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Aiming for the complete utilization of bamboo biomass, an integrated process which combines ethanol production with the recovery of silica and lignin was proposed. To reduce chemical charge required for the fractionation of silica and lignin from bamboo and improve the digestibility of the obtained substrate, a sequentially two-stage pretreatment process of autohydrolysis and alkaline extraction was carried out. From the view of enhancing enzymatic hydrolysis and recovery of silica and lignin, a two-stage treatment of autohydrolysis at 180°C for 90min followed by alkaline extraction at 100°C with 6% NaOH (based on pretreated chips) for 120min was optimized. About 93.7% of original silica and 75.7% of original lignin could be recovered from bamboo. Enzymatic hydrolysis and fermentation of carbohydrates showed that an overall sugar yield of 88.6% of original sugar content and an ethanol recovery of 0.467g/g sugar were achieved based on the proposed scheme., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Dilute acid pre-extraction enhanced the mechanically refined poplar pulp substrates' enzymatic hydrolysis efficiency obviously. The results showed that the surface lignin distribution was changed significantly in residual wood chips and pulp substrates, and the surface lignin distribution showed important impact on the following enzymatic hydrolysis. Acid pre-extraction can lead to a redistribution of lignin in fiber cell walls, i.e., the lignin was degraded and migrated to fiber surface in the form of re-deposited lignin and pseudo-lignin. However, higher pre-extraction intensity was not desired due to the formation of redeposited lignin and pseudo-lignin. This study will help to reach a deeper understanding on the lignin distribution in the view of molecular and ultrastructure, and promote the development of a cost-efficient pretreatment strategy for biomass processing., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This work is aimed at investigating the influence of changes in the content of hemicelluloses of the autohydrolyzed poplar sapwood on the subsequent alkali impregnation for chemi-mechanical pulping (CMP). An alkali impregnation process was conducted using the autohydrolyzed poplar sapwood with different content of hemicelluloses as raw materials. The results showed that both the amount of NaOH consumption and swelling degree of poplar sapwood increased with the removal of hemicelluloses, thus enhancing the alkali impregnation effectiveness. The hemicelluloses removal can also shorten the alkali impregnation time for the autohydrolyzed poplar sapwood to achieve the similar impregnation effectiveness of unautohydrolyzed poplar sapwood. All of these can be attributed to the fact that the hemicelluloses removal would result in the exposure of more free hydroxyl groups on the cellulose and an increase in the porosity of the fiber cell walls., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The objective of this study was to investigate the effects of organosolv and hydrotropic pretreatments on improving enzymatic hydrolysis of eucalyptus. The chemical composition of the fiber surface was analyzed using X-ray photoelectron spectroscopy (XPS) to determine the surface characteristics of pretreated eucalyptus. Other than the significant decrease of surface coverage by lignin, hydrotropic pretreatment was more effective in removing the lignin and xylose from fiber cell walls than organosolv pretreatment. The restriction of acetyl and phenolic groups in pretreated substrates was typically eliminated by hydrotropic pretreatments. Moreover, fiber structure and morphology after pretreatments were more suitable for enzymatic hydrolysis. Cellulase adsorption capacity was notably improved by hydrotropic pretreatment, which indicating the better enzyme accessibility of cellulose in pretreated substrates. Eventually, higher glucose yield was obtained with hydrotropic pretreatment. In addition, the precipitated lignin as an important by-product of pretreatments was characterized by Fourier transforms infrared spectroscopy (FTIR) also., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Pyrolysis was demonstrated to investigate the thermal decomposition characteristics and potential of lignin-rich cotton by-products cotton exocarp (CE) and spent mushroom substrate consisted of cotton by-products (MSC) for biorefineries. The chemical component and structure alteration of CE and MSC was found to affect their thermochemical behaviors. The bio-oil yield from CE was 58.13wt% while the maximum yield from MSC was 45.01% at 600°C. The phenolic compounds obtained from CE and MSC were 33.9% and 39.2%, respectively. The yield of acetic acid from MSC between 400 and 600°C was about 30-38% lower than that from CE, which suggests the high quality of bio-oil was obtained. Biochar from MSC via slow pyrolysis had a high mass yield (44.38wt%) with well-developed pore structure., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Herein, the oxidative ionic liquid (IL) pretreatment for overcoming recalcitrance of lignocellulose with selective delignification was investigated, and the subsequent enzymatic hydrolysis was evaluated. IL pretreatment incorporating oxygen delignification could enhance lignin extraction with high selectivity at low carbohydrate loss. The dual-action of oxidative decomposition and dissolution by 1-butyl-3-methlimidazolium chloride (BmimCl) on biomass were synergistically acted, accounting for efficient recalcitrance removal. In addition, the mild oxidative IL treatment only slightly converted crystalline cellulose into amorphous structure, and the extensive extraction of the amorphous lignin and carbohydrate resulted to the expose of cellulose with high susceptibility. Correspondingly, the enzymatic hydrolysis of the pretreated lignocellulose was greatly enhanced. The oxidative IL treatment at mild conditions, collaborating BmimCl treatment with oxygen delignification is a promising and effective system for overcoming the robust structure of lignocellulose., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aim of this work was to study the impact of shortening kraft pulping (KP) process integrated with extended oxygen delignification (OD) on the biorefinery process performance of eucalyptus. Data showed that using kraft pulps with high kappa number could improve the delignification efficiency of OD, reduce hexenuronic acid formation in kraft pulps. Pulp viscosity for a target kappa number of ∼10 was comparable to that obtained from conventional KP and OD process. The energy and alkali consumption in the integrated biorefinery process could be optimized when using a KP pulp with kappa number of ∼27. The process could minimize the overall methanol formation, but greater amounts of carbonate and oxalate were formed. The information from this study will be helpful to the future implementation of short-time KP integrated with extended OD process in actual pulp mill applications for biorefinery, aiming at further improvement in the biorefinery effectiveness of hardwood., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this study, mild acid hydrolysis using γ-valerolactone (GVL)/water system integrated with enzymatic hydrolysis was carried out for the enhancement of enzymatic saccharification efficiency. The quantitative analysis of soluble carbohydrates and structural characterizations of solid residues were conducted. Results showed that the soluble carbohydrates in the water-phase were mainly composed of monomers and oligomers from xylose and glucose, while the contents of which were depended on the ratio of GVL to water. Moreover, the inhibitors were hardly detected due to the moderate pretreatment severity. Compared with the untreated feedstock, the yields of enzymatic hydrolysis from pretreated samples increased by two-fold with the mixture of 80/20 GVL/H2O. Combined with the amount of glucose (14.6%) dissolved in the water-phase, over 92.6% of glucose in cotton stalk was released and recovered. Based on the comprehensive analysis, treatment with GVL/H2O system provided us a more effective approach for sugar production from biomass., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Sodium lignosulfonate (SXSL) and long-chain fatty alcohols (LFAs) could enhance the enzymatic hydrolysis of xylan, and the compound of SXSL and LFAs have synergies on the enzymatic hydrolysis. SXSL shows a strong enhancement in buffer pH range from 4.0 to 6.0. The enhancement increased with the SXSL dosage and the xylanase loading. The cellulose and lignin in corncob substrate could not only adsorb xylanase nonproductively, but also seriously reduce the accessibility of xylanase on xylan to impede the enzymatic hydrolysis of xylan. Cellulase could break the plant cell wall structure of corncob and make additives work better. The xylose yield of corncob at 72h increased from 59.4% to 73.7% by adding the compound of 5g/L SXSL and 0.01% (v/v) n-decanol, which was higher than that without cellulase and additives by 30.7%. Meanwhile, the glucose yield at 72h of corncob increased from 45.8% to 62.3%., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study investigated the thermal decomposition characteristics and pyrolytic products of anaerobic digested rice straw (ADRS) by thermogravimetric (TG) and pyrolysis-gas chromatograph/mass spectrometry (Py-GC/MS) analysis. Compared with the raw rice straw (RS), the thermal decomposition temperature of ADRS was shifted to higher temperature zone and the second decomposition zone of cellulose (Toffset(c)-Tpeak) became narrower (14 °C less), which indicated that the composition of rice straw were changed significantly by the anaerobic digestion pretreatment. Py-GC/MS analysis showed that the quality of the bio-oil and the selectivity of pyrolytic products could be obviously improved by anaerobic digestion. The total yields of alcohols, acids, aldehydes, furans, anhydrosugars, and ketones pyrolysis substances decreased, while the yield of phenols increased. The yield of 4-Vinylphenol (4-VP) increased from 29.33%, 8.21% and 5.76% to 34.93%, 12.46% and 7.68% at 330, 450 and 650 °C, respectively, after anaerobic digestion., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study demonstrated at the pilot-scale (50 kg) use of Douglas-fir forest harvest residue, an underutilized forest biomass, for the production of high titer and high yield bioethanol using sulfite chemistry without solid-liquor separation and detoxification. Sulfite Pretreatment to Overcome the Recalcitrance of Lignocelluloses (SPORL) was directly applied to the ground forest harvest residue with no further mechanical size reduction, at a low temperature of 145°C and calcium bisulfite or total SO2 loadings of only 6.5 or 6.6 wt% on oven dry forest residue, respectively. The low temperature pretreatment facilitated high solids fermentation of the un-detoxified pretreated whole slurry. An ethanol yield of 282 L/tonne, equivalent to 70% theoretical, with a titer of 42 g/L was achieved. SPORL solubilized approximately 45% of the wood lignin as directly marketable lignosulfonate with properties equivalent to or better than a commercial lignosulfonate, important to improve the economics of biofuel production., (Published by Elsevier Ltd.)

