基于高底物浓度的纤维素酶三段水解桑木粉得率与形貌分析

为改善高底物浓度酶水解过程中产物抑制问题,采用三段酶水解方法,通过在水解过程中及时移除反应产物纤维二糖和葡萄糖,降低产物抑制作用,增加酶反应速率,从而提高酶水解得率、缩短酶反应时间。与原料和经NaOH预处理的桑木比较,NaOH-Fenton预处理后的桑木中木聚糖含量明显降低,纤维素含量相对增加,木质素含量变化较小。无论是一段水解还是三段水解,纤维素酶水解得率均随底物质量浓度的升高而下降。在0.30 g/m L(m/V)底物质量浓度下,当酶用量增加为40 U/g(以纤维素质量计)时,三段(10+10+10)h酶水解得率74.16%,比一段水解72 h得率45.61%增长了62.60%,并且水解时间缩短了42 h。该研究结果对提高纤维素酶水解得率、降低纤维资源制取燃料乙醇成本具有指导意义。     

几种纤维素酶制剂水解和吸附性能的研究

比较了商品纤维素酶和自产纤维素酶在蛋白组分及蛋白组分含量上存在的差异。商品纤维素酶水解稀酸预处理和蒸汽爆破预处理的玉米秸秆,其水解得率均低于自产纤维素酶。以蒸汽爆破的玉米秸秆为碳源制备纤维素酶,添加外源8 IU/g(以纤维素计)的β-葡萄糖苷酶,水解蒸汽爆破的玉米秸秆48 h,纤维素水解得率为90.08%;水解液中纤维二糖的质量浓度从17.06 g/L降低到1.12 g/L,相应葡萄糖质量浓度从21.09 g/L提高到44.01 g/L,可发酵性糖从55.28%提高到97.52%。微晶纤维素对商品酶和自产酶的吸附在30 m in达到平衡,且符合Langmu ir等温吸附方程;由Langmu ir常数分析得知两类酶均来自里氏木霉,且对微晶纤维素的亲和力相差不大。     

亚硫酸盐蔗渣浆酶解工艺及外源物辅助作用的研究

以亚硫酸盐蔗渣浆为研究对象,研究了底物浓度、外源添加物种类和浓度对纤维素酶解工艺的影响以及PEG6000强化酶解效率的作用机理。研究结果表明,纤维素酶用量15 FPIU/g(以绝干纤维素计,下同)、β-葡萄糖苷酶用量30 CBU/g,纤维素质量浓度80 g/L条件下水解48 h,葡萄糖质量浓度达72.51 g/L,葡萄糖得率、纤维素酶解得率和总糖得率达81.58%、86.79%和84.23%。PEG6000可有效强化酶解,添加量为2 g/L时,水解48 h葡萄糖质量浓度可升至78.54 g/L,葡萄糖得率、纤维素酶解得率和总糖得率达88.36%、95.02%和92.54%。添加2 g/L的PEG6000使纤维素酶Celluclast1.5 L滤纸酶活力提高到原酶活力的117.33%;同时50℃,pH值4.8,保温48 h,残余酶活力同比增加38.99%。     

The Study about Enzymatic Hydrolysis of Bagasse Sulfite Pulp and the Assistant Effect of Additives

以亚硫酸盐蔗渣浆为研究对象,研究了底物浓度、外源添加物种类和浓度对纤维素酶解工艺的影响以及PEG6000强化酶解效率的作用机理.研究结果表明,纤维素酶用量15 FPIU/g(以绝干纤维素计,下同)、β-葡萄糖苷酶用量30 CBU/g,纤维素质量浓度80 g/L条件下水解48 h,葡萄糖质量浓度达72.51 g/L,葡萄糖得率、纤维素酶解得率和总糖得率达81.58％、86.79％和84.23％.PEG6000可有效强化酶解,添加量为2g/L时,水解48 h葡萄糖质量浓度可升至78.54 g/L,葡萄糖得率、纤维素酶解得率和总糖得率达88.36％、95.02％和92.54％.添加2g/L的PEG6000使纤维素酶Celluclast 1.5 L滤纸酶活力提高到原酶活力的117.33％;同时50℃,pH值4.8,保温48 h,残余酶活力同比增加38.99％.     

