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     

Optimization of the enzymatic hydrolysis conditions of steam‐exploded wheat straw for maximum glucose and xylose recovery

BACKGROUND: The enzymatic hydrolysis of steam‐exploded wheat straw using commercial enzyme complexes has been studied. A cellulase enzyme complex (Accellerase 1500), along with specific xylanase complements (Accellerase‐XC and Accellerase‐XY) provided by Genencor, have been used to enhance glucose and xylose recovery. A systematic study with response surface methodology (RSM) was used to check the effect of the operating conditions: pH (4–5), temperature (50–60 °C) and enzyme/substrate ratio (0.1–0.5 mL g_cellulose^?1) on the enzymatic hydrolysis with Acellerase 1500 to maximize the sugar yield. Xylanases were used as complements to increase the release of xylose. RESULT: Statistical results from ANOVA analysis demonstrated that the enzymatic hydrolysis was clearly improved by temperature and enzyme/substrate ratio. The optimum conditions for higher glucose and xylose releases were obtained with the higher enzyme dosage ratio (0.5 mL g^?1_cellulose), 50 °C and pH 4. CONCLUSION: Model validation at optimum operating conditions showed good agreement between the experimental results and the predicted responses for a confidence level of 95%. The use of the xylanase complements, Accellerase‐XY (accessory xylanase enzyme complex) and Accellerase‐XC (accessory xylanase/cellulase enzyme complex), increases the conversion of hemicellulose. Accellerase‐XC supplementation was more effective, obtaining an increase in yields of glucose and xylose of 11.8% and 23.6%, respectively, using a dosage of 0.125 mL g^?1_cellulose. © 2012 Society of Chemical Industry     

Effect of process variables on liquid hot water pretreatment of wheat straw for bioconversion to fuel‐ethanol in a batch reactor

BACKGROUND: Crop residues as wheat straw are potential sources for fuel‐ethanol production as an alternative to current production based on starch‐ or sugar‐containing feedstocks. In this work, the effect of liquid hot water (LHW) process parameters, i.e. temperature (170 and 200 °C), residence time (0 and 40 min), solid concentration (5% and 10% (w/v)) and overpressure applied in the reactor (30 bar and no overpressure), on pretreatment of wheat straw was studied using a full factorial experimental design. Pretreatment effectiveness was evaluated based on the composition of the solid and liquid fractions obtained after filtration of pretreated material, and the susceptibility of the solid fraction to enzymatic hydrolysis (EH) using commercial cellulases. RESULTS: Statistical analysis showed that only temperature and time, within the limits of the experimental range, have a significant effect on the responses studied. While the effect of pretreatment time in hemicellulose‐derived sugar recovery in prehydrolyzate depends on temperature, EH yield was enhanced as both temperature and time were increased. Maximum EH yield was 96 g glucose per 100 g potential glucose in pretreated residue. Xylan and acetyl groups content remaining in solid residue after pretretament, which were found to be directly correlated, had a marked effect on pretreated substrate degradability. CONCLUSIONS: LHW is an effective pretreatment to enhance the potential of wheat straw as substrate for ethanol production. Maximum hemicellulose‐derived sugar recovery (53% of content in raw material) and EH yield (96% of theoretical) fall within different temperature and time intervals, suggesting separate optimization designs for these responses. Copyright © 2007 Society of Chemical Industry     

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     

表面活性剂耦合离子液体对稻秆酶解糖化的影响

酶解糖化是木质纤维素材料制备生物质乙醇的关键环节,因此提高稻秆等木质纤维素材料的酶解糖化效率具有重要意义。以稻秆为原料,采用表面活性剂耦合离子液体为预处理方法,考察预处理温度、时间、表面活性剂的添加比例对稻秆酶解的影响。结果表明,预处理温度为110℃、时间为60 min、表面活性剂添加比例为1%,稻秆的酶解效果最佳,与单独离子液体处理的稻秆相比,纤维转化率可提高8%～15%。同时分别通过稻秆成分分析、FTIR、XRD、SEM等对预处理前后的稻秆结构进行表征,证实预处理后酶解效率提高的合理性。     

