表面活性剂对离子液体预处理纤维素的影响

采用离子液体1-甲基-3乙基咪唑磷酸二甲酯（[MEIM][DMP]）与表面活性剂耦合处理纤维素,考察表面活性剂对于酶解的影响,并用红外光谱、X射线衍射分析其机理。结果表明[MEIM][DMP]/聚乙二醇4000（PEG4000）处理的纤维素酶解率比未处理的纤维素高78.2%,比未加表面活性剂处理的再生纤维素高6.5%。红外光谱显示有PEG4000分子特征峰出现,X射线衍射分析表明PEG4000处理再生的纤维素几乎为无定形区。因此,PEG4000参与的处理有利于进一步提高纤维素酶解率,使结晶度降低,从而酶解率提高。     

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。     

表面活性剂与离子液体对β-葡萄糖苷酶的协同影响

为考察表面活性剂和离子液体1-乙基-3-甲基咪唑磷酸二乙酯盐（[EMIM]DEP）对类芽孢杆菌sp. LLZ1 β-葡萄糖苷酶活性的影响,在酶活测定体系中加入一定浓度的表面活性剂和[EMIM]DEP。结果表明：添加5%的[EMIM]DEP使β-葡萄糖苷酶的活性增强了12.00%,进一步添加0.1%鼠李糖脂、Span20、PEG4000和Tween80分别使酶活增强了21.85%、12.07%、8.57%和5.25%,而Triton X-100和SDS分别使酶活降低了4.59%和10.63%。动力学曲线和动力学参数表明随着表面活性剂和5%[EMIM]DEP对β-葡萄糖苷酶活性的增强,米氏常数K_m随之减小。圆二色谱（CD）分析表明分别经0.1%鼠李糖脂、Span20、PEG4000和Tween80处理后,β-葡萄糖苷酶的α-螺旋分别增加1.00%、0.78%、0.72%和0.80%,添加SDS导致α-螺旋减少5.72%。荧光光谱表明同时添加表面活性剂和5%[EMIM]DEP改变了β-葡萄糖苷酶的最大发射波长。差示扫描量热法(DSC)表明0.1%鼠李糖脂和5%[EMIM]DEP提高了β-葡萄糖苷酶的中点温度和平均展开焓。使用0.1%鼠李糖脂协同5%[EMIM]DEP水解纤维二糖,转化率提高了21.93%。     

非离子表面活性剂对木质纤维素酶解的促进作用

纤维素酶单位酶活力较低、酶用量较高及酶自身易失活等因素依然是木质纤维素工业生产能源和生物基产品的瓶颈性问题。本文尝试在木质纤维素基质水解时添加一些非离子型表面活性剂以减少纤维素酶用量,并对这些非离子型表面活性剂促进酶解效率提高的原因进行了初步探讨。研究发现,添加非离子性表面活性剂能提高木质纤维素的酶解,添加浓度为0.05 g/g底物,常压甘油自催化预处理麦草经过添加两种非离子表面活性剂Tween-80和PEG 6000后葡萄糖产量分别可提高20%左右;非离子表面活性剂对不含木质素的原料酶解产糖也有较大的提高,以滤纸为底物时葡萄糖产量提高近90%,以微晶纤维素为底物时分别提高70%以上;添加非离子表面活性剂使得酶解体系中扩散系数k升高,异相反应效率提高,酶促反应动力学Km值明显减小,显著提高底物对纤维素酶的亲和力。     

离子液体表面活性剂的合成与应用(Ⅱ)——离子液体表面活性剂的合成

按照离子液体表面活性剂的种类,分别介绍了不同类型离子液体表面活性剂的合成方法。阳离子型离子液体表面活性剂可以采用直接季铵化法、复分解法和离子交换法合成;阴离子型离子液体表面活性剂是采用传统阴离子表面活性剂与离子液体在有机溶剂或水/有机溶剂中复分解反应完成的;两性离子液体表面活性剂通常采用直接季铵化法合成;双子和Bola型离子液体表面活性剂与传统双子和Bola型表面活性剂的合成方法相似;微波和超声等新的辅助合成方法将明显促进离子液体表面活性剂的合成。     

离子液体表面活性剂的合成与应用(I)——离子液体表面活性剂的结构和分类

在介绍了离子液体的结构特点和特性的基础上,重点综述了离子液体表面活性剂的结构特征,并且按阳离子型、阴离子型、两性型、双子型和Bola型五类分别介绍了离子液体表面活性剂的典型结构和文献发表的主要品种,显示了离子液体表面活性剂具有较强的结构可设计性和未来品种的多样性。     

