Enhanced saccharification of lignocellulosic biomass with1-allyl-3-methylimidazolium chloride（Amim Cl） pretreatment

A simple and efficient method of enhancing biomass saccharification by microwave-assisted pretreatment with dimethyl sulfoxide/1-allyl-3-methylimidazolium chloride is proposed. Softwood（pine wood（PW））, hardwoods（poplar wood, catalpa bungi, and Chinese parasol）, and agricultural wastes（rice straw, wheat straw, and corn stover（CS）） were exploited. Results showed that the best pretreatment effect was in PW with 54.3% and 31.7% dissolution and extraction ratios, respectively. The crystal form of cellulose in PW extract transformed from I to II, and the contended cellulose ratio and glucose conversion ratio reached 85.1% and 85.4%, respectively. CS after steam explosion achieved a similar pretreating effect as PW, with its cellulose hydrolysis ratio reaching as high as 91.5% after IL pretreatment.     

2. The raw materials of CA 2.1 Wood as natural raw materials for cellulose acetate production

The molecular arrangement of wood cell wall is described in relation to the physical and mechanical properties of wood. The chemical composition of wood is also summarized to illustrate the heterogeneity in distribution of cell wall constituents to use wood plup fibers judiciously as natural raw materials for cellulose acetate production.     

2.3 Wood pulp manufacturing and quality characteristics

Cellulose acetate being important in the fiber and textile industries is usually prepared from high quality cellulose such as cotton linters and wood pulps with an alpha cellulose content of more than 95%. In this section, therefore, wood pulps and cotton linters appropriate for cellulose acetate production were discussed in their chemical and physical properties so as to use them judiciously as natural raw materials for cellulose acetate production.     

One Step Conversion of Wheat Straw to Sugars by Simultaneous Ball Milling, Mild Acid, and Fungus Penicillium simplicissimum Treatment

Wheat straw is one of the major lignocellulosic plant residues in many countries including China. An attractive alternative is the utilization of wheat straw for bioethanol production. This article mainly studies a simple one-step wet milling with Penicillium simplicissimum and weak acid to hydrolysis of wheat straw. The optimal condition for hydrolysis was ball milling 48?h in citrate solvent (pH?=?4) with P. simplicissimum H5 at the speed of 500?rpm and the yield of sugar increased with increased milling time. Corresponding structure transformations before and after milling analyzed by X-ray diffraction, transmission Fourier transform infrared spectroscopy, and environmental scanning electron microscopy clearly indicated that this combined treatment could be attributed to the crystalline and chemical structure changes of cellulose in wheat straw during ball milling. This combined treatment of ball milling, mild acid, and fungus hydrolysis enabled the conversion of the wheat straw. Compared with traditional method of ball milling, this work showed a more simple, novel, and environmentally friendly way in mechanochemical treatment of wheat straw.     

Improved sulfuric acid decrystallization of wheat straw to obtain high yield carbohydrates

Wheat straw is an abundant residue of agriculture which is increasingly considered as a feedstock for the production of fuels, energy and chemicals. The concentrated acid hydrolysis of wheat straw has been investigated in this work. Hemicellulose and cellulose have been efficiently converted into monomers of pentoses and glucose in high yields by a one-pot decrystallization-hydrolysis procedure. This process differs from usual concentrated acid biomass fractionation methodologies as a low quantity of acid is used and the supplementary use of a costly acid is not necessary to yield efficiently carbohydrates. The influence of the acid native concentration, and of the time of the decrystallization step have been studied so as to optimise yields of carbohydrates using a minimum of sulfuric acid so as to preserve a potential market value of the process. One can also imagine that this procedure will not impact dramatically the subsequent purification costs. In view of the growing importance of renewable resource-based molecules in the chemical industry, and the necessity to produce fermentable substrate for biofuels, this approach may open a new avenue for the use of wheat straw as raw material for various applications.     

