木质纤维素预处理技术研究进展

木质纤维素转化燃料乙醇一般需要经过原料预处理、酶水解和发酵过程。由于木质纤维原料化学结构复杂、直接酶解效率非常低,一般在酶水解之前需要进行适当的预处理以打破其致密结构,增加纤维表面积,提高后续纤维素酶的可及性。预处理程度直接影响纤维底物后续酶水解的效果。本文在木质纤维素常用预处理技术分析的基础上,重点讨论了3种相对高效的预处理技术：微波辅助离子液体预处理、两阶段深度共熔溶剂（DES）预处理和氯化铁预处理技术,分析了它们的优势、不足及发展现状。文中指出微波辅助离子液体预处理可有效解构木质素和半纤维素,破坏纤维素结晶区域,利于后续酶解,但微波加热过程会使离子液体分解和部分底物碳化。两阶段DES预处理可有效提高酶水解效率,但是预处理后原料中残留的DES可能会对后续反应中纤维素酶和微生物产生抑制作用。氯化铁预处理可有效破坏木质素与碳水化合物间的结合键,脱除底物中的半纤维素,而对木质素和纤维素降解较少,具有很好的发展前景。由于单一预处理技术的局限性,寻求低成本高效的联合预处理技术将是未来重点发展的方向。     

基于离子液体的生物质组分分离研究进展

生物质资源的开发利用是解决资源危机和能源危机的重要途径,但传统的生物质组分分离工艺效率较低且污染严重,极大地制约了生物质资源的高值化利用。作为一类新型溶剂,离子液体可以溶解纤维素、木质素和天然生物质材料,为生物质的组分分离及加工转化提供了有力的工具。本文简述了离子液体在生物质组分分离中的应用,包括离子液体作为溶剂直接从木质纤维素类生物质中提取分离纤维素和木质素,以及在离子液体介质中通过化学反应降解生物质来分离主要组分的方法。从离子液体优选、反应路径设计、生物质预处理、溶解条件和再生剂等方面分析了生物质组分分离工艺。成本高、效率低且容易引起二次污染是阻碍离子液体用于生物质组分分离的主要因素。为了提高生物质组分分离的经济性和绿色性,今后应着力设计低成本、低黏度、热稳定性强和低毒的离子液体,研发绿色高效的生物质组分分离工艺和离子液体再生方法。     

Comparison of atmospheric aqueous glycerol and steam explosion pretreatments of wheat straw for enhanced enzymatic hydrolysis

BACKGROUND: The oversupply of cheap glycerol by the oleochemicals industry together with problems occurring in low‐boiling‐point organosolv pretreatments, has generated an interest in the use of glycerol in the organosolv pretreatment of lignocellulosic biomass. Atmospheric aqueous glycerol autocatalytic organosolv pretreatment (AAGAOP) is a promising strategy that can effectively enhance enzymatic hydrolysis of lignocellulosic biomass. As a cost‐effective technique, steam explosion pretreatment (SEP) is being adopted in industrial applications. Accordingly, work has been carried out to investigate how AAGAOP enhanced enzymatic hydrolysis of lignocellulosic biomass compares with the SEP method. RESULTS: Under controlled laboratory conditions, based on ≥ 90% cellulose recovery, AAGAOP removed ≥ 60% hemicellulose and ≥ 60% lignin from wheat straw while SEP led to ～80% hemicellulose and 10% lignin removal. Enzymatic hydrolysis yields of AAGAOP and SEP reached ～90% and ～70%, respectively. Physical‐chemical structural characterization by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT‐IR), helped explain the above results. The two methods gave priority to dissociating the guaiacyl lignin and had a relatively small effect on syringyl units. However, AAGAOP exhibited a superior performance. CONCLUSION: The two methods enhanced the enzymatic hydrolysis of lignocellulosic biomass by removing and/or altering physical‐chemical structural impediments. The AAGAOP technique, with some special advantages, was more effective than SEP in enhancing the recovery and enzymatic digestibility of cellulose. Copyright © 2008 Society of Chemical Industry     

