玉米芯残渣的碱性亚硫酸盐预处理及其反应动力学模型

玉米芯提取木糖后残留了大量富含纤维素和木质素的废弃物。针对玉米芯残渣(corncob residues,CCR)中木质素含量高和半纤维素含量很低的特点,采用碱性亚硫酸盐法进行预处理。研究了预处理p H、液固比、温度、亚硫酸盐用量等条件对纤维素保留率、木质素去除率、底物酶解效率以及预处理液中木质素磺酸钠含量的影响规律。结果表明,当亚硫酸钠用量为10%(质量)、氢氧化钠为5%(质量)、液固比为6:1、160℃预处理1 h时,可去除86.1%的木质素、保留82.4%的纤维素,底物的72 h酶解率达85.1%[酶载量为5 FPU·(g葡聚糖)-1],预处理液中木质素磺酸钠的收率为31.5 g·(100 g CCR)-1。为了指导放大试验和工程应用,提出了一个能准确预测底物木质素含量的参数——木质素因子(lignin factor,LF),在此基础上成功建立了脱木质素反应动力学经验公式以及底物酶解效率的预测方程,预测值与实测值误差在10%之内。     

NaOH/AQ预处理对玉米秸秆脱木质素及酶解性能的影响

对玉米秸秆进行氢氧化钠/蒽醌（NaOH/AQ）去木质化预处理,考察了预处理温度、时间和NaOH用量对玉米秸秆脱木质素程度的影响,并探讨了脱木质素程度对提高预处理后物料酶解性能的影响。L₉（3⁴）正交试验得出较适宜预处理工艺条件为：温度160℃,时间60 min,NaOH用量（以绝干原料质量计）2.8%;其他条件为AQ用量0.05%,固液比1：5（g：mL）,此时木质素脱除率为75%,酶解后聚糖转化率达到73.79%。随着物料脱木质素程度的提高,其酶解效率相应增加;当木质素脱除率达到一定程度后,预处理后的聚糖转化率达到最大值,继续提高木质素脱除率,聚糖转化率反而降低。响应面优化的酶水解工艺条件为纤维素酶用量30 FPU/g,β-葡萄糖苷酶10 IU/g,反应时间72 h,温度50℃,底物质量分数2.5%,此时还原糖得率为85.62%。对酶解液进行HPLC分析,酶解液中的葡萄糖质量浓度为14.83 g/L,木糖质量浓度为4.83 g/L。XRD分析显示,预处理前后纤维素的晶型没有变化,而结晶度由31.40%提高至46.91%,表明物料中木质素和半纤维素发生了不同程度的溶出。     

玉米芯氨水预处理及酶解工艺研究

为有效提高木质纤维素酶解转化率,文中以玉米芯为研究对象,在常压中温下采用氨水浸泡工艺处理原料,考察了预处理条件对木质素脱除率和纤维素、半纤维素酶解转化率的影响规律。确定了最适预处理条件:氨水质量分数为15%、固液质量体积比为1∶6 g/mL、反应温度为60℃和预处理时间为12 h。该条件下纤维素、半纤维素回收率和木质素脱除率分别为94.5%,86.7%和48.1%;在每g葡聚糖加入30 FPU纤维素酶和60 CBUβ-葡萄糖苷酶条件下,酶解24 h后纤维素和半纤维素酶解转化率分别可达83.0%和81.6%。     

慈竹机械浆（RMP）氨法预处理工艺研究

研究了在氨水中添加少量KOH或K3PO4预处理慈竹机械浆（RMP）的新工艺。分别采用氨水加KOH和氨水加K3PO4两种方法对原料进行预处理,考察了预处理条件对酶解还原糖产率的影响规律。单因素试验得到氨水加KOH最佳预处理条件为：预处理温度120℃、固液质量体积比1：6g/ mL、时间3.5 h、氨水用量70%(g/g绝干)、KOH用量5%(g/g绝干)。在此最佳条件下,慈竹RMP的纤维素回收率为90.66%、半纤维素回收率为92.90%、木质素去除率为41.05%；在pH4.8、加酶量20FPU/g预处理后底物、反应温度50℃的条件下酶解24 h,还原糖产率为23.95%,纤维素转化率为44.61%。 虽然氨水加K3PO4预处理酶解纤维素转化率可以达到56.95%,但是纤维素回收率仅为74.59%,与氨水加KOH相比,纤维素损失较大。     