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     

A kinetic model for pretreated wheat straw saccharification by cellulase

A kinetic model for enzymatic hydrolysis of pretreated wheat straw able to describe the reaction process considering only macroscopic properties of enzyme and substrate would be useful in reactor design and scale-up. In this study Michaelis-Menten equations were used for different reaction schemes to fit experimental results obtained, working with enzyme loads between 5 and 44 i.u. g^?1 pretreated straw. Kinetic parameters were obtained by means of an optimization computer program.     

碱预处理小麦秸秆制备乙酰丙酸甲酯的工艺

小麦秸秆作为一种农业副产品,是制备生物质化学品的重要原料。乙酰丙酸甲酯（methyl levulinate,ML）是一种具有广泛应用前景的生物质化学品。本文以碱液预处理后的小麦秸秆为原料,硫酸铜为催化剂,研究了制备ML的工艺,考察了反应温度、反应时间、催化剂用量等对ML产率的影响。经过工艺优化,在反应温度183℃、反应时间3.3h、催化剂用量0.53g条件下,ML的收率达到23.0%（质量分数）。硫酸铜重复使用后仍具有良好的催化活性,在重复使用5次后ML收率达到18.7%（质量分数）。在相同的优化条件下,所开发的工艺比未处理小麦秸秆制备ML的收率提高了8.6%（质量分数）。     

Enzymatic hydrolysis and fermentation of lime pretreated wheat straw to ethanol

BACKGROUND: The objective of this work is to develop an efficient pretreatment method that can help enzymes break down the complex carbohydrates present in wheat straw to sugars, and to then ferment of all these sugars to ethanol. RESULTS: The yield of sugars from wheat straw (8.6%, w/v) by lime pretreatment (100 mg g^?1 straw, 121 °C, 1 h) and enzymatic hydrolysis (45 °C, pH 5.0, 120 h) using a cocktail of three commercial enzyme preparations (cellulase, β‐glucosidase, and xylanase) at the dose level of 0.15 mL of each enzyme preparation g^?1 straw was 568 ± 13 mg g^?1 (82% yield). The concentration of ethanol from lime pretreated enzyme saccharified wheat straw (78 g) hydrolyzate by recombinant Escherichia coli strain FBR5 at pH 6.5 and 35 °C in 24 h was 22.5 ± 0.6 g L^?1 with a yield of 0.50 g g^?1 available sugars (0.29 g g^?1 straw). The ethanol concentration was 20.6 ± 0.4 g L^?1 with a yield of 0.26 g g^?1 straw in the case of simultaneous saccharification and fermentation by the E. coli strain at pH 6.0 and 35 °C in 72 h. CONCLUSION: The results are important in choosing a suitable pretreatment option for developing bioprocess technologies for conversion of wheat straw to fuel ethanol. Copyright © 2007 Society of Chemical Industry     

小麦秸秆的预处理对球拟假丝酵母产槐糖脂的影响

考察小麦秸秆的预处理方式对球拟假丝酵母(Starmerella bombicola)利用其糖化液发酵产槐糖脂(SLs)的影响，并对发酵进行优化。分别选择稀酸预处理(DAP)、NaOH预处理(SHP)和SO3微热爆预处理(STMEP)对小麦秸秆进行预处理，使用纤维素酶酶解糖化后将糖化液用于SLs的发酵，采用补加葡萄糖和活性炭脱毒的方法提高SLs的产量。结果显示，SHP最利于小麦秸秆的酶解糖化，所得糖化液中葡萄糖含量达61.30 g/L，其次为STMEP和DAP，葡萄糖含量分别为48.33 g/L和40.00 g/L。STMEP糖化液中抑制物的总含量最低，其次为SHP和DAP。S. bombicola可以直接利用上述糖化液发酵产SLs，但发酵特性有所不同。SHP和STMEP糖化液更利于酸型槐糖脂(ASL)的积累，相比于化学合成培养基，其产量分别提高了74.27%和92.33%，达到100.45 g/L和110.86 g/L。补加葡萄糖和活性炭脱毒可以进一步提高SLs的产量。对于SHP糖化液，补加葡萄糖及其与活性炭脱毒的联合可将ASL的产量进一步提高至124.49 g/L；对于STMEP糖化液，则可将内酯型槐糖脂(LSL)的产量进一步提高至32.02 g/L，与化学合成培养基的LSL发酵水平相当。因此，小麦秸秆具备发酵产SLs的潜力，且不同预处理方式及发酵方式可用于获得不同类型的SLs，本研究有助于降低SLs的生产成本并拓展其应用领域。     