Laccase treatment is a promising approach to remove lignin from prehydrolysis liquor (PHL) for value added utilization of hemicellulose rich waste streams. Modeling the lignin removal process is of practical interest for prediction and control of laccase treatment of PHL. The present study focused on the lignin removal through variation of laccase charge and treatment time. Results showed that the lignin removal may be divided into two phases, i.e. a fast initial phase followed by a second slow phase. A kinetic model based on the experimental results was developed, which can be used to predict the lignin removal of PHL during the laccase treatment., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Laccase enzymes are promising detoxifying agents during lignocellulosic bioethanol production from wheat straw. However, they affect the enzymatic hydrolysis of this material by lowering the glucose recovery yields. This work aimed at explaining the negative effects of laccase on enzymatic hydrolysis. Relative glucose recovery in presence of laccase (10IU/g substrate) with model cellulosic substrate (Sigmacell) at 10% (w/v) was almost 10% points lower (P<0.01) than in the absence of laccase. This fact could be due to an increase in the competition of cellulose binding sites between the enzymes and a slight inhibition of β-glucosidase activity. However, enzymatic hydrolysis and infrared spectra of laccase-treated and untreated wheat straw filtered pretreated residue (WS-FPR), revealed that a grafting process of phenoxy radicals onto the lignin fiber could be the cause of diminished accessibility of cellulases to cellulose in pretreated wheat straw., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study investigated the autohydrolysis pre-treatment prior to chemi-thermomechanical pulping (CTMP) process including the effects of autohydrolysis pretreatment with a lower severity on characteristics of the autohydrolysis liquor and hydrolyzed chips. The intensity of autohydrolysis, characterized by the severity factor, increased from 1.76 to 3.54, the hydrolyzed chips yield decreased from 99.0% to 86.7% and the xylose extraction yield increased from 0.8% to 44.0%. The content of holocellulose, pentosan and acid soluble lignin remained in the hydrolyzed chips decreased dramatically with increasing the treatment severity. After the autohydrolysis pretreatment, the resultant poplar chemi-thermomechanical pulp with a severity factor of 2.37 could obtain a 15.3 Nm/g tensile index, 58.6% ISO brightness and a 2.39 cm(3)/g bulk., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Steam explosion and steam pre-treatment have proved capable of enhancing enzymatic saccharification of lignocellulosic materials. However, until now, these methods had not been compared under the same operational conditions and using the same raw material. Both pre-treatments lead to increased yields in the saccharification of Eucalyptus globulus; but results have been better with steam pre-treatments, despite the more accessible surface of exploded samples. The reason for this finding could be enzymatic inhibition: steam explosion causes a more extensive extraction of hemicelluloses and releases a greater amount of degradation products which can inhibit enzymatic action. Enzymatic inhibition is also dependent on the amount and chemical structure of lignin, which was also a contributing factor to the lower enzymatic yields obtained with the most severe pre-treatment. Thus, the highest yields (46.7% glucose and 73.4% xylose yields) were obtained after two cycle of steam treatment, of 5 and 3 min, at 183°C., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Sulfite pretreatment to overcome the recalcitrance of lignocelluloses (SPORL) was applied to an empty fruit bunches (EFB) for ethanol production. SPORL facilitated delignification through lignin sulfonation and dissolution of xylan to result in a highly digestible substrate. The pretreated whole slurry was enzymatically saccharified at a solids loading of 18% using a relatively low cellulase loading of 15 FPU/g glucan and simultaneously fermented without detoxification using Saccharomyces cerevisiae of YRH400. An ethanol yield of 217 L/tonne EFB was achieved at titer of 32 g/L. Compared with literature studies, SPORL produced high ethanol yield and titer with much lower cellulase loading without detoxification., (Published by Elsevier Ltd.)

