C and the volatile pyrolysis products were analyzed in real time by the MBMS. The mass spectral data were further analyzed by multivariate statistical techniques (Factor Analysis). The contents of nitrogen compounds, pentosans and hexosans estimated from the pyrolysis mass-spectrometric/multivariate analysis techniques correlated well with the results obtained by conventional wet chemical methods. However, lignin correlation was very weak because of the presence of microbial degradation products of biomass (humic material) that interfered with the Klason lignin analysis.

This rapid analytical technique was used to analyze various fractions of the stored biomass feedstocks. A comparison of exposed surface biomass materials and the unexposed materials showed that the exposed fraction lost 30% (wt) of the carbohydrate component of the biomass relative to the fresh material.