β-葡萄糖苷酶的制备及在纤维素辅助水解上的应用研究

研究了固体发酵法制备β-葡萄糖苷酶及其在纤维素水解上的应用.黑曲霉NL02以玉米芯和麸皮为碳源固体发酵制备β-葡萄糖苷酶,培养5d,酶活力达到225.43IU/g(以干曲计).粗β-葡萄糖苷酶酶液经硫酸铵沉淀、离子交换层析、凝胶过滤层析纯化,获得单一β-葡萄糖苷酶组分,酶活回收率和比活力分别为69.34%和133.88IU/mg.底物质量浓度为100g/L的稀硫酸预处理玉米秸秆,经酶用量为20FPIU/g(以纤维素计)的里氏木霉纤维素酶和4IU/g(以纤维素计)的β-葡萄糖苷酶水解48h,水解糖液中纤维二糖和葡萄糖质量浓度分别为1.12和42.68g/L,纤维素水解得率和可发酵性糖的比例分别为62.85%和97.44%.     

酶法糖化玉米芯发酵生产乙醇的研究

研究了玉米芯的酶法水解及酶解液的乙醇发酵。采用里氏木霉ZU-02纤维素酶水解酸预处理后的玉米芯为原料,适宜的酶用量为20 FPIU(以每克底物计,下同),48 h后酶解得率为67.5%;添加黑曲霉ZU-07所产纤维二糖酶可有效解除纤维二糖累积引起的反馈抑制作用,当纤维二糖酶用量为6.5 CB IU时,48 h后酶解得率提高到83.9%。采用分批补料酶解工艺,使底物质量浓度提高到200 g/L,酶解60 h后还原糖质量浓度达到116.3 g/L,酶解得率为80.1%。利用一株耐高温酿酒酵母HTR-11在38℃下对酶解液进行乙醇发酵,质量浓度95.3 g/L的葡萄糖在18 h内发酵生成质量浓度为45.7 g/L的乙醇,其得率达到理论值的94%。     

阔叶材(山杨和速生杨)漂白浆和未漂浆水解降解及其产物性质的研究(英文)

本文研究了木素含量为0.2—1.2％的山杨和速生杨漂白浆和未漂浆的水解降解过程。研究结果表明,该过程与先前已研究过的其它种类的木浆具有相类似的特点,即水解过程存在两个明显的阶段(快速降解阶段和缓慢降解阶段),最终纤维素降解至“极限”聚合度。由不同原料用不同方法制成的不同种类的浆,其水解速度以递减的顺序排列为:山杨浆(漂白浆和未漂浆)→白桦浆→速生杨浆(漂白浆和未漂浆)→针叶材硫酸盐浆→针叶材亚硫酸盐浆(3.7×10~(-4)/分,1.7×10~(-4)/分→1.6×10~(-4)/分→1.3×10~(-4)/分,0.9×10~(-4)/分→1.2×10~(-4)/分,0.8×10~(-4)/分) 水解后纤维索达到“极限”聚合度,后者大小取决于原料种类。山杨硫酸未漂浆分别为206和135;氧碱法山杨浆为160;速生杨硫酸盐未漂浆和漂白浆分别为250和240。水解后试样呈白色粉末状,得率82～85％。试样以其吸水能力为显著特征。未经超声波分散作用的试样,其吸水值比原浆低(从未漂浆90～115％和漂白浆75～95％降至70～80％)。反之,于水中经超声波分散作用后,试样的吸水值急剧增大(山杨微晶纤维素为160％,速生杨微晶纤维素为260％),接近于桦木浆和棉浆微晶纤维素的水平。对原浆纤维和微晶纤维颗粒形状和大小进行了显微观测。测得的数量分布微分曲线表明,在酸水解     

4种木质纤维素预处理方法的比较

采用4种方法对玉米秸秆预处理,研究了不同预处理方法对酶水解性能和可发酵性糖得率的影响,分析了预处理物料主要成分,预水解液中糖组成、碳水化合物降解产物及木质素降解产物含量.100 g玉米秸秆经稀酸、稀酸磨浆、中性蒸汽爆破和稀酸蒸汽爆破预处理、洗涤后,物料中纤维素由37.17g分别降为33.96、33.54、32.63和32.88 g,木聚糖由22.84 g分别降为2.77、2.47、3.56和2.05 g,木质素由18.76 g分别降为17.63、17.42、16.90和17.25 g.稀酸蒸汽爆破预处理物料在底物质量浓度100 g/L、纤维素酶用量20 FPIU/g(以纤维素计,下同)、β-葡萄糖苷酶用量3 IU/g下酶水解48 h,纤维素水解得率为75.91％.玉米秸秆经稀酸蒸汽爆破预处理、纤维素酶水解后可发酵性糖得率为44.93％(以玉米秸秆为基准).     