Lignin removal is essential for value-added utilization of hemicelluloses and acetic acid present in the prehydrolysis liquor (PHL) of a kraft-based hardwood dissolving pulp production. In this paper, a novel process concept, consisting of laccase-induced lignin polymerization, followed by filtration/flocculation, was developed to enhance the lignin removal. The results showed that the lignin removal increased from 11% to 46-61% at laccase concentration of 1-4 U mL(-1). The GPC results showed that the molecular weight of the lignin from the laccase treated PHL was increased by 160% in comparison with the original one. The subsequent flocculation using singular Poly-DADMAC system or dual polymer system of Poly-DADMAC/CPAM can further remove 10-15% lignin. The concentrations of hemicelluloses and acetic acid were negligibly affected during the laccase treatment, while flocculation caused 12-15% of total sugar loss. Additionally, the process incorporates this new concept into the kraft-based dissolving pulp production process was proposed., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Bamboo was non-isothermally pretreated with hot water at 140-200°C for different times (10-120 min). The effects of pretreatment conditions on the degradation of carbohydrates, cellulose crystallinity, partial removal/relocation of lignin, morphologic change of the feedstock, and glucose yield during the enzymatic hydrolysis were investigated. The effective removal of amorphous cellulose and hemicelluloses led to the increase of crystalline index of the residues. In comparison with the raw material, the surface of the pretreated samples was irregular and numerous lignin droplets appeared on the cellulose bundle surface under the intense pretreatment conditions. The glucose conversion increased with the raise of pretreatment temperature and the prolongation of time, and the maximum conversion of 75.7% was achieved for the sample pretreated at 200°C for 120 min, whereas the untreated sample was only 15.7%. The result illustrated that hydrothermal pretreatment affected the composition of bamboo, and remarkably enhanced the enzymatic hydrolysis efficiency., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The commercial pre-hydrolysis kraft-based dissolving pulp production process can be a typical example for the demonstration/implementation of the integrated forest biorefinery concept. In this study, the concept of cellulase treatment of this dissolving pulp for enhancement of accessibility/reactivity in terms of viscose rayon production was demonstrated. The cellulase treatment resulted in the formation of additional openings/surface areas in the fiber structure via the possible action of "etching". As a result, the pore volume of pulp fibers increased, which led to the increase in the accessibility to xanthation, and thus Fock reactivity. Results showed that the cellulase treatment was effective in increasing the Fock reactivity, at a cellulase dosage of 2u/g (based on the dry weight of pulp), the Fock reactivity increased from 47.67% to 79.9%. The adoption of cellulase treatment to hardwood kraft-based dissolving pulp can provide an efficient approach for enhancing its performance in the commercial viscose-rayon process., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The effects of Na as organic bound form or as inorganic salts form on the pyrolysis products characteristics of alkali lignin were investigated by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR), tube furnace and thermo-gravimetric analyzer (TGA). Results of TG-FTIR and tube furnace indicated that the two chemical forms Na reduced the releasing peak temperature of CO and phenols leading to the peak temperature of the maximum mass loss rate shifted to low temperature zone. Furthermore, organic bound Na obviously improved the elimination of alkyl substituent leading to the yields of phenol and guaiacol increased, while inorganic Na increased the elimination of phenolic hydroxyl groups promoting the formation of ethers. It was also found the two chemical forms Na had different effects on the gasification reactivity of chars. For inorganic Na, the char conversion decreased with increasing the char forming temperature, while organic bound Na was opposite., (Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.)