碱性臭氧预处理对稻草秸秆酶水解的影响

以稻草秸秆为原料经碱性臭氧预处理后进行酶水解,研究了处理前后稻草秸秆半纤维素、纤维素、木质素含量的变化,通过测定酶水解还原糖含量来判断预处理的效果。结果表明,碱性臭氧预处理与碱预处理相比,在稻草秸秆木质素含量与降解上没有什么差异,但酶水解糖化效果更优。经O3/2%NaOH预处理过的稻草秸秆,在pH值5.0、酶用量31.2mg.（g底物）-1、45℃条件下酶水解120h时,还原糖含量达到了902mg.（g稻草秸秆）-1,糖化率达到了92.57%。     

低共熔溶剂预处理提高甘草渣酶解效果优化

近年来，低共熔溶剂（deep eutectic solvent，DES）以易制备、成本低、易回收等优势，在生物质预处理方面受到广泛关注。本研究以氯化胆碱为氢键受体，乙醇胺为氢键供体，合成DES，研究了不同温度、时间和固液比预处理条件对中药渣组分和酶解效果的影响。结果表明：固液比1∶20、120℃、预处理4h后原料中木质素去除率达到78.42%，纤维素回收率为83.89%。随后对不同条件下所得底物进行酶水解，反应96h后发现，较优条件下所得底物酶解效率为78.57%，较未处理中药渣（30.40%）提高了1.58倍。类分形动力学分析表明，预处理温度对酶解效果影响最大。SEM、XRD和FTIR检测发现，预处理后底物形貌、结晶指数和官能团变化有利于酶解效果的提高。     

枯草芽孢杆菌发酵甘草渣产2,3-丁二醇和乙偶姻的初步研究

甘草渣是甘草提取完活性成分后的剩余物，富含木质纤维素。以甘草渣为研究对象，以2种稀碱（Na2CO3水溶液和NaOH水溶液）以及稀碱（Na2CO3水溶液或NaOH水溶液）和醋酸乙醇胺离子液体混合液为溶剂对甘草渣进行预处理，研究不同碱浓度和预处理温度对甘草渣组成及酶解效果的影响。结果表明，质量分数2%的NaOH水溶液在固液比（w/v）1:10（即每克甘草渣加入10毫升溶剂）、100 ℃条件下预处理甘草渣1.5 h，木质素去除率达54.1%、纤维素回收率为77.2%；样品酶解24 h，葡萄糖得率可达53.5%，较预处理前甘草渣（10.6%）提高了4.0倍。最后，对预处理后的甘草渣进行高固酶解，在固液比3:10、酶用量45 FPU/g生物质条件下酶解72 h，葡萄糖产量达到86.2 g/L、木糖18.9 g/L。以此酶解液为碳源进行发酵，96 h后发酵液中2,3-丁二醇和乙偶姻总产量为43.9 g/L，还原糖转化率为0.42 g/g；与对照组相比，酶解液更有利于菌体生长，生产强度提高，但转化率略低。     