甘蔗渣的酸催化常压甘油有机溶剂预处理及其酶解

预处理可以打破木质纤维素原料纤维素、半纤维素和木质素三大组分间的顽抗结构,从而提升纤维素基质可酶解性。本文针对目前常压甘油有机溶剂预处理花费时间过长的问题,尝试开展酸催化的常压甘油有机溶剂预处理研究以缩短预处理时间。实验通过单因素选择和响应面Box-Behnken设计优化,获得酸催化常压甘油有机溶剂预处理的最佳条件为：预处理温度245℃,预处理时间38min,硫酸添加质量0.1%。在此条件下获得基质48h酶解率的响应面预测值为94.0%,实际值为91.4%。结果表明响应面优化方案和回归模型适用于本实验,预处理显著提高了基质可酶解性。高浓度基质（15%～20%）酶解进一步证明了预处理后基质具有突出的可酶解性,20%浓度基质在酶载量5FPU/g干基质条件下批次酶解72h,酶解率达60%,葡萄糖浓度达83.4g/L。酸催化常压甘油有机溶剂酸预处理在明显缩短预处理时间的同时,能显著提高木质纤维素基质可酶解性,使后续工业化意义的浓醪酶解糖化成为可能。     

Application of optical microscopy as a screening technique for cellulose and lignin solvent systems

Rapid and facile screening techniques to determine the effectiveness of solvents for cellulose or biomass dissolution can advance biomass processing research. Here, we report the use of a simple optical microscopy method to screen potential cellulose and lignin solvents. The described methodology was used to screen the dissolution of cellulose and lignin in two imidazolium‐based ionic liquids (ILs), two phosphonium‐based ILs, as well as a N,N‐dimethylacetamide/lithium chloride (DMAc/LiCl) solution in less time than other techniques. The imidazolium‐based ILs and the DMAc/LiCl were found to dissolve both cellulose and lignin. Also, it was observed that one of the phosphonium‐based ILs dissolved lignin and not cellulose, demonstrating a potential for biomass fractionation applications. © 2011 Canadian Society for Chemical Engineering     

深度共熔溶剂预处理木质纤维素生物质研究进展

木质纤维素生物质转化为生物燃料或化工产品一般需经历预处理、酶解及发酵过程,因其复杂的化学结构,在酶解前通常进行预处理以破坏其致密结构,提高酶与纤维素的可及性。深度共熔溶剂（DES）是一类新型的“绿色”溶剂,具有制备简单、价格低廉、性质可调、可生物降解、可循环使用等优势,可有效去除木质素组分,同时保留大部分纤维素,在生物质预处理方面具有巨大的潜力。本文介绍了DES的构成、分类及理化性质,总结了DES预处理对生物质组分的影响,并对预处理效果的影响因素如底物和DES的类型、溶剂黏度、温度、生物载量、微波及超声波辅助工艺和两阶段处理工艺等方面进行分析,探讨了DES和生物的相容性,最后针对DES存在的问题及缺点,提出了理性设计和大规模利用DES的机遇与挑战,本文可为实现生物质的低成本预处理和高价值利用提供新的思路。     

木质纤维原料组分分离的研究

从木质纤维原料预处理对微生物转化的必要性和回收利用半纤维素、木质素意义两个方面分析了木质纤维原料组分分离的必要性。木质纤维原料组分分离意味着木质纤维原料的精制,不是把木质纤维原料仅作为纤维素单一资源看待,而是把它视为一种多组分物料,将木质纤维原料精制成为具有一定纯度的各种组分,并分别加工成有价值的产品,这也是生物量全利用对于木质纤维原料预处理提出的新要求,赋予新的哲理思想。根据生物量全利用的要求,提出了木质纤维原料组分分离技术的新定性评价标准。根据利用汽爆和乙醇萃取法联合对麦草组分分离的研究结果,可提出一条经济可行的麦草组分分离的工艺过程,半纤维素和木质素回收率分别达到了80%和75%,纤维素酶解率达90%以上。     

Enzymatic hydrolysis from carbohydrates of barley straw pretreated by ionic liquids

BACKGROUND: Lignocellulosic biomass offers many potential advantages in comparison with the traditionally used sugars or starchy biomass since it is very widely available and does not compete with food and feed production. The abundance and high carbohydrates content of barley straw make it a good candidate for bioethanol production in Europe. Since biomass must be pretreated before enzymatic hydrolysis to improve the digestibility of both the cellulose and the hemicellulose biomass, the use of ionic liquids (IL) has been proposed as an environment‐friendly pretreatment of biomass. RESULTS: Different pretreatment conditions were investigated to determine the effects of the experimental conditions (temperature and time) on the enzymatic digestibility of pretreated material. The pretreatment of barley straw with 1‐ethyl‐3‐methyl imidazolium acetate treatment resulted in up to a 9‐fold increase in the cellulose conversion and a 13‐fold increase in the xylan conversion when compared with the untreated barley straw. CONCLUSION: Ionic liquid pretreatment of barley straw at 110°C for 30 min, followed by enzymatic hydrolysis, leads to a sugar yield of 53.5 g per 100 g raw material. It is then ready available for conversion into ethanol and is equivalent to more than 86% from potential sugars. The increase in saccharification was possible due to rupture of the lignin–hemicellulose linkages by treatment with 1‐ethyl‐3‐methyl imidazolium acetate. © 2012 Society of Chemical Industry     