低聚木糖生产废渣纤维素酶诱导和水解特性的研究

研究了生产低聚木糖(XOS)所得的废渣对里氏木霉纤维素酶合成的诱导作用和纤维素酶水解特性.废渣对里氏木霉合成纤维素酶的诱导作用较差,而纤维素酶水解性能优异.里氏木霉以含纤维素15 g/L的废渣为碳源合成纤维素酶,滤纸酶活为0.48 FPIU/mL,酶产率为6.67 FPIU/(L·h),酶得率为每克纤维素32.00 FPIU,而在相同条件下以玉米芯为碳源时滤纸酶活为3.20 FPIU/mL、酶产率19.00 FPIU/(L·h)和酶得率每克纤维素213.33 FPIU.质量浓度为20 g/L的废渣在酶用量为每克纤维素10 FPIU条件下水解24 h,水解得率达92.8 %;底物废渣质量浓度为100 g/L时,48 h纤维素酶水解得率达到80.6 %.     

酶水解过程中纤维素聚合度和结晶度的变化

分别采用复合纤维素酶Celluclast 1.5L和内切纤维素酶Novozym 476对漂白针叶木纤维进行水解,通过分析酶水解后纤维素聚合度和结晶度的变化情况,研究2种纤维素酶对纤维素聚合度和聚集态结构的影响。结果显示:漂白针叶木纤维经2种纤维素酶分别水解后,随着酶用量的增加,纤维素聚合度都逐渐降低,当Celluclast 1.5 L用量为3.0 FPU/g时,纤维得率为94.34%,纤维素聚合度降至862,较原样(1 164)下降了25.95%;而Novozym 476用量为50.0 U/g时,纤维得率为94.93%,纤维素聚合度降至711,较原样下降了38.92%。由此可见,在得率相同的情况下,经Novozym 476水解的纤维素较经Celluclast 1.5 L水解的纤维素具有更低的聚合度,说明内切葡聚糖酶是导致纤维素聚合度下降的主要因素。随着复合纤维素酶Celluclast 1.5 L用量的增加,纤维素结晶度呈现先增加后降低再增加再降低的M型变化;随着内切纤维素酶Novozym 476用量的增加,纤维素结晶度呈现先降低后增加再降低的变化。     

Evaluation of pulp and paper making characteristics of certain fast growing plants

Summary Four species of fast growing annual plant viz.Hibiscus sabdariffa, Crotalaria juncea, Tephrosia candida andHibiscus cannabinus and a variety of reed, Neyraudia reynaudiana were evaluated in the laboratory for their pulp and paper making properties. Data on proximate chemical analysis of raw materials, unbleached and bleached pulp properties, morphological properties of fibres and physical strength properties of paper sheets were evaluated. The unbleached pulp yields were 44.90–53.20% with all the five plant materials, while bleached pulp yields varied from 39.80–50.60%. The average fibre lengths and diameters of the unbleached pulp obtained from the five plant species were within the range of 0.75 mm–2.15 mm and 20–22 pun respectively. Paper hand sheets, made with bleached pulps (45° SR) obtained from the five plant species, gave burst indices 2.75–3.92 kPa m²/g, tear indices 3.73–9.61 m N m²/g and tensile indices 37.27–47.81 N mg^–1, indicating adequate strength properties for writing and printing type of paper.The authors thank Director, Regional Research Laboratory (CSIR), Jorhat, India, for his kind permission to publish this paper. The authors also wish to thank B. N. Tosh, JPF for his assistance.     

Antibody-based assay for galacturonan deesterification on wood pulp fibers during bleaching

Antibodies recognizing galacturonan were used in immunoassays for industrial unbleached and hydrogen peroxide-bleached chemithermomechanical pulp (CTMP). The assays were based on a colorimetric method using specific monoclonal antibody recognition of acidic and methylated homogalacturonan, respectively, on the pulp fiber surfaces. Alkaline phosphatase-conjugated antibodies were linked to the galacturonan specific antibodies, and an alkaline phosphatase substrate (p-nitrophenylphosphate) was used to develop a yellow reaction product that can be followed spectrophotometrically. Together the newly developed immunoassays were able to describe the deesterification, specifically, of surface-localized galacturonan on CTMP, induced by alkaline hydrogen peroxide bleaching. Unbleached CTMP showed relatively more labeling by methylated galacturonan recognizing antibodies, whereas bleached CTMP was relatively more labeled for acidic galacturonan. The increase in negative charge of the bleached pulp was also shown by polyelectrolyte titration; the negative surface charge was 9.3 μeq g⁻¹ in unbleached CTMP and 21.7 μeq g⁻¹ in bleached pulp.     