Ethanol production from steam-explosion pretreated wheat straw

Bioconversion of cereal straw to bioethanol is becoming an attractive alternative to conventional fuel ethanol production from grains. In this work, the best operational conditions for steam-explosion pretreatment of wheat straw for ethanol production by a simultaneous saccharification and fermentation process were studied, using diluted acid [H₂SO₄ 0.9% (w/w)] and water as preimpregnation agents. Acid-or water-impregnated biomass was steam-exploded at different temperatures (160–200°C) and residence times (5, 10, and 20 min). Composition of solid and filtrate obtained after pretreatment, enzymatic digestibility and ethanol production of pretreated wheat straw at different experimental conditions was analyzed. The best pretreatment conditions to obtain high conversion yield to ethanol (approx 80% of theoretical) of cellulose-rich residue after steam-explosion were 190°C and 10 min or 200°C and 5 min, in acid-impregnated straw. However, 180°C for 10 min in acid-impregnated biomass provided the highest ethanol yield referred to raw material (140 L/t wheat straw), and sugars recovery yield in the filtrate (300 g/kg wheat straw).     

Fermentation of Biologically Pretreated Wheat Straw for Ethanol Production: Comparison of Fermentative Microorganisms and Process Configurations

The pretreatment of lignocellulosic biomass with white-rot fungi to produce bioethanol is an environmentally friendly alternative to the commonly used physico-chemical processes. After biological pretreatment, a solid substrate composed of cellulose, hemicellulose and lignin, the two latter with a composition lower than that of the initial substrate, is obtained. In this study, six microorganisms and four process configurations were utilised to ferment a hydrolysate obtained from wheat straw pretreated with the white-rot fungus Irpex lacteus. To enhance total sugars utilisation, five of these microorganisms are able to metabolise, in addition to glucose, most of the pentoses obtained after the hydrolysis of wheat straw by the application of a mixture of hemicellulolytic and cellulolytic enzymes. The highest overall ethanol yield was obtained with the yeast Pachysolen tannophilus. Its application in combination with the best process configuration yielded 163 mg ethanol per gram of raw wheat straw, which was between 23 and 35 % greater than the yields typically obtained with a conventional bioethanol process, in which wheat straw is pretreated using steam explosion and fermented with the yeast Saccharomyces cerevisiae.     

过氧酸体系提取小麦秸秆中纤维素及其水溶液的制备

首先通过甲酸/乙酸/水体系对小麦秸秆粉末进行预处理,随后通过添加过氧化氢,制备过氧甲酸-过氧乙酸平衡体系,以有效地去除小麦秸秆中木质素、半木质素,最终获得高纯度的纤维素.把该纤维素加入到6.0%(wt)的氢氧化钠与4.0%(wt)的尿素混合水溶液中,在低温下溶解,得到了均相的纤维素水溶液,实现了由生物质制备纤维素均相水溶液,该溶液具有潜在的应用价值。     

Grafting of wheat straw fibers with poly (ε‐caprolactone) via ring‐opening polymerization for poly(lactic acid) reinforcement

The use of natural materials has grown in the last years in the plastics industry. Natural lignocellulose fibers derived from agricultural waste present potential to be used as a replacement for glass fibers for polymer reinforcement, leading to lower CO₂ footprint products. This work focuses on the modification of the cellulose fibers in order to improve the compatibility with poly(lactic acid) (PLA). The scoured wheat straw fibers were grafted with polycaprolactone (PCL) through ring opening polymerization. Thermal stability of the wheat straw fibers improved after chemical modifications enabling higher processing temperatures. Flexural and tensile moduli were improved by 23% and 15%, respectively, compared with neat PLA, using 20 wt% modified fibers. An improvement of 20% in the impact strength was obtained using PCL grafted fibers because of entanglements and molecular interactions between PCL grafted on the wheat straw fibers and PLA molecules. Copyright © 2015 John Wiley & Sons, Ltd.     