木薯酒精渣的预处理及补料同步糖化发酵制取乙醇

木薯酒精渣的处置是制约木薯燃料乙醇大规模产业化的问题之一。本文立足于探索木薯酒精渣利用途径,分析了木薯酒精渣的主要成分,对比了氨水、氢氧化钠、氨水组合稀硫酸3种预处理方式对于木薯酒精渣纤维素和木素含量及纤维素酶水解效率的影响,分析了处理前后木薯酒精渣的表面结构及纤维素结晶度,并以氨水处理后的木薯酒精渣为底物,进行了同步糖化发酵。结果表明,3种预处理方法中组合预处理能更好地增加纤维素含量和提高纤维素酶水解效率,与未处理原料相比,组合预处理后纤维素含量增加了111.26%,木素下降了35.05%,酶水解72h纤维素转化率从42.10%增加到61.71%。氨水预处理后,原料的木素含量降低,处理后木薯酒精渣的表面变得更加粗糙,纤维素结晶度有所增加,以氨水处理后的木薯酒精渣为底物进行分批补料同步糖化发酵,当初始底物浓度为100.0g/L,分别在20h、40h、60h进行补料至最终底物浓度为400.0g/L时,发酵120h乙醇浓度达到51.0g/L。     

Catalytic organosolv fractionation of willow wood and wheat straw as pretreatment for enzymatic cellulose hydrolysis

BACKGROUND: Ethanol‐based organosolv fractionation of lignocellulosic biomass is an effective pretreatment technology for enzymatic cellulose hydrolysis to produce sugars and lignin within a biorefinery. This study focuses on the catalytic effect of H₂SO₄, HCl, and MgCl₂ on organosolv pretreatment of willow wood and wheat straw. RESULTS: The use of catalysts improved fractionation of both feedstocks. The maximum enzymatic cellulose digestibility obtained was 87% for willow wood (using 0.01 mol L^?1 H₂SO₄ as catalyst) and 99% for wheat straw (0.02 mol L^?1 HCl). Non‐catalytic organosolv fractionation at identical conditions resulted in 74% (willow wood) and 44% (wheat straw) glucose yield by enzymatic hydrolysis. Application of catalysts in organosolv pretreatment was particularly effective for wheat straw. The influence of the acid catalysts was found to be primarily due to their effect on the pH of the organosolv liquor. Acid catalysts particularly promoted xylan hydrolysis. MgCl₂ was less effective than the acid catalysts, but it seemed to more selectively improve delignification of willow wood. CONCLUSION: Application of catalysts in organosolv pretreatment of willow wood and wheat straw was found to substantially improve fractionation and enzymatic digestibility. The use of catalysts can contribute to achieving maximum utilization of lignocellulosic biomass in organosolv‐based biorefineries. Copyright © 2011 Society of Chemical Industry     

Specific surface to evaluate the efficiencies of milling and pretreatment of wood for enzymatic saccharification

Sieving methods have been almost exclusively used for feedstock size-reduction characterization in the biomass refining literature. This study demonstrates a methodology to properly characterize specific surface of biomass substrates through two dimensional measurement of each fiber of the substrate using a wet imaging technique. The methodology provides more information than sieving methods about biomass substrate. The measured dimensions of individual fibers were used to estimate the substrate external surface based on a cylinder model. The substrate specific surface and mechanical milling energy consumption were then correlated to enzymatic hydrolysis glucose yield. Results indicated that the developed methodology is effective in differentiating various size-reduction and chemical pretreatment processes in terms of cellulose to glucose conversion efficiency and size-reduction energy consumption. Thermomechanical disk milling (DM-I), exposing cellulose, is more effective than a high pressure thermomechanical disk milling (DM-II), exposing lignin, in subsequent enzymatic hydrolysis. However, DM-I is more energy intensive than DM-II. Both DMs that produce fibers are more efficient in enzymatic hydrolysis than hammer milling that produces fiber bundles. Chemical pretreatment not only increased cellulose conversion, but also reduced mechanical milling energy consumption. The present methodology identified the sulfite pretreatment C as the most efficient pretreatment in terms of glucose yield and milling energy consumption.     