Steam explosion pretreatment used to remove hemicellulose to enhance the production of a eucalyptus organosolv dissolving pulp

The steam explosion (SE) pretreatment associated with the organosolv process was investigated to produce dissolving pulp from eucalyptus. Prehydrolysis Kraft (PHK) pulping was also done to produce viscose and acetate grade pulps as reference. The organosolv pulps were delignified in two steps with sodium chlorite. Viscose and acetate grade PHK pulps were bleached by OD₀(EH)D₁P and OD₀(EP)D₁PCCE sequences, respectively. Dilute acid-catalyzed (with acid addition) SE pretreatment dissolved more xylan than auto-catalyzed (no acid addition) SE pretreatment. Steam-exploded unbleached organosolv pulps showed lower residual lignin content and screened yield than unbleached organosolv pulps without SE pretreatment. Steam explosion pretreatment helped to decrease lignin content and damaged fiber length of unbleached organosolv pulps. The 1.0% H₂SO₄ organosolv pulp (organosolv dissolving pulp at bioconversion conditions) showed the highest reactivity. Even showing low viscosity for some applications, in general, the organosolv dissolving pulps produced in this study can be used for making lyocell fibers.     

氧漂过程中脱木质素与木质素氧化之间定量关系的研究

对氧碱漂白过程中木质素氧化进行定量分析，分析方法是基于氧化前后高锰酸钾消耗量的变化。该方法对溶出残余木质素的氧化结果分析发现其呈明显3个阶段：第一段木质素氧化的当量电荷数约4～5／木质素单元；木质素总氧化电荷数大约为9／木质素单元。这些数据以及甲氧基的脱除（75％）均表明：木质素的氧化不仅发生在酚型木质素单元，同时也发生在非酚型结构单元上。只有第一阶段氧化反应是木质素与氧气直接反应，而在第二、三阶段主要是协同氧化作用，氧化反应过程中产生的活性氧基团扮演了一定角色。通过对低浓度针叶材硫酸盐浆的氧漂研究发现：当卡伯值下降一半（25．4至13．4）时平均每个木质素单元氧化3当量电子，氧漂后的纸浆中仍然有大量未被氧化的残余木质素。定量地证明了在氧漂过程中木质素氧化是脱木质素反应的实质。     

阔叶材（山杨和速生杨）纤维素的形态结构

采用日立Ｓ－１５０型扫描电镜观测了山杨和速生杨纤维素的形态结构。通过观测发现，漂白浆样和未漂浆样显示了各自的某些特点。同时，探讨了原浆和水解后浆样纤维素形态结构的变化状态。     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

杨木制浆技术的新进展

本文介绍了用杨木生产漂白化学浆,包括硫酸盐法,硫酸盐-蒽醌法,烧碱-蒽醌法和碱性亚硫酸钠-蒽醌法制浆;用杨木生产漂白化学热磨机械浆;用杨木生产碱性过氧化氢机械浆;特别是杨木碱性过氧化氢机械浆是90年代发展研制成功的高得率、高白度和强度性好的新化学机械浆种,它适用于配抄低定量胶印新闻纸、低定量涂布纸等。     

桉树制浆综述

本文介绍了(1)用桉木生产漂白化学浆,包括硫酸盐法和碱一蒽醌法制浆;(2)用按木生产漂白半化学浆,主要是中性亚硫酸盐半化学高得率浆;(3)用桉木生产漂白化学机械浆,包括冷碱法和亚硫酸盐法制浆;(4)用桉木生产漂白化学热磨机械浆。     

铈盐引发阔叶浆与GMA接枝共聚的研究

研究了铈盐引发体系引发漂白化学桉木浆与甲基丙烯酸缩水甘油酯(GMA)的接枝共聚.用接枝率、环氧基含量和环氧基水解率评价了体系pH值、反应温度和时间、引发剂浓度和单体浓度对接枝效果的影响,并用红外光谱对接枝产物进行了分析鉴定.结果表明:控制体系pH值在1.3,适当提高反应温度、延长反应时间、增加引发剂浓度和单体浓度,都能提高接枝率;在适当的条件下,可合成接枝率高碄100%、环氧基含量达1.4～2.7mmol/g的接枝纤维;与此同时接枝纤维也存在一定程度的环氧基开环水解反应.