Enzymatic delignification with laccase from Trametes villosa used in combination with chemical mediators (acetosyringone, acetovanillone and 1-hydroxybenzotriazole) to improve the totally chlorine-free (TCF) bleaching of kenaf pulp was studied. The best final pulp properties were obtained by using an LHBTQPo sequence developed by incorporating a laccase-mediator stage into an industrial bleaching sequence involving chelation and peroxide stages. The new sequence resulted in increased kenaf pulp delignification (90.4%) and brightness (77.2%ISO) relative to a conventional TCF chemical sequence (74.5% delignification and 74.5% brightness). Also, the sequence provided bleached kenaf fibers with high cellulose content (pulp viscosity of 890 g·mL(-1) vs 660 g·mL(-1)). Scanning electron micrographs revealed that xylanase altered fiber surfaces and facilitated reagent access as a result. However, the LHBTX (xylanase) stage removed 21% of hexenuronic acids in kenaf pulp. These recalcitrant compounds spent additional bleaching reagents and affected pulp properties after peroxide stage., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Green liquor (Na2S+Na2CO3, GL) pretreatment is a proven pathway to improve the enzymatic saccharification for the production of bioethanol. In this work, the effects of GL pretreatment on the chemical composition and enzymatic digestibility of rice straw at various total titratable alkali (TTA) charge and temperature were investigated. The GL pretreatment showed excellent performance in high polysaccharides retention and delignification selectivity. Under the optimized GL pretreatment condition (4% TTA charge, 20% sulfidity and 140°C), 92.5% of glucan, 82.4% of xylan and 81.6% of arabinan in rice straw were recovered with a delignification of 39.4%. The maximum sugar yields of 83.9%, 69.6% and 78.0%, respectively for glucan, xylan and total sugar, were achieved at the same GL pretreatment condition with an enzyme loading of 40 FPU/g-substrate. The results suggested that GL pretreatment is a practicable method for rice straw to enhance enzymatic saccharification for bioethanol production., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The present work investigated the effects of subcritical CO2 pretreatment of sugarcane bagasse at different CO2 pressure, pretreatment time, and temperature with relative high-solid concentration (15% w/v) to the composition of prehydrolyzate and the enzymatic hydrolysis. The results indicated that the maximum xylose yields in prehydrolyzate liquid were 15.78 g (combined 3.16 g xylose and 12.62 g xylo-oligosaccharides per 100g raw material). Due to the effective removal of hemicellulose, the maximum glucose yield in enzyme hydrolyzate reached 37.99 g per 100g raw material, representing 91.87% of glucose in the sugarcane bagasse. The maximal total sugars yield (combined xylose and glucose both in prehydrolyzate and enzymatic hydrolyzate) were 52.95 g based on 100g raw material. These results indicated that subcritical CO2 pretreatment can effectively improve the enzymatic hydrolysis, so it could be successfully applied to sugarcane bagasse., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Bleached cellulose with good end-properties (≈ 90% ISO brightness and 62% cellulose preservation) was obtained by using a totally chlorine-free biobleaching process (TCF). Unbleached sulphite cellulose was treated with Trametes villosa laccase in combination with violuric acid. This enzymatic stage (L) was followed by a chelating stage (Q) and then by a hydrogen peroxide stage reinforced with pressurized oxygen (Po), resulting to an overall LQPo sequence. The use of violuric acid was dictated by the results of a preliminary study, where the bleaching efficiency of various natural (syringaldehyde and p-coumaric acid) and synthetic mediators (violuric acid and 1-hydroxybenzotriazole) were assessed. The outstanding results obtained with laccase-violuric acid system fulfil most of the characteristics of commercial dissolving pulp, totally acceptable for viscose manufacturing or CMC derivatives, with the added advantage that the enzymatic treatment saved 2h of reaction time and about 70% of hydrogen peroxide consumption, relative to a conventional sequence (Po)., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Acetic acid was one of the main compositions of the pre-hydrolysis liquor (PHL), which was recovered by reactive extraction with triisooctylamine (TIOA) diluted with decanol. Dilution of TIOA played an important role in extracting acetic acid from the PHL. The recovery of acetic acid from the PHL by TIOA was increased from 10.34% to 66.60% with the dilution of TIOA to 20% by decanol at the HAc to TIOA molar ratio of 1, consequently, the equilibrium distribution coefficient KD increased. The effects of time, temperature and pH on the extraction process were also studied. The extraction process was very fast. The acetic acid extraction decreased from 65.13% to 57.34% with the rise of temperature to 50°C from 20°C. A higher pH increased the dissociation of acetic acid, as a result, decreased acetic acid extraction. The hemicelluloses in the PHL were unaffected on the extraction process of acetic acid., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