木糖渣的有机溶剂预处理及酶解性能

木糖渣是玉米芯经稀酸处理提取木糖后的残余物,一般作为燃料焚烧以提供部分热能。由于其含有丰富的纤维素组分,故可通过生物转化来生产多种化工产品,但残渣中大量木素的存在严重抑制了纤维素酶的水解效率。采用一些有机溶剂预处理可将部分木素溶出,因而可改善物料的酶解性能。采用乙醇对木糖渣进行预处理,研究了预处理条件（如温度、时间、固液比等）对木糖渣化学组分和纤维素酶解转化率的影响,并与玉米秸秆和玉米芯等进行了对比。结果表明预处理降低了木糖渣的木素含量,在固液（质量/体积）比1︰8、处理液中乙醇浓度50%（体积）、预处理温度210℃、预处理时间60 min时,木素脱除率为53.26%,预处理后木糖渣在酶解72 h时的纤维素转化率达到84.42%,比预处理前提高 14.58%。研究还发现,与木糖渣相比,有机溶剂乙醇更适合用于玉米芯和玉米秸秆酶解前的预处理。     

碱性过氧化氢预处理对稻草秸秆酶解的影响

木质纤维素生物转化的关键是预处理和酶解,为了提高木质纤维素的生物转化效率,在温和条件下对稻草秸秆进行弱碱性过氧化氢处理。研究了稻草秸秆处理固液比、过氧化氢和纤维素酶添加量对酶解糖化的影响,结果表明:稻草秸秆固液比为800 g/L,过氧化氢添加量为0.125 g/g,酶解时纤维素酶浓度25 FPU/g底物为较好,红外分析表明稻草秸秆处理后,秸秆纤维素的结晶度和木质素含量都有所下降,促进了生物转化后续过程中的酶解糖化。     

玉米芯稀酸预处理和分步糖化与发酵工艺生产燃料乙醇的中试研究

利用正交试验在中试水平考察了玉米芯的稀硫酸预处理和分步糖化与水解生产乙醇的工艺。结果:最佳预处理工艺为稀硫酸浓度1.1%,温度120℃,固液比1∶8,时间3 h;酶解糖化最佳工艺为:起始底物浓度180 g/L,滤纸酶活:纤维二糖酶活=20 IU/g底物:7 IU/g底物,pH=5.0,48 h;利用运动发酵单胞菌发酵酶解液,35℃,48 h,发酵液中乙醇浓度最高67.8 g/L。     

Modification of Alkaline Pulping to Facilitate the Isolation of Aliphatic Acids Part 1. Sodium hydroxide pretreatment of pine wood

Pretreating pine chips (Pinus sylvestris) with sodium hydroxide prior to the alkaline delignification (kraft, kraft-anthraquinone, and soda-anthraquinone) can facilitate the recovery of the carbohydrate degradation products from alkaline pulping liquors. Under suitable pretreatment conditions large amounts of carbohydrate degradation products (aliphatic acids) were formed relative to lignin. The lignin fraction was composed of comparatively low-molecular-weight fragments. Although the delignification was considerably retarded and the yield (based on wood) was decreased by 1–3%, the properties of the resulting pulp were essentially maintained despite pretreatment. Finally, data are given for the composition of aliphatic acids in liquors resulting from pretreatments.     

亚硫酸钠预处理提高稻草酶水解糖化效率的研究

研究了亚硫酸钠预处理对稻草化学组分变化及酶水解性能的影响。结果表明,提高温度或增加Na2SO3用量可以脱除更多的木质素和半纤维素,酶水解效率也相应提高,但木质素脱除率达到50%以后,继续增强预处理条件,对酶水解糖得率无显著的促进作用。相比而言,加大Na2SO3用量更有利于使木质素溶出,提高温度更有利于使高聚糖溶出,加大Na2SO3用量比提高温度对酶水解效率的提高影响更显著。通过实验得到亚硫酸钠预处理稻草的最优条件,在温度为140℃,Na2SO3用量为16%,纤维素酶用量为20 FPU/g(对纤维素)时,总糖转化率达到最大,为74.9%,此时的总糖得率为43.5%。     

Pretreatment Strategies to Enhance Enzymatic Hydrolysis and Cellulosic Ethanol Production for Biorefinery of Corn Stover