A technical and economic analysis of acid-catalyzed steam explosion and dilute sulfuric acid pretreatments using wheat straw or aspen wood chips

Lignocellulosic biomass is one of the most plentiful and potentially cheapest feedstocks for ethanol production. The cellulose component can be broken down into glucose by enzymes and then converted to ethanol by yeast. However, hydrolysis of cellulose to glucose is difficult, and some form of pretreatment is necessary to increase the susceptibility of cellulose to enzymatic attack. An analysis has been completed of two pretreatment options, dilute sulfuric acid hydrolysis and sulfur dioxide impregnated steam explosion, for two feedstocks, wheat straw and aspen wood chips. Detailed process flow sheets and material and energy balances were used to generate equipment cost information. A technical and economic analysis compared the two feedstocks for each of the two pretreatments. For the same pretreatment, sugars produced from aspen wood hydrolysis were cheaper because of the higher carbohydrate content of aspen, whereas dilute acid pretreatment is favored over acid-catalyzed steam explosion.     

Stimulatory Effect of Different Lignocellulosic Materials for Phenolic Compound Production and Antioxidant Activity from Inonotus obliquus in Submerged Fermentation

White-rot fungus Inonotus obliquus grown in submerged culture produces antioxidative phenolic compounds. In this study, addition of lignocellulosic materials into the liquid culture increased the production and antioxidant activity of extra- and intra-cellular phenolic compounds (EPC and IPC, respectively). The production of EPC and IPC was significantly enhanced by wheat straw (by 151.2 and 45.3 %), sugarcane bagasse (by 106.9 and 26.1 %), and rice straw (by 67.6 and 38.9 %). Both of the EPC and IPC extracts from the three substrates showed a higher hydroxyl and 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity than those from the control medium. The highly active polyphenols such as tea catechins of epicatechin-3-gallate (ECG) and epigallocatechin-3-gallate (EGCG), and phelligridin G in the EPC extracts increased by 113.1, 75.0, and 86.3 % in the sugarcane bagasse medium. Davallialactone and inoscavin B in the EPC extracts were generated in large amounts in the lignocellulose media but not found in the control medium. The IPC extract from the wheat straw medium had the highest production of EGCG and ECG (17.6 and 18.1 mg/l). The different enhancement among the materials was attributed to the content and degradation rate of cellulose, hemicellulose, and lignin. The different antioxidant activity of the EPC and IPC extracts was related to their phenolic compositions.     

Optimization of a Natural Medium for Cellulase by a Marine Aspergillus niger Using Response Surface Methodology

The components of a natural medium were optimized to produce cellulase from a marine Aspergillus niger under solid state fermentation conditions by response surface methodology. Eichhornia crassipes and natural seawater were used as a major substrate and a source of mineral salts, respectively. Mineral salts of natural seawater could increase cellulase production. Raw corn cob and raw rice straw showed a significant positive effect on cellulase production. The optimum natural medium consisted of 76.9?% E. crassipes (w/w), 8.9?% raw corn cob (w/w), 3.5?% raw rice straw (w/w), 10.7?% raw wheat bran (w/w), and natural seawater (2.33 times the weight of the dry substrates). Incubation for 96?h in the natural medium increased the biomass to the maximum. The cellulase production was 17.80?U/g the dry weight of substrates after incubation for 144?h. The natural medium avoided supplying chemicals and pretreating substrates. It is promising for future practical fermentation of environment-friendly producing cellulase.     

Screening and Production Study of Microbial Xylanase Producers from Brazilian Cerrado