Evaluation of enzymatic hydrolysis of wheat straw pretreated by atmospheric glycerol autocatalysis

BACKGROUND: Because ethanol organosolv pulping requires high pressure and is highly volatile, an atmospheric autocatalytic glycerol organosolv pretreatment process has been investigated. Enzymatic hydrolysis of wheat straw pretreated using this method was evaluated to explore a novel, economically competitive and environmentally friendly pretreatment technology for bioconversion of lignocellulosic biomass. The method also provides economical utilization of industrial glycerol, helping to cope with the challenge of the excess production of glycerol and to further defray the cost of biodiesel production. RESULTS: With preliminary optimization of the parameters in the pretreatment process, pretreatment performed at 240 °C for 4 h with the glycerol addition of 15 g g^?1 dry feedstock and wash at 80 °C led to high recovery of cellulose (95%) and good removal of lignin (>70%), which formed, respectively, 80% and 10% of the pulp. The enzymatic hydrolysis of the pretreated wheat straw yielded 90% of theoretically achievable sugar after 24 h and 92% after 48 h. CONCLUSION: Atmospheric autocatalytic glycerol organosolv pretreatment removed significant amounts of hemicellulose and lignin without affecting good cellulose recovery. The proposed novel strategy increased the susceptible of wheat straw to enzyme attack and led to enzymatic hydrolysis that was comparable with that achieved using ethanol organosolv pretreatment. Copyright © 2007 Society of Chemical Industry     

Effect of ultrasonic pretreatment on the composition of lignocellulosic material in biotechnological processes

The ultrasonic impact and possibilities of using its damaging effect on lignocellulosic material in order to increase the reactivity of plant biomass are studied. The main aim of pretreatment is the disruption of the crystalline, highly ordered structures of cellulose and lignin, or the removal of the latter. At the selected optimum parameters of ultrasonic pretreatment (frequency, 30 kHz) of the raw material, degradation of cellulose reaches 16% of a.d.s. (absolutely dry substance) while that of lignin is 11.4 % of a.d.s. Pretreatment of a substrate with ultrasound changes the rate and depth of the destruction of the initial material in the course of cultivation and can be used to accelerate the bioconversion of lignocellulosic substrates in biodiesel fuel production.     

Influence of organic liquids on the nanostructure of precipitated cellulose

Organic liquids have been used in pretreatments to improve the digestibility of lignocellulosic biomass, ultimately reducing the amount of enzyme required to digest the material to its constituent sugars. To understand the influence of these solvents on cellulose nanostructure, phosphoric acid was used to solubilize cellulose (PAS cellulose) followed by washing of the PAS cellulose with organic liquids previously demonstrated to aid pretreatment. PAS cellulose washed using methanol, ethanol, and ethylene glycol had gel‐like properties with disrupted nanostructures. PAS cellulose washed with acetone, 2‐propanol, and water yielded an opaque white precipitate. Small‐angle neutron scattering indicated the formation of loosely bundled rods of cellulose in the gel‐like material. Fourier transform infrared resonance of solvent‐washed, flash‐dried PAS cellulose suggested an increase in interchain hydrogen bonds in the gel‐like precipitates relative to the more obvious precipitates formed in other solvents. The optimal wash liquid was determined to be 40% by volume ethanol in water to induce a highly digestible, gel‐like material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Application of a microassay method to study enzymatic hydrolysis of pretreated wheat straw

BACKGROUND: The conversion of lignocellulosic biomass to ethanol includes a disruptive pretreatment process followed by enzyme‐catalyzed hydrolysis of the cellulose and hemicellulose components to fermentable sugars. As the cost and hydrolytic efficiency of enzymes are major factors that restrict the commercialization of biomass conversion processes, significant efforts are made nowadays to improve the enzymatic mixtures and make the process cost‐effective. RESULTS: In this work, enzymatic microassays have been developed and validated to test new different enzymatic formulations on real lignocellulosic substrates. Homogeneous handsheets from steam pretreated wheat straw were elaborated to be used as substrate. The microassay was adapted to test both water‐insoluble solids and the whole slurry as substrates. Results in hydrolysis microassays were comparable with those obtained in standard flask assays using pretreated wheat straw. Moreover, using the enzymatic microassays, two novel preparations have been evaluated, demonstrating the ability of microassays to discriminate between different enzymatic mixtures. CONCLUSIONS: This enzymatic microassay represents a rapid method to test the performance of new selected cellulase enzymes on real pretreated lignocellulosic substrates. This microassay will enable evaluation of enzyme components separately, or optimized mixtures. Copyright © 2010 Society of Chemical Industry     