There is a rising interest in bioethanol production from lignocellulose such as corn stover to decrease the need for fossil fuels, but most research mainly focuses on how to improve ethanol yield and pays less attention to the biorefinery of corn stover. To realize the utilization of different components of corn stover in this study, different pretreatment strategies were used to fractionate corn stover while enhancing enzymatic digestibility and cellulosic ethanol production. It was found that the pretreatment process combining dilute acid (DA) and alkaline sodium sulfite (ASS) could effectively fractionate the three main components of corn stover, i.e., cellulose, hemicellulose, and lignin, that xylose recovery reached 93.0%, and that removal rate of lignin was 85.0%. After the joint pretreatment of DA and ASS, the conversion of cellulose at 72 h of enzymatic hydrolysis reached 85.4%, and ethanol concentration reached 48.5 g/L through fed-batch semi-simultaneous saccharification and fermentation (S-SSF) process when the final concentration of substrate was 18% (w/v). Pretreatment with ammonium sulfite resulted in 83.8% of lignin removal, and the conversion of cellulose and ethanol concentration reached 86.6% and 50 g/L after enzymatic hydrolysis of 72 h and fed-batch S-SSF, respectively. The results provided a reference for effectively separating hemicellulose and lignin from corn stover and producing cellulosic ethanol for the biorefinery of corn stover.     

SO2-Ethanol-Water (SEW) Pulping: I. Lignin Determination in Pulps and Liquors

Abstract

Quantitative determination of lignin in SO₂-ethanol-water (SEW) pulps and spent liquors is described. The methods developed for conventional sulfite pulping are successfully applied to the SEW process. Linear correlations between Klason/total lignin content and kappa number are found over a wide pulp yield range for spruce, beech, and wheat straw. Lignin content of the spruce spent SEW liquors is determined using either hydrogen peroxide to remove SO₂ and dilution by 3% sulfuric acid or simply by dilution with 0.1M sodium hydroxide. The recommended wavelength is 280 nm. The experimentally found values for the extinction coefficient of dissolved lignin in 3% sulfuric acid and in 0.1M NaOH are 19 and 23 L/(g·cm), respectively. The interference of furanic compounds is eliminated by reduction with sodium borohydride.     

废纸脱墨浆预处理及其酶解性能研究

以预处理后的废纸脱墨浆为底物,纤维素酶和纤维二糖酶为水解酶,研究了不同预处理方法（包括Na₂SO₃、H₂O₂、HCl）对酶解得率的影响。结果表明：与原料相比,3种预处理方法都不同程度地提高了纤维素含量,增加底物的比表面积,降低纤维素的结晶度,促进酶水解;其中,H₂O₂预处理后的废纸脱墨浆的酶解得率最高,为91.67%,其次是亚硫酸钠预处理和盐酸预处理,得率分别为87.57%和82.49%。     

Structural Properties and Hydrolysability of Paulownia elongate: The Effects of Pretreatment Methods Based on Acetic Acid and Its Combination with Sodium Sulfite or Sodium Sulfite

The effects of CH₃COOH and Na₂SO₃ pretreatment on the structural properties and hydrolyzability of fast-growing Paulownia elongate were investigated. Acetic acid increased cellulose’s crystallinity and hydrolyzability when combined with alkaline sodium sulfite and sodium hydroxide. The cellulose content increased by 21%, the lignin content decreased by 6%, and the product showed better enzymatic digestibility. With a cellulase dose of 30 FPU/g DM, after 72 h hydrolysis, the hydrolysis yields of glucose and xylose were 78% and 83%, respectively, which were 51% and 69% higher than those of untreated materials. When the enzyme dosage was 20 FPU/g DM, after 72 h hydrolysis, the hydrolysis yields of glucose and xylose were 74% and 79%, respectively. The high hydrolyzability, low enzyme loading, and high hydrolysis yield demonstrate the potential of the proposed system for producing platform sugars from fast-growing Paulownia elongate.     