离子液体表面活性剂的合成与应用(Ⅳ)——离子液体表面活性剂的表面活性

按照离子液体表面活性剂的分类,分别综述了表面活性剂分子结构对临界胶束浓度(cmc)、最低表面张力(γ_(cmc))、表面吸附效率(pc_(20))、表面饱和吸附量(Γ_(max))和分子最小截面积(A_(min))等表面活性参数的影响。与传统表面活性剂相比,离子液体结构的引入提高了表面活性剂的表面活性,丰富了表面活性剂的品种。烷基碳链长度对表面活性的影响与传统表面活性剂相似。     

离子液体表面活性剂的合成与应用(III)——离子液体表面活性剂的物化性能

重点介绍了离子液体表面活性剂的熔点与结构的关系。阳离子母体结构越不对称熔点越低,烷基链长增加熔点稍有提高;对阴离子型离子液体表面活性剂,阳离子的半径越大,其熔点越低;双子和Bola型离子液体表面活性剂比单疏水基离子液体表面活性剂的熔点高。室温呈液态的离子液体表面活性剂一般为黏稠液体,密度比一般有机溶剂大,在1 g/cm3左右,其表面张力为25~35 mN/m。     

离子液体系中原位酶解高效糖化玉米秸秆

合成了14种具有代表性的离子液体,从中筛选了具有较好秸秆溶解能力和环境友好特性的室温离子液[Meim]DMP。该离子液体可以高效处理秸秆,并且可以进行原位酶解糖化,比未处理秸秆的糖化率提高了2.4倍,实现了天然纤维素材料利用的绿色转化工艺。而且,经过原位酶解之后离子液体[Meim]DMP可以有效地回收使用,重复使用5次后仍然保持很好的性能。     

离子液体表面活性剂的合成与应用(Ⅵ)——离子液体表面活性剂的界面张力

离子液体表面活性剂在油/水界面吸附,降低界面张力。随着疏水烷基链长的增加,降低表面张力的能力增大。吡啶基表面活性剂比咪唑基表面活性剂具有更高的疏水性和降低界面张力能力。在高浓度无机盐存在下,离子液体表面活性剂降低界面张力的能力提高,界面张力可达10~(-2)mN/m,优于传统表面活性剂。     

超高压环境下离子液体微乳液预处理对水稻秸秆的影响

以水稻秸秆为原料,对比了中低温条件下单独超高压（UHP）、单独离子液体微乳液（ILM）和超高压环境下离子液体微乳液（ILM+UHP）3种预处理方法,系统分析了预处理前后样品的化学组成、晶体结构、表面形貌以及酶水解的变化规律。结果表明,采用1-乙基-3甲基咪唑醋酸盐/环己烷/TX-100/正丁醇微乳液处理水稻秸秆,在压强为500 MPa、温度为50℃下处理4 h后,样品中木质素去除率为61.5%,纤维素结晶度指数下降17.3%,微观表面粗糙多孔,酶水解48 h的还原糖产率达75.3%。     

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     

树脂型固体酸催化水解稻草秸秆的新工艺研究

对利用树脂型固体酸催化剂催化水解稻草秸秆制备可溶性糖工艺进行了研究,单因素考察了固固比、固液比、反应温度、反应时间、秸秆目数对秸秆水解产率的影响。研究结果表明:秸秆粉碎至100目,常压下固液比(反应体系中固形物与液体质量比)为1∶10、固固比(树脂型固体酸与秸秆质量比)为1∶1、反应温度100℃、反应时间15 h为最适反应条件,在该条件下树脂型固体酸催化水解稻草秸秆反应的水解产率为32.5%。该新工艺为稻草秸秆的水解利用开辟了一条绿色环保的新途径。     

离子液体[BMIM]Cl处理汽爆活化玉米秸秆及酶解

为了提高玉米秸秆酶解还原糖产率,利用蒸汽爆破法活化玉米秸秆原料,并利用离子液体[BMIM]Cl进行处理,考察了汽爆压力和维压时间对处理后物料酶解还原糖产率的影响。结果表明,汽爆压力2.6 MPa,维压时间90 s下汽爆活化秸秆原料,[BMIM]Cl处理后,酶解24 h后还原糖产率较汽爆活化后物料提高了84.03%,较原料提高了286.83%。秸秆化学组分分析表明,[BMIM]Cl处理后物料纤维素质量分数增加了64.86%,X射线衍射(XRD)与扫描电镜(SEM)分析表明,其晶形结构转变为无定形结构,更有利于纤维素酶与底物作用。说明汽爆活化[BMIM]Cl处理能显著提高玉米秸秆的酶解还原糖产率。     

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 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