Enhancing Lignocellulosic Biomass Hydrolysis by Hydrothermal Pretreatment, Extraction of Surface Lignin, Wet Milling and Production of Cellulolytic Enzymes.

Acetone and ethanol extraction of lignin deposits from the surface of hydrothermally (liquid hot water) pretreated beech wood biomass alleviates the lignin inhibitory effects during enzymatic hydrolysis of cellulose to glucose and boosts the enzymatic digestibility to high values (≈70 %). Characterization of the extracted lignins (FTIR, pyrolysis/GC-MS, differential thermogravimetry, gel permeation chromatography) indicated high purity, low molecular weight, and features that suggest that it consists mainly of fragments of the native wood lignin partially depolymerized and recondensed on the biomass surface during the hydrothermal pretreatment. The pyrolysis products of the extracted surface lignins suggest their high potential as a feedstock for the production of high added value phenolic compounds. When the enzymatic hydrolysis of the pretreated and extracted biomass solids was assisted by mild wet milling, near complete cellulose digestibility (≥95 %) could be achieved. In the context of the biorefinery and whole-biomass valorization concept, it was also shown that the hydrothermally (hemicellulose-deficient) pretreated and delignified biomass solids could be also successfully used for the production of crude cellulase from Trichoderma reesei cultures, providing a simple and low-cost method for the complementary production of cellulases by utilizing fractions of the integrated hydrolysis process.

Optimization of hydrothermal pretreatment of lignocellulosic biomass in the bioethanol production process.

The natural resistance to enzymatic deconstruction exhibited by lignocellulosic materials has designated pretreatment as a key step in the biological conversion of biomass to ethanol. Hydrothermal pretreatment in pure water represents a challenging approach because it is a method with low operational costs and does not involve the use of organic solvents, difficult to handle chemicals, and "external" liquid or solid catalysts. In the present work, a systematic study has been performed to optimize the hydrothermal treatment of lignocellulosic biomass (beech wood) with the aim of maximizing the enzymatic digestibility of cellulose in the treated solids and obtaining a liquid side product that could also be utilized for the production of ethanol or valuable chemicals. Hydrothermal treatment experiments were conducted in a batch-mode, high-pressure reactor under autogeneous pressure at varying temperature (130-220 °C) and time (15-180 min) regimes, and at a liquid-to-solid ratio (LSR) of 15. The intensification of the process was expressed by the severity factor, log R(o). The major changes induced in the solid biomass were the dissolution/removal of hemicellulose to the process liquid and the partial removal and relocation of lignin on the external surface of biomass particles in the form of recondensed droplets. The above structural changes led to a 2.5-fold increase in surface area and total pore volume of the pretreated biomass solids. The enzymatic hydrolysis of cellulose to glucose increased from less than 7 wt% for the parent biomass to as high as 70 wt% for the treated solids. Maximum xylan recovery (60 wt%) in the hydrothermal process liquid was observed at about 80 wt% hemicellulose removal; this was accomplished by moderate treatment severities (log R(o)=3.8-4.1). At higher severities (log R(o)=4.7), xylose degradation products, mainly furfural and formic acid, were the predominant chemicals formed.