Hemicelluloses are polysaccharides of low molecular weight containing 100 to 200 glycosidic residues. In plants, the xylans or the hemicelluloses are situated between the lignin and the collection of cellulose fibers underneath. The xylan is the most common hemicellulosic polysaccharide in cell walls of land plants, comprising a backbone of xylose residues linked by β-1,4-glycosidic bonds. So, xylanolytic enzymes from microorganism have attracted a great deal of attention in the last decade, particularly because of their biotechnological characteristics in various industrial processes, related to food, feed, ethanol, pulp, and paper industries. A microbial screening of xylanase producer was carried out in Brazilian Cerrado area in Selviria city, Mato Grosso do Sul State, Brazil. About 50 bacterial strains and 15 fungal strains were isolated from soil sample at 35 °C. Between these isolated microorganisms, a bacterium Lysinibacillus sp. and a fungus Neosartorya spinosa as good xylanase producers were identified. Based on identification processes, Lysinibacillus sp. is a new species and the xylanase production by this bacterial genus was not reported yet. Similarly, it has not reported about xylanase production from N. spinosa. The bacterial strain P5B1 identified as Lysinibacillus sp. was cultivated on submerged fermentation using as substrate xylan, wheat bran, corn straw, corncob, and sugar cane bagasse. Corn straw and wheat bran show a good xylanase activity after 72 h of fermentation. A fungus identified as N. spinosa (strain P2D16) was cultivated on solid-state fermentation using as substrate source wheat bran, wheat bran plus sawdust, corn straw, corncob, cassava bran, and sugar cane bagasse. Wheat bran and corncobs show the better xylanase production after 72 h of fermentation. Both crude xylanases were characterized and a bacterial xylanase shows optimum pH for enzyme activity at 6.0, whereas a fungal xylanase has optimum pH at 5.0–5.5. They were stable in the pH range 5.0–10.0 and 5.5–8.5 for bacterial and fungal xylanase, respectively. The optimum temperatures were 55C and 60 °C for bacterial and fungal xylanase, respectively, and they were thermally stable up to 50 °C.     

Ionic liquid extraction method for upgrading eucalyptus kraft pulp to high purity dissolving pulp

High purity cellulose from wood is an important raw material for many applications such as cellulosic fibers, films or the manufacture of various cellulose acetate products. Hitherto, multi-step refining processes are needed for an efficient hemicellulose removal, most of them suffering from severe cellulose losses. Recently, a novel method for producing high purity cellulose from bleached paper grade birch kraft pulp was presented. In this so called IONCELL process, hemicelluloses are extracted by an ionic liquid–water mixture and both fractions can be recovered without yield losses or polymer degradation. Herein, it is demonstrated that bleached Eucalyptus urograndis kraft pulp can be refined to high purity acetate grade pulp via the IONCELL process. The hemicellulose content could be reduced from initial 16.6 to 2.4 wt% while persevering the cellulose I crystal form by using an optimized 1-ethyl-3-methylimidazolium dimethylphosphate-water mixture as the extraction medium. The degree of polymerization was then reduced by a sulfuric acid treatment for subsequent acetylation of the pulp, resulting in a final hemicellulose content of 2.2 wt%. When pre-treating the pulp enzymatically with endoxylanase, the final hemicellulose content could be reduced even to 1.7 wt%. For comparison, the eucalyptus kraft pulp was also subjected to cold caustic extraction and the same subsequent acid treatment which led to 3.9 wt% of residual hemicelluloses. The performance in acetylation of all produced pulps was tested and compared to commercial acetate grade pulp. The endoxylanase-IONCELL-treated pulp showed superior properties. Thus, an ecologically and economically efficient alternative for the production of highest value cellulose pulp is presented.     

Biological pretreatment of lignocellulose for enzymatic hydrolysis of cellulose

Pretreatment of lignocellulosic materials is considered as the rate-limiting step in an economically feasible process for enzymatic hydrolysis of cellulose. Biological delignification techniques have not been developed as intensively as physical and chemical methods. However, white-rot fungi are effective degraders of lignin, and some of them even preferentially remove lignin from wood compared with carbohydrates, and therefore might be suitable for biological pretreatment of lignocellulose. White-rot fungi were cultivated on wheat straw and the residue was hydrolyzed withTrichoderma reesei cellulase. Of nineteen fungi examined,Pleurotus ostreatus, Pleurotus sp. 535,Pycnoporus cinnabarinus 115,Ischnoderma benzoinum 108,Phanerochaete sordida 37,Phlebia radiata 79, and two unidentified fungi were found suitable for pretreatment of straw: the yields of reducing sugars and glucose based on original straw were markedly better compared with uninoculated straw, and these fungi also gave better results thanPolyporus versicolor, a nonselective reference fungus (Cowling, 1961). In the best cases the efficiency of the biological pretreatment was comparable with that of alkali treatment (2% NaOH, 0.4 g NaOH/g straw, 10 min at 115‡C), but the fungal treatment resulted in a higher proportion of glucose in the hydrolyzates. Combined fungal and (strong) alkali treatment did not give better results than alkali or fungal treatment alone. When culture flasks were periodically flushed with oxygen the treatment time could be reduced by about 1 wk with the two fungi,P. sordida 37 andP. cinnabarinus 115, tested. The effect of oxygen in pretreatment reflected the effect of oxygen in the degradation of¹⁴C-lignin of poplar wood to¹⁴CO₂ by these fungi (Hatakka and Uusi-Rauva, 1983). The economic feasibility of the biological pretreatment process is poor due to the long cultivation times needed. The best results were obtained with the longest treatment time studied, which was 5 wk. However, the rapid progress in the field of biological lignin degradation may help to accelerate the delignification process, and also find factors that favor lignin degradation, but suppress the utilization of carbohydrates.     