This work validates a new strategy for complete utilization of palm residues by separating fibers and parenchyma for the respective purposes of pulping and biorefining. The parenchyma cells were fractionated from royal palm sheath (RPS) after neutral sulfite semichemical (NSSC) cooking for producing fermentable sugars, leaving vascular bundles for manufacturing pulp and paper. Parenchyma cells could be readily and completely screened out prior to defibration. They were more digestible by cellulase than vascular bundles or the pulp derived from them. Cellulose enzymatic digestibility (CED) of parenchyma cells rapidly reached 82% in 12-h hydrolysis and finally up to 92%. The CEDs of parenchyma were maintained around 90% at a medium solid consistency, 12% (w/w). The average length, retention and drainability of RPS pulp were all improved without loss of physical strength after removing parenchyma. This work may help establish a new platform for maximizing the utilization efficiency of parenchyma-rich biomass., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Filamentous fungi are widely used to produce cellulase, but how the fermentation conditions affect their production is not well known. In this study, cellulase production by Trichoderma viride in submerged fermentations with free cells in a stirred-tank reactor (STR) and immobilized cells in a rotating fibrous-bed bioreactor (RFBB) were investigated. Compared to free-cell fermentation, immobilized-cell fermentation gave 35.5% higher FPase activity and 69.7% higher saccharification yield of sugarcane bagasse (SCB). The secretory proteins in the fermentation broths were analyzed with two-dimensional gel electrophoresis (2-DE) and MALDI-TOF-TOF mass spectrometry, which identified 24 protein spots with differential expression levels. Among them, cellobiohydrolase CBH II and endoglucanase EG II were highly expressed and secreted in the immobilized-cell fermentation, while the free-cell fermentation produced more CBH І and EG ІV. These results showed that immobilized-cell fermentation with T. viride in the RFBB was advantageous for cellulase production., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Pseudo-lignin, which can be broadly defined as aromatic material that yields a positive Klason lignin value and is not derived from native lignin, has been recently reported to form during the dilute acid pretreatment of poplar holocellulose. To investigate the chemistry of pseudo-lignin formation, GPC, FT-IR and 13C NMR were utilized to characterize pseudo-lignin extracted from dilute-acid pretreated α-cellulose and holocellulose. The results showed that pseudo-lignin consisting of carbonyl, carboxylic, aromatic and aliphatic structures was produced from dilute acid pretreated cellulose and hemicellulose. Pseudo-lignin extracted from holocellulose pretreated at different conditions had similar molecular weights (Mn∼1000 g/mol; Mw∼5000 g/mol) and structural features (carbonyl, carboxylic, aromatic and methoxy structures). These characterizations have provided the pseudo-lignin formation mechanisms during pretreatment. The presence and structure of pseudo-lignin is important since pseudo-lignin decreases the enzymatic conversion., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Selective production of 4-ethylphenolics from lignin via mild hydrogenolysis was reported in this short communication. The hydrogenolysis of lignin was carried out in an autoclave with 65 vol.% ethanol/water as solvent, with 5% Ru/C, Pd/C and Pt/C as catalysts. The influences of catalysts, lignin species, and reaction conditions including reaction temperature, reaction time, and initial H(2) pressure on yield of target compounds were investigated. 3.1% 4-Ethylphenol and 1.3% 4-ethylguaiacol based on lignin could be obtained simultaneously from hydrogenolysis of corn stalk lignin, which is approximate to the yield obtained from petrochemical route. The results of this work showed that this novel method is a quite promising technique for the substitution of petrochemical route., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A process for removing inhibitors from pre-hydrolysis liquor (PHL) of a kraft-based dissolving pulp production process by adsorption and flocculation, and the characteristics of this process were studied. In this process, industrially produced PHL was treated with unmodified and oxidized activated carbon as an absorbent and polydiallyldimethylammonium chloride (PDADMAC) as a flocculant. The overall removal of lignin and furfural in the developed process was 83.3% and 100%, respectively, while that of hemicelluloses was 32.7%. These results confirmed that the developed process can remove inhibitors from PHL prior to producing value-added products, e.g. ethanol and xylitol via fermentation., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