Effects of Green Liquor (GL) and Sodium Carbonate (SC) Pretreatment on Structural Characteristics of Wheat Stem Lignin

The content and structure of lignin have been considered as important factors that affect both pretreatment and enzymatic hydrolysis of lignocellulosic biomass. In this work, wheat stems (WS) were pretreated using mild alkali including green liquor (GL) and sodium carbonate (SC). The results indicate that GL pretreatment exhibits better delignification selectivity and higher enzymatic digestibility than SC pretreatment. Analysis of ¹H–¹³C HSQC NMR and FTIR on cellulolytic enzyme lignin (CEL) preparations isolated from untreated and pretreated WS also proves that a certain amount of lignin degrades which leads to a decrease of β-O-4′ linkages. Under mild alkaline conditions, more guaiacyl units in lignin are removed than syringyl units, which results in a higher condensation degree and S/G ratio of CELs isolated from GL- and SC-pretreated stems. Compared with p-coumarate structures, ferulates in lignin are more stable under mild alkaline conditions.     

Evaluation of Prosopis juliflora as a potential feedstock for the production of sodium lignosulfonate from the spent liquor of a laboratory digester

Abstract

Chopped stems of Prosopis juliflora, an invasive xerophyte, were digested in a laboratory digester following alkaline sulfite pulping process to generate spent liquor whereby lignin underwent sulfonation to produce sodium lignosulfonate (SLS). SLS was concentrated from the spent liquor by ultrafiltration. Raw wood was featured by high lignin (23.5%), low extractives (1.0%), low wax (0.41), and low ash (2.25%) content thus making it an ideal feedstock to produce lignosulfonates with appreciable physico-chemical property and relatively high mechanical strength. Attempts were made to provide basic information on SLS structure and structural changes that might occur during pulping of P. juliflora under the present experimental conditions. Spectral and X-ray diffraction studies on as-produced SLS revealed substantial depolymerization and structural modification of lignin during sulfite pulping. The derived SLS had higher crystallinity index than the feedstock wood. Effect of average size of raw wood chip and dose of sodium sulfite in the overall yield of pulp and SLS along with the kappa number of the pulp were also analyzed. Findings from this study would serve to cultivate a better understanding of the potential of P. juliflora as a feedstock, so far unexplored, to produce SLS???a value-added product with numerous commercial applications. The use of this particular plant species in paper and pulp industry could also be considered as an effective means of integrated agro management in rural areas.     

蒸煮助剂对低用碱量硫酸盐法预处理毛竹竹屑的影响

毛竹竹屑经10%低用碱量 (以Na₂O计)、20%硫化度、160 ℃下保温1 h预处理,木质素脱除率达到62.35%,预处理物料酶水解48 h葡萄糖和木糖得率分别为56.04%和53.47%。研究了硼氢化钠、三聚磷酸钠、2-蒽醌磺酸钠3种蒸煮助剂对毛竹竹屑10%用碱量硫酸盐预处理的成分以及糖化效果影响,其中2-蒽醌磺酸钠影响最大。在10%用碱量和20%硫化度的预处理液中添加0.15%的2-蒽醌磺酸时,160 ℃下保温1 h的葡聚糖回收率和木质素脱除率分别为94.93%和68.55%,与空白对比分别提高5.45%和9.94%;预处理物料酶解48 h葡萄糖和木糖得率分别为62.88%和58.97%,与空白对比分别提高12.21%和10.29%。     

芦苇与荻木素结构及对制浆性能的影响

对芦苇和荻的制浆性能进行了比较。结果表明 ,在硫酸盐法和碱性亚硫酸钠法制浆中 ,芦苇比荻较难蒸煮 ,芦苇浆卡伯值高、得率低。这是由于芦苇木素与荻木素在结构上的差异所致。在芦苇碱性亚硫酸钠 -蒽醌法蒸煮中 ,蒽醌可显著地加速脱木素作用。