Optimization of β-1,4-Endoxylanase Production by an Aspergillus niger Strain Growing on Wheat Straw and Application in Xylooligosaccharides Production

Plant biomass constitutes the main source of renewable carbon on the planet. Its valorization has traditionally been focused on the use of cellulose, although hemicellulose is the second most abundant group of polysaccharides on Earth. The main enzymes involved in plant biomass degradation are glycosyl hydrolases, and filamentous fungi are good producers of these enzymes. In this study, a new strain of Aspergillus niger was used for hemicellulase production under solid-state fermentation using wheat straw as single-carbon source. Physicochemical parameters for the production of an endoxylanase were optimized by using a One-Factor-at-a-Time (OFAT) approach and response surface methodology (RSM). Maximum xylanase yield after RSM optimization was increased 3-fold, and 1.41- fold purification was achieved after ultrafiltration and ion-exchange chromatography, with about 6.2% yield. The highest activity of the purified xylanase was observed at 50 °C and pH 6. The enzyme displayed high thermal and pH stability, with more than 90% residual activity between pH 3.0–9.0 and between 30–40 °C, after 24 h of incubation, with half-lives of 30 min at 50 and 60 °C. The enzyme was mostly active against wheat arabinoxylan, and its kinetic parameters were analyzed (K_m = 26.06 mg·mL⁻¹ and V_max = 5.647 U·mg⁻¹). Wheat straw xylan hydrolysis with the purified β-1,4 endoxylanase showed that it was able to release xylooligosaccharides, making it suitable for different applications in food technology.     

Nanotechnology for Vasa Wood De-Acidification

The conservation of the seventeenth-century Swedish warship Vasa is a challenge due the unique history of its recovery and the delicate interventions made for its preservation. In the past years the strong acidity of wood came out as a threat for its conservation. The large amount of sulfur, produced by metabolic action of bacteria in the seabed, partly converted to sulfuric acid, catalyzes the chemical degradation of the wood through the acid hydrolysis of cellulose. This contribution reviews recent studies on the degradation of Vasa wood. We show how wood acidity can be neutralized by the application of calcium or magnesium hydroxide nanoparticles, forming an alkaline reservoir inside the wood that protect it from further acid attack. This has been evidenced by the thermal analysis carried out on fresh wood, Vasa wood, artificially degraded wood, and paper samples studied as reference cellulose-made materials. Pyrolysis temperature of cellulose was studied, as an important parameter of degradation, also related to the acidity of wood. Decreases in the pyrolysis temperature of degraded cellulose were correlated to decreases of its polymerization degree. Thermal analysis has been also used to investigate the wood de-acidification efficacy after the treatment with alkaline nanoparticles. Hydro-thermally aging, carried out on de-acidified Vasa wood samples demonstrated that de-acidification with nanoparticles facilitates protection of wood toward further acid degradation.     

