碳水化合物降解产物对酿酒酵母乙醇发酵的影响

研究了木质纤维原料预处理产生的主要碳水化合物降解产物对酿酒酵母乙醇发酵的影响,以及酿酒酵母对玉米秸秆酶水解液的乙醇发酵.碳水化合物降解产物对酿酒酵母NLH13乙醇发酵毒性依次为:甲酸>乙酸>糠醛>羟甲基糠醛,酿酒酵母NLH13乙醇发酵可耐受的甲酸和乙酸质量浓度分别为1和4 g/L,酿酒酵母NLHl3在2～10 g/L范...     

杨木稀酸预处理液木糖发酵产乙醇工艺条件的研究

以1.0%H2SO4在150℃预处理杨木屑20 min可水解溶出66.5%木聚糖和7.1%葡聚糖,生成以木糖为主、含有乙酸和甲酸等发酵抑制物的预处理液,脱毒后可采用Candida shehatae R发酵产乙醇,而Pichia stipitisNL23不能生长。减压蒸发加石灰中和法对预处理液的脱毒效果最佳,可脱除70.0%乙酸和40.0%甲酸,糖损失仅为5.0%~6.0%,C.shehataeR的耗糖率和乙醇得率可达到93.2%和83.6%。采用廉价的无机盐能够满足C.shehataeR发酵脱毒液的营养要求。由于包括乙酸和甲酸以外其它毒性物的抑制,C.shehataeR发酵脱毒液的适宜糖质量浓度为30.0 g/L,发酵12 h,耗糖率和乙醇得率为84.7%和75.3%,乙醇质量浓度达到最高值8.54 g/L,同时生成6.08 g/L木糖醇,C.shehataeR对木糖的利用未受葡萄糖的抑制。     

利用基因组DNA诱变技术选育高抑制物耐受性工业酵母菌

通过化学诱变和基于基因组DNA诱变的遗传重组技术,对乙醇工业酵母菌(Saccharomyces cerevisiae)的抑制物耐受性进行改造,获得了重组酿酒酵母HN-1-24,其抑制物耐受性能和发酵性能均得到了提高。重组菌株在含7 g/L乙酸和1 g/L糠醛的抑制物耐受性发酵培养基中,具有良好的糖转化率和乙醇产量,发酵100 g/L葡萄糖能够产生38 g/L乙醇。在纤维素水解液发酵培养中进行乙醇发酵,发现重组菌株的乙醇发酵效率明显快于原始菌株,发酵时间提前6 h,且发酵终点乙醇产量为37 g/L,比原始菌株HN-1提高了8.8%。     

糠醛渣/木薯渣混合底物同步糖化发酵转化乙醇研究

研究了糠醛渣(FR)经不同强度绿液-过氧化氢预处理脱木质素后,与木薯渣(CR)混合进行同步糖化发酵生产乙醇,通过改变原料底物浓度、纤维素酶用量和添加无患子表面活性剂来优化混合底物同步糖化发酵条件,并分析了发酵过程中乙醇和副产物的浓度变化。结果表明,在糠醛渣预处理条件为:底物质量浓度5g/L、温度80℃、H_2O_2用量为0.6g/g、绿液用量为2mL/g(以糠醛渣计)预处理时间3h,在此条件下糠醛渣木质素脱除率可达56.5%。同步糖化发酵产乙醇条件为无患子皂素表面活性剂添加量0.5g/L,纤维素酶用量12FPU/g,纤维二糖酶用量15IU/g,预处理后的糠醛渣与木薯渣混合作底物(质量比为2∶1),底物质量浓度200g/L时,发酵120h最终乙醇质量浓度可达56.6g/L,乙醇得率为86.3%。同步糖化发酵过程中添加无患子皂素表面活性剂不仅降低了