Acidic pretreatment of wheat straw in decanol for the production of surfactant, lignin and glucose

Wheat straw is an abundant residue of agriculture which is increasingly being considered as feedstock for the production of fuels, energy and chemicals. The acidic decanol-based pre-treatment of wheat straw has been investigated in this work. Wheat straw hemicellulose has been efficiently converted during a single step operation into decyl pentoside surfactants and the remaining material has been preserved keeping all its promises as potential feedstock for fuels or value added platform chemicals such as hydroxymethylfurfural (HMF). The enzymatic digestibility of the cellulose contained in the straw residue has been evaluated and the lignin prepared from the material characterized. Wheat-based surfactants thus obtained have exhibited superior surface properties compared to fossil-based polyethoxylates decyl alcohol or alkyl oligoglucosides, some of which are largely used surfactants. In view of the growing importance of renewable resource-based molecules in the chemical industry, this approach may open a new avenue for the conversion of wheat straw into various chemicals.     

Effect of several factors on peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis

BACKGROUND: Lignocellulose should undergo pretreatment to enhance its enzymatic digestibility before being saccharified. Peracetic acid (PAA) is a strong oxidant that can remove lignin under mild conditions. The sulfuric acid in the PAA solution also can cause degradation of hemicelluloses. The objective of the present work is to investigate the effect of several factors on peracetic acid pretreatment of sugarcane bagasse. RESULTS: It was found that PAA charge, liquid/solid (l/s) ratio, temperature, time, interactions between PAA charge and l/s ratio, temperature and time, all had a very significant effect on the enzymatic conversion ratio of cellulose. The relative optimum condition was obtained as follows: PAA charge 50%, l/s ratio 6:1, temperature 80 °C and time 2 h. More than 80% of the cellulose in bagasse treated under the above conditions was converted to glucose by cellulase of 20 FPU g^?1 cellulose. Compared with H₂SO₄ and NaOH pretreatments under the same mild conditions, PAA pretreatment was the most effective for enhancement of enzymatic digestibility. CONCLUSION: PAA pretreatment could greatly enhance the enzymatic digestibility of sugarcane bagasse by removing hemicelluloses and lignin, but removal of lignin was more helpful. This study can serve as a step to further optimization of PAA pretreatment and understanding the mechanism of enhancement of enzymatic digestibility. Copyright © 2007 Society of Chemical Industry     

响应曲面法优化小麦秸秆纤维素酶水解条件

利用响应曲面试验设计方法(RSM),选择底物质量分数、酶投加量、温度、pH值及水解时间为试验因子,还原糖(RS)产率为响应值,考察小麦秸秆纤维素酶水解过程中各影响因子对还原糖产率的影响,对小麦秸秆纤维素酶水解条件进行优化。结果表明,所考察的5个影响因子对还原糖产率均具有显著影响(p<0.05)。所得回归方程R² 值为 0.946 9,p<0.05,变异系数(C_V)值为4.37%,足够精度值为26.396,说明模型高度显著,可以在设计范围内对响应值进行预测。模型预测最佳水解条件为底物质量分数8.0%,酶投加量为35 FPU/g(以秸杆质量计),温度50 ℃,pH值5.4,水解时间96 h。利用最优水解条件进行验证试验,所得还原糖产率为60.73%,水解液中葡萄糖和木糖质量浓度分别为31.84和 16.74 g/L。     

