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The native form of lignocellulosic biomass is resistant to enzymatic breakdown. A well-designed pretreatment that can promote enzymatic hydrolysis of biomass with reasonable processing cost is therefore necessary. To this end, a number of different types of pretreatment technologies have been developed with a common goal of making biomass more susceptible to enzymatic saccharification. Among those, a pretreatment method using alkaline reagent has emerged as one of the most viable process options due primarily to its strong pretreatment effect and relatively simple process scheme. The main features of alkaline pretreatment are that it selectively removes lignin without degrading carbohydrates, and increases porosity and surface area, thereby enhancing enzymatic hydrolysis. In this review, the leading alkaline pretreatment technologies are described and their features and comparative performances are discussed from a process viewpoint. Attempts were also made to give insights into the chemical and physical changes of biomass brought about by pretreatment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Pretreatment of switchgrass using aqueous ammonia or NaOH was investigated as a means to enhance the enzymatic digestibility. To increase the effectiveness of pretreatment, H(2)O(2) was supplemented with the alkaline reagents. Since H(2)O(2) is unstable at high temperature, low-to-high step-change of temperature was applied, and this scheme was found to be effective in the case of NH(3)/H(2)O(2) treatment. The composition of pretreatment liquid indicates that hemicellulose solubilized during alkaline treatment exists either in the form of oligomers or as lignin-carbohydrate complex (LCC). LCC formation was prominent in ammonia treatment and in NaOH/H(2)O(2) treatment, and that LCC formation protects the hemicelluloses sugars from degradation. Lignin in the pretreatment liquor was precipitated and subjected to TGA and FTIR analyses. TGA data indicate that NaOH-lignin has more uniform structure and higher O/C ratio than ammonia-lignin. FTIR analysis indicates that NaOH-lignin has lower aromatic content but higher guaiacyl type structure than ammonia-lignin.

The methods of pretreatment of lignocellulosic biomass using aqueous ammonia are described. The main effect of ammonia treatment of biomass is delignification without significantly affecting the carbohydrate contents. It is a very effective pretreatment method especially for substrates that have low lignin contents such as agricultural residues and herbaceous feedstock. The ammonia-based pretreatment is well suited for simultaneous saccharification and co-fermentation (SSCF) because the treated biomass retains cellulose as well as hemicellulose. It has been demonstrated that overall ethanol yield above 75% of the theoretical maximum on the basis of total carbohydrate is achievable from corn stover pretreated with aqueous ammonia by way of SSCF. There are two different types of pretreatment methods based on aqueous ammonia: (1) high severity, low contact time process (ammonia recycle percolation; ARP), (2) low severity, high treatment time process (soaking in aqueous ammonia; SAA). Both of these methods are described and discussed for their features and effectiveness.

For the first time, a single source of cellulosic biomass was pretreated by leading technologies using identical analytical methods to provide comparative performance data. In particular, ammonia explosion, aqueous ammonia recycle, controlled pH, dilute acid, flowthrough, and lime approaches were applied to prepare corn stover for subsequent biological conversion to sugars through a Biomass Refining Consortium for Applied Fundamentals and Innovation (CAFI) among Auburn University, Dartmouth College, Michigan State University, the National Renewable Energy Laboratory, Purdue University, and Texas A&M University. An Agricultural and Industrial Advisory Board provided guidance to the project. Pretreatment conditions were selected based on the extensive experience of the team with each of the technologies, and the resulting fluid and solid streams were characterized using standard methods. The data were used to close material balances, and energy balances were estimated for all processes. The digestibilities of the solids by a controlled supply of cellulase enzyme and the fermentability of the liquids were also assessed and used to guide selection of optimum pretreatment conditions. Economic assessments were applied based on the performance data to estimate each pretreatment cost on a consistent basis. Through this approach, comparative data were developed on sugar recovery from hemicellulose and cellulose by the combined pretreatment and enzymatic hydrolysis operations when applied to corn stover. This paper introduces the project and summarizes the shared methods for papers reporting results of this research in this special edition of Bioresource Technology.

A strain of Clostridium thermoaceticum (ATCC 49707) was evaluated for its homoacetate potential. This thermophilic anaerobe best produces acetate from glucose at pH 6.0 and 59 degrees C with a yield of 83% of theoretical. Enzyme hydrolysis of two substrates, a-cellulose and a pulp mill sludge, yielded 68% and 70% digestion, respectively. The optimum conditions for the simultaneous saccharification and fermentation (SSF) were substrate dependent: 55 degrees C, pH 6.0 for alpha-cellulose, and 55 degrees C, pH 5.5 for the pulp mill sludge. In the SSF with alpha-cellulose, the overall yield of acetate was strongly influenced by the enzyme loading. In a fed-batch operation of SSF with alpha-cellulose, an overall acetic acid yield of 60 wt% was obtained. Among the factors limiting the yields were incomplete digestion by the enzyme and the end-product inhibition. In the SSF of pulp mill sludge, inhibitors present in the sludge severely limited bacterial action. A large accumulation of glucose developed over the entire process, changing the intended SSF operation into a separate hydrolysis and fermentation operation. Despite a long lag phase of microbial growth, a terminal yield of 85% was obtained with this substrate.

Current technology for conversion of biomass to ethanol is an enzyme-based biochemical process. In bioethanol production, achieving high sugar yield at high solid loading in enzymatic hydrolysis step is important from both technical and economic viewpoints. Enzymatic hydrolysis of cellulosic substrates is affected by many parameters, including an unexplained behavior that the glucan digestibility of substrates by cellulase decreased under high solid loadings. A comprehensive study was conducted to investigate this phenomenon by using Spezyme CP and Avicel as model cellulase and cellulose substrate, respectively. The hydrolytic properties of the cellulase under different substrate concentrations at a fixed enzyme-to-substrate ratio were characterized. The results indicate that decreased sugar yield is neither due to the loss of enzyme activity at a high substrate concentration nor due to the higher end-product inhibition. The cellulase adsorption kinetics and isotherm studies indicated that a decline in the binding capacity of cellulase may explain the long-observed but little-understood phenomenon of a lower substrate digestibility with increased substrate concentration. The mechanism how the enzyme adsorption properties changed at high substrate concentration was also discussed in the context of exploring the improvement of the cellulase-binding capacity at high substrate loading. [ABSTRACT FROM AUTHOR]