A new biotechnological procedure using laccase in combination with a hydrophobic phenolic compound (lauryl gallate) for the hydrophobization of cellulose fibres and internal sizing of paper was developed. Cellulose fibres from hardwood kraft pulp were incubated with laccase (Lac), in combination with lauryl gallate (LG). The Lac-LG treatment resulted in the internal sizing of paper, and also in significantly reduced water penetration in the handsheets and wettability of the paper surface. Paper was found not to be effectively rendered hydrophobic by LG alone. SEM images of the fibre network revealed the presence of the sizing agent: a product of the reaction between laccase and lauryl gallate. Binding of lauryl gallate to cellulose fibres was suggested by the increase in kappa number of the pulp and further confirmed by IR spectroscopy., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

This study presents a novel, efficient and environmentally friendly process for the cooking of corn stalk that uses active oxygen (O2 and H2O2) and a recoverable solid alkali (MgO). The structural changes on the surface of corn stalk before and after cooking were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The results showed that lignin and extractives were effectively removed, especially those on the surface of corn stalk. Additionally, the changes included becoming fibrillar, the exposure of cellulose and hemi-cellulose and the pitting corrosion on the surface, etc. The results also showed that the removal reaction is from outside to inside, but the main reaction is possibly on the surface. Furthermore, the results of active oxygen cooking with a solid alkali are compared with those of alkaline cooking in the paper., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Liquefaction is a process for the production of biofuel or value-added biochemicals from non-food biomass. SO(3)H-, COOH-functionalized and HSO(4)-paired imidazolium ionic liquids were shown to be efficient catalysts for bagasse liquefaction in hot compressed water. Using SO(3)H-functionalized ionic liquid, 96.1% of bagasse was liquefied and 50.6% was selectively converted to low-boiling biochemicals at 543 K. The degree of liquefaction and selectivity for low-boiling products increased and the average molecular weight of the tetrahydrofuran soluble products decreased with increasing acidic strength of ionic liquids. Analysis of products and comparative characterization of raw materials and residues suggested that both catalytic liquefaction and hydrolysis processes contribute to the high conversion of bagasse. A possible liquefaction mechanism based on the generation of 3-cyclohexyl-1-propanol, one of the main products, is proposed., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Ground spruce wood was extracted with water at 170 °C at four different pH levels (3.8, 4.0, 4.2 and 4.4) achieved by using phthalate buffers. Static batch extractions were carried out in an accelerated solvent extractor (ASE-300). The extracted non-cellulosic carbohydrates, predominantly galactoglucomannans (GGMs), were characterised mainly by sugar unit analysis and molar mass determination. Compared to extraction with plain water, extractions with phthalate buffer solutions gave similar yields of non-cellulosic carbohydrates, but gave up to 70% less monosaccharides, and consequently higher molar masses of extracted GGMs. Moreover, at these pH levels, the hydrolysis of acetyl groups were decreased by 40% compared to extraction with plain water, thus maintaining the water solubility of GGMs. It is concluded that hot water extraction of hemicelluloses in high-molar-mass form (average Mw about 10 kDa) from wood in good yields (8% of wood) demands appropriate control of pH, to a level of about 4., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

Although the moderate load (COD of 5000-10,000 mg/L) and biodegradability of the APMP pulping effluent should allow biological treatment, toxic compounds in the effluent can interfere with this type of treatment. Studies were conducted to determine if treatment of the effluent with Aspergillus niger S13 was feasible. Under the optimized conditions (3% inoculum, pH 6, shaking at 160 rpm, 60-72 h, and 30°C), this fungus was able to remove about 97% of the methyl tertiary butyl ether (MTBE) extractives, and 60%, 77% and 43% of the chemical oxygen demand, turbidity and color even without a pre-flocculation step. These results are of practical interest in China because the APMP process has become popular, and efficient and cost-effective effluent treatment technologies are in high demand., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Hydrothermal pretreatment was performed on the leaves and internodes portions of Alamo switchgrass, Panicum virgatum L., to enhance the digestibility of cellulose towards cellulase. It was observed that extractives free leaves portion provided 18.1% lower pretreatment gravimetrical yield and 33.8% greater cellulose-to-glucose yield than internodes portion. The degree of polymerization (DP) and ultrastructure of cellulose were determined by gel-permeation chromatography and solid-state cross polarization/magic angle spinning (13)C NMR experiments. The results suggested that hydrothermal pretreatment hydrolyzed amorphous cellulose and yielded a product enriched in paracrystalline cellulose. Furthermore, the DP of cellulose was reduced to one third of the origin value after hydrothermal pretreatment. The resulting biomass after pretreatment for leaves and internodes has similar cellulose ultrastructure and chemical profiles. The results of the enzymatic hydrolysis studies of cellulose suggest that the reduced DP of cellulose of pretreated switchgrass was an important factor influencing the enhanced digestibility of pretreated switchgrass., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Flax soda/AQ pulps were treated with different fungal laccase-mediator combinations followed by physical and chemical characterization of the pulps to obtain a thorough understanding of the laccase/mediator effects on hexenuronic acid (HexA) removal and the coupling of mediator onto pulps for fiber functionalization. Large differences were found and the presence of lauryl gallate (LG) during Trametes villosa laccase (TvL) treatment (TvL+LG) resulted in a much larger reduction of pulp-linked HexA than the combination of p-coumaric acid (PCA) and Pycnoporus cinnabarinus laccase (PcL). A major portion of LG became attached to the pulp as revealed by an increase in the kappa number and further confirmed by thioacidolysis and (1)H NMR analysis of solubilized pulp fractions. Additional experiments with other chemical pulps and isolated pulp xylan and lignin revealed that HexA seems to be the sole pulp component attacked by TvL+LG. As a substrate for TvL, the reaction preference order is PCA>HexA>LG., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