Evaluation of a hydrothermal process for pretreatment of wheat straw—effect of particle size and process conditions

BACKGROUND: Hydrothermal processes are an eco‐friendly processes that provide an interesting alternative for chemical utilization of lignocellulosic materials, in which water and crop residues are the only reagents. In this work the effect of process conditions (size distribution of the wheat straw, temperature and time) was evaluated against production of fermentable products. RESULTS: The use of milled wheat straw fractions as a raw material containing blends of different particle size distribution showed that the latter had an influence on the final sugars in the hydrolysate. Improved values of glucose (21.1%) and xylose yields (49.32%) present in the hydrolysate were obtained with treatment severity factors of 2.77 and 3.36, respectively. Mathematical models were developed aimed at establishing the effect of process conditions on monosaccharide concentration and its degradation in the liquor. CONCLUSION: This work shows that the use of wheat straw blends with various particle sizes has a significant effect on the extraction of fermentable products. The effect of treatment severity, which takes into account both processing time and temperature was also evaluated. These results are of importance for process design. Copyright © 2010 Society of Chemical Industry     

醋酸预水解对稻草化学成分及酶水解性能的影响

研究了醋酸预处理对稻草主要化学成分及酶水解糖化效率的影响。在160℃下以不同的醋酸用量(0～4%)对稻草进行处理,预处理后稻草的Klason木质素含量基本保持不变,约60%的酸溶木质素被脱除;灰分含量(质量分数)约下降30%,灰分中SiO2则几乎全部保留在预处理浆料中。预处理醋酸用量的增加对酸溶木质素和灰分含量的变化均无显著影响。预处理后高聚糖的降解程度随醋酸用量的增加而上升,其中半纤维素的降解程度尤为显著,阿拉伯聚糖、半乳聚糖大量溶出。对经醋酸预处理稻草的酶水解研究表明,预处理中醋酸用量的增加无助于酶水解液中还原糖得率的提高。稻草于160℃下经不添加醋酸的自水解预处理后,其酶解还原糖得率均高于经醋酸预处理的稻草,当纤维素酶用量为40 FPU/g(对底物)时,稻草中高聚糖的酶水解转化效率最高,葡聚糖、木聚糖的转化率分别为67.8%和45.3%,总糖转化率为58.8%。     

麦秸秆的氢氧化钙预处理及酶解试验研究

采用氢氧化钙对麦秸秆进行预处理,以酶解还原糖得率为目的,分别优化预处理及酶解条件。结果表明,氢氧化钙预处理麦秸秆的最佳条件是:Ca(OH)2添加量为0.06g/g(对秸秆),固液比为1:10,在120℃下反应时间为2h;最佳酶解条件是:温度50℃,pH4.8,纤维素酶17FPU/g(对秸秆),木聚糖酶160IU/g,在添加0.15g/g(对秸秆)Tween80条件下,酶解液中还原糖质量浓度为62.32g/L,酶解还原糖得率达85.23%。     

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。     

PB试验和BBD响应面优化酶解鱼鳞制备抗菌肽工艺

以酶解液的多肽含量和抑菌活性作为考察指标,采用酸性蛋白酶酶解制备草鱼鱼鳞抗菌肽。在单因素的基础上,运用PB试验设计进行影响因素的显著性筛选,确定出显著性影响因素为pH、温度和时间,进而通过BBD试验得到草鱼鱼鳞抗菌肽制备的最佳工艺条件为:pH 2.72、40.22℃、97.33min,在该条件下酶解液对金黄色葡萄球菌的抑菌圈直径为18.49mm,对大肠杆菌的抑菌圈直径为17.31 mm。结果表明,利用酸性蛋白酶酶解制备草鱼鱼鳞抗菌肽是行得通的,为草鱼鱼鳞等下脚料实现低值原料高值化提供了新的思路。