A novel approach for extracting cellulose nanofibers from lignocellulosic biomass by ball milling combined with chemical treatment

Cellulose nanofibers (CNFs) were isolated from kenaf fibers and wheat straw by formic acid (FA)/acetic acid (AA), peroxyformic acid (PFA)/peroxyacetic acid (PAA), hydrogen peroxide (H₂O₂) treatment; and subsequently through ball milling treatment. Characterization of extracted cellulose and cellulose nanofibers was carried out through Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA). TEM images showed that extracted cellulose nanofibers had diameter in the range of 8–100 nm. FTIR and XRD results implied that hemicellulose and lignin were mostly removed from lignocellulosic biomass with an increase in crystallinity, and isolation of cellulose nanofibers was successful. The TGA results showed that decomposition temperature of cellulose nanofibers increased by about 27°C when compared with that of untreated lignocellulosic biomass. No significant change was observed in the decomposition temperature of bleached celluloses after ball milling. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42990.     

纤维素的酶水解糖化

纤维素为自然界存在最多的再生有机资源，能水解成葡萄糖，加工成食品、燃料、化工产品等。酸和酶都能催化水解，但酶法效果好，所得水解液的纯度高。多年来对于纤维素的酶法水解研究工作很多，但还有若干问题有待解决，尚未发展成适于工业生产应用的好工艺。本文扼要地综述纤维素的酶水解机理和纤维素物料的应用工艺。纤维素酶系内切葡聚糖酶、外切葡聚糖酶和β-葡萄糖甙酶的混合物，这三种酶协同起水解作用。纤维素物料不纯，还有伴生物半纤维素和木质素共同存在，需要预先处理，破坏纤维素的结晶性，提高水解效能，分离开半纤维素和木质素，加以好的利用，提高经济效益。     

A review of the potential of pretreated solids to improve gas biofuels production in the context of an OFMSW biorefinery

The organic fraction of municipal solid waste (OFMSW), mainly composed of lignocellulosic polymers, is extremely complex. Therefore, it is necessary to apply pretreatments to remove the lignin content and decrease the cellulose crystallinity in order to use the OFMSW for gas biofuels production in the context of biorefineries from waste. This work focused on critically reviewing the conventional pretreatments applied to OFMSW, with the goal of improving the H₂ production, as well as other biofuels in modern biorefineries. There are a wide variety of pretreatments that have successfully been used, mainly alkaline, milling and dilute acid. In addition, some research has focused on the recovery and reutilization of the alkali, acid or solvents after the pretreatment, to be incorporated into new cycles of production, minimizing the environmental impacts. Moreover, it would be necessary to incorporate analytical tools, in order to determine the sustainability of the biorefinery project. It is concluded that waste pretreatments could significantly contribute to increased yields of biogas fuels in organic waste‐based biorefineries. Therefore, establishing preliminary stages for conditioning biomass or wastes is essential to improve the degradation of wastes and bio‐product generation. © 2016 Society of Chemical Industry     

木质纤维素新型预处理与顽抗特性

木质纤维素是地球上最丰富的可再生生物质资源,其中纤维类多糖的酶催化降解是木质纤维素生物精炼的关键环节之一。对木质纤维素进行预处理,破坏底物的顽抗特性,是实现木质纤维素高效酶解糖化的必要途径。为此,各国学者围绕预处理技术开发以及底物顽抗特性开展了大量研究,本文对近几年来在这两方面取得的最新成果进行了综述和分析。在预处理方面,重点介绍了组合预处理、低温预处理、绿色溶剂与电化学预处理4类新型预处理技术,并对预处理效果与技术优势进行了评价;在底物顽抗特性方面,综述了木质素、结晶度、酶可及度等不同顽抗特性对纤维素酶解的影响规律,重点总结了近年来顽抗特性研究方面的新方法、新认识与新理解。上述研究成果有助于了解当前木质纤维素预处理研究的导向以及明确制约纤维素酶解的关键因素,为设计和筛选适宜的预处理方式、深刻理解纤维素酶解机制提供基础和指导。