In this paper, we proposed a new modification for an ethanol-based pulping process, which would consist of the pre-hydrolysis (pre-extraction) of wood chips for removing hemicelluloses; the ethanol extraction of pre-hydrolyzed wood chips for removing lignin; and the post purification of cellulose, leading to the production of pure cellulose. We also experimentally evaluated the separation of hemicelluloses from the pre-hydrolysis liquor (PHL) obtained from a pulp mill. To remove lignin from the PHL, it was acidified to a pH of 2, which resulted in 47% lignin precipitation. The lignin separation from the acidified PHL was further improved via adding polyethylene oxide and poly aluminum chloride or adding ethyl acetate. To recover the hemicelluloses from the acidified PHL, ethanol was added to the acidified PHL with a volumetric ratio of 4 to 1. The isolated lignin and hemicelluloses were characterized by a Fourier transform infrared spectroscopy (FTIR) and a gas permeation chromatography (GPC)., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Chitosan-guanidine complexes were prepared by reacting chitosan and polyhexamethylene guanidine hydrochloride or crosslinked polyhexamethylene guanidine hydrochloride in the presence of sodium tripolyphosphate as a crosslinking agent. The complexes, used as functional additives for paper, synergistically improved wet-strength and antimicrobial activities. In comparison with the control sample, the wet/dry strength ratio of hand-sheets treated with the complexes was increased from 2.65% up to 23.3%. The MIC values of the chitosan-PHGH and chitosan-PHGHE complexes against Escherichia coli were 15.6 and 31.2 microg mL(-1), respectively, thus demonstrating excellent antimicrobial activity. Hand-sheets treated with the complexes exhibited antibacterial activity against E. coli and Staphylococcus aureus. The release of the guanidine polymers included in the complexes was dynamically monitored using UV and the results showed the amount released exceeded 80%. Atomic force microscopy images indicated that the antimicrobial mechanism of the complexes was likely due to membrane damage., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

Three different pretreatment methods for switchgrass were studied. Aqueous sodium hydroxide (0.5-10% w/v, 90 degrees C, 1h), dilute H(2)SO(4) (0.5-6.0% v/v, 121 degrees C, 1h) and hot water (100 degrees C, 1h) were employed in this study to determine how each method affected the digestibility of switchgrass during enzymatic hydrolysis. Switchgrass pre-treated with 0.5% w/v sodium hydroxide generally produced glucose in higher concentrations than sulfuric acid and hot water pre-treated samples. SEM studies on the pre-treated samples revealed a great deal of pore formation in the NaOH pre-treated samples and little or no physical changes on the acid and hot water pre-treated samples. Lignin analysis carried out on the pre-treated samples showed a considerable decrease in lignin content in the NaOH pre-treated samples and only a slight decrease in lignin content for the other pretreatment methods studied., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

There is a commercial need to increase the amount of industrial produced lignin. An 86.24 wt.% formic acid solution with 0.2M H(2)SO(4) as the catalyst was used to isolate the lignin of dewaxed wheat straw at different residence times and reaction temperatures. Lignin was extracted and purified separately from hydrolysates and residual solids after treatment. The lignin obtained has been characterized by FTIR (Fourier transform infrared), GPC (Gel permeation chromatography), and (1)H NMR (Nuclear magnetic resonance). Results from these analyses indicated that oxidative cleavage of bonds in the lignin macromolecule has occurred during the formic acid treatment, leading to formation of oligomers of lignin with lower molecular weight. Moreover, it was found that guaiacyl unit is the main structure, the content of syringyl unit is higher than that of the hydroxybenzyl unit and beta-O-4 together with beta-5 ether bonds is also identified in the molecular structure of lignin of wheat straw obtained from the formic acid process., (Copyright 2009 Elsevier Ltd. All rights reserved.)

This study investigated the effects of chemical pretreatment and disk-milling conditions on energy consumption for size-reduction and the efficiency of enzymatic cellulose saccharification of a softwood. Lodgepole pine wood chips produced from thinnings of a 100-year-old unmanaged forest were pretreated by hot-water, dilute-acid, and two SPORL processes (Sulfite Pretreatment to Overcome Recalcitrance of Lignocellulose) at acid charge on oven dry (od) wood of 0% and 2.21%. The pretreated wood chips were then milled using a laboratory disk mill under various solids-loadings and disk-plate gaps to produce substrates for enzymatic hydrolysis. We found that post-chemical-pretreatment size-reduction of forest biomass can decrease size-reduction energy consumption by 20-80% depending on the pretreatment applied under 20% solids-loading and a disk-plate gap of 0.76 mm in milling. SPORL with a sodium bisulfite charge of 8% and sulfuric acid charge of 2.21% on wood was the most effective in decreasing size-reduction energy consumption. Solids-loading had the most significant effect on disk-milling energy. When solids-loading was reduced from 30% to 3%, disk-milling energy could be decreased by more than a factor of 10 for wood chips pretreated by both SPORL and dilute-acid at an acid charge of 2.21%. The enzymatic hydrolysis glucose yields (EHGY) from the substrates produced by all pretreatments were independent of the solids-loading in milling, indicating that these energy savings in size-reduction can be realized without affecting EHGY. When wood chips were pretreated by SPORL with 2.21% acid charge, size-reduction energy consumption was decreased to less than 50 Wh/kg od wood at a practical solids-loading of approximately 10-20%, equivalent to that used in size-reduction of agriculture biomass, with excellent EHGY of about 370 g per kg od wood. Similar effects on size-reduction energy savings and excellent EHGY were also achieved when large disk-plate gaps (up to 1.52 mm studied) were applied in disk-milling of wood chips pretreated by SPORL with acid., (Published by Elsevier Ltd.)