Application of catalysts for obtaining 1,6-anhydrosaccharides from cellulose and wood by fast pyrolysis

The present work is devoted to the estimation of the effect of phosphoric acid and Fe³⁺ ions on the 1,6-anhydrosaccharides levoglucosan (LG) and levoglucosenone (LGone) contents in volatile products obtained from wood and microcrystalline cellulose by analytical pyrolysis. It was shown that the LG and LGone contents can be influenced by the pre-treatment. Iron was introduced into the biomass either by soaking in iron(III) sulfate solution alone or in the presence of ammonium, a treatment, in the course of which iron oxihydroxide is formed. It was demonstrated that a previous decationization of wood plays an important role for the subsequent results of Fe³⁺ ion treatment.The 1,6-anhydrosaccharides content in volatile products and the ratio of LG/LGone is governed by the phosphoric acid concentration. The same is true for cellulose soaked by iron sulfate: at higher concentration, the LGone content increases and the LG/LGone ratio decreases. The mechanism of the action of iron ions depends on the iron species formed upon the cellulose-containing raw materials pre-treatment procedures with iron sulfate. Upon pyrolysis, the adsorbed iron sulfate increases the amount of both LG and LGone in volatile products through the acidic catalysis mechanism owing to sulfate anions activity. The pre-treatment by the ion-exchange method could be considered as an efficient technique for obtaining the biooil containing levoglucosan in high content: 44.8% from cellulose and 27.3% from wood. The results are interpreted based on the quantitative evaluation of the pyrograms and the ESR spectra of the treated wood.     

Hydrothermal pretreatment conditions to enhance ethanol production from poplar biomass

Pretreatment has been recognized as a key step in enzyme-based conversion processes of lignocellulose biomass to ethanol. The aim of this study is to evaluate two hydrothermal pretreatments (steam explosion and liquid hot water) to enhance ethanol production from poplar (Populus nigra) biomass by a simultaneous saccharification and fermentation (SSF) process. The composition of liquid and solid fractions obtained after pretreatment, enzymatic digestibility, and ethanol production of poplar biomass pretreated at different experimental conditions was analyzed. The best results were obtained in steam explosion pretreatment at 210°C and 4 min, taking into account cellulose recovery above 95%, enzymatic hydrolysis yield of about 60%, SSF yield of 60% of theoretical, and 41% xylose recovery in the liquid fraction. Large particles can be used for poplar biomass in both pretreatments, since no significant effect of particle size on enzymatic hydrolysis and SSF was obtained.     

Cytotoxicity tests of cellulose nanofibril-based structures

Cellulose nanofibrils based on wood pulp fibres are most promising for biomedical applications. Bacterial cellulose has been suggested for some medical applications and is presently used as wound dressing. However, cost-efficient processes for mass production of bacterial cellulose are lacking. Hence, fibrillation of cellulose wood fibres is most interesting, as the cellulose nanofibrils can efficiently be produced in large quantities. However, the utilization of cellulose nanofibrils from wood requires a thorough verification of its biocompatibility, especially with fibroblast cells which are important in regenerative tissue and particularly in wound healing. The cellulose nanofibril structures used in this study were based on Eucalyptus and Pinus radiata pulp fibres. The nanofibrillated materials were manufactured using a homogenizer without pre-treatment and with 2,2,6,6-tetramethylpiperidine-1-oxy radical as pre-treatment, thus yielding nanofibrils low and high level of anionic charge, respectively. From these materials, two types of nanofibril-based structures were formed; (1) thin and dense structures and (2) open and porous structures. Cytotoxicity tests were applied on the samples, which demonstrated that the nanofibrils do not exert acute toxic phenomena on the tested fibroblast cells (3T3 cells). The cell membrane, cell mitochondrial activity and the DNA proliferation remained unchanged during the tests, which involved direct and indirect contact between the nano-structured materials and the 3T3 cells. Some samples were modified using the crosslinking agent polyethyleneimine (PEI) or the surfactant cetyl trimethylammonium bromide (CTAB). The sample modified with CTAB showed a clear toxic behaviour, having negative effects on cell survival, viability and proliferation. CTAB is an antimicrobial component, and thus this result was as expected. The sample crosslinked with PEI also had a significant reduction in cell viability indicating a reduction in DNA proliferation. We conclude that the neat cellulose nanostructured materials tested in this study are not toxic against fibroblasts cells. This is most important as nano-structured materials based on nanofibrils from wood pulp fibres are promising as substrate for regenerative medicine and wound healing.