The chemical compositions and fiber morphology of stem and branch samples from Trema orientalis at three different sites planted in Bangladesh were determined and their pulping, bleaching and the resulting pulp properties were investigated. A large difference between the stem and branch samples was observed. The stem samples have consistently higher alpha-cellulose and lower lignin content, and longer fibers than the branch samples in all sites. T. orientalis from the Dhaka and Rajbari region had higher alpha-cellulose content and longer fiber length, resulting in higher pulp yield and better papermaking properties. The T. orientalis pulp from Rajbari region also showed the best bleachability., (Copyright (c) 2009 Elsevier Ltd. All rights reserved.)

The effects of laccase-natural mediator systems (LMS) on sisal pulp and their potential for either biobleaching or functionalizing (via radical-coupling) its fibres were investigated. The enzyme treatment (L stage) was followed by extraction with hydrogen peroxide in order to determine whether observable effects could be enhanced by removing LMS-modified lignin. Four different plant phenols [viz. the p-hydroxycinnamic compounds sinapic acid (SNC), ferulic acid (FRC), coniferyl aldehyde (CLD) and sinapyl aldehyde (SLD)] were used as laccase redox mediators and their effects on pulp and effluents compared with those of the synthetic compound 1-hydroxybenzotriazole (HBT). During the L stage performed with HBT, laccase underwent a loss of 99% and 78% of the initial activity, in the absence and presence of pulp, respectively. With natural mediators inactivation was markedly reduced, being the residual activity between 65% and 100% of the initial one, in the presence of pulp. The pulp was found to protect the enzyme against inactivation: the activity was only reduced by 45% in its presence. Under the operating conditions used the natural mediators proved less efficient than HBT in facilitating pulp bleaching; rather, they tended to bind to pulp fibres. This effect could be used to functionalize fibres in order to improve intrinsic properties of pulp or introducing novel ones (e.g. antimicrobial, antioxidant, optical properties, etc.). This paper shows for the first time the application of laccase-mediator systems to sisal pulp.

The biocatalytic reduction of 4-(trimethylsilyl)-3-butyn-2-one to enantiopure (R)-4-(trimethylsilyl)-3-butyn-2-ol was successfully conducted with high enantioselectivity using immobilized whole cells of a novel strain Acetobacter sp. CCTCC M209061, newly isolated from kefir. Compared with other microorganisms that were investigated, Acetobacter sp. CCTCC M209061 was shown to be more effective for the bioreduction reaction, and afforded much higher yield and product enantiomeric excess (e.e.). The optimal buffer pH, co-substrate concentration, reaction temperature, substrate concentration and shaking rate were 5.0, 130.6 mM, 30 degrees C, 6.0 mM and 180 r/min, respectively. Under the optimized conditions, the maximum yield and the product e.e. were 71% and >99%, respectively, which are much higher than those reported previously. Additionally, the established biocatalytic system proved to be efficient for the bioreduction of acetyltrimethylsilane to (R)-1-trimethylsilylethanol with excellent yield and product e.e. The immobilized cells manifested a good operational stability under the above reaction conditions since they retained 70% of their catalytic activity after ten cycles of use.

By following the solute exclusion technique, we determined the pore characteristics of 3 hardwood high-yield pulps (aspen, birch, maple). The fiber saturation point (FSP) was 1.40, 1.36 and 1.19 g water/g pulp, for aspen, birch, maple, respectively, which is lower than that of chemical pulps. Different fractions obtained from the Bauer-McNett classifier showed that the HYP fines have much more pore volume than their long fiber counterparts. The effects of beating, drying and re-wetting on the pore characteristics of HYP were also studied. Beating led to increased total pore volumes. Upon drying and re-wetting, much of the small pores from the HYP underwent permanent closure while the big pores were only slightly affected. Finally, the relationship between the water retention value (WRV) and FSP for HYP was examined.

This paper describes the fibre morphology of switchgrass (Panicum virgatum L.) and its pulping characteristics using sodium hydroxide and a combination of sodium hydroxide and sodium sulphite as the cooking agents. It was found that the fibre length of switchgrass is similar to that of poplar despite its high population of short fibre elements (< 0.2 mm). The switchgrass used in this study had a lignin content comparable to that of poplar, but a particularly high content of extractable materials. The soda pulp from switchgrass showed excellent mechanical properties and showed a great potential as a reinforcement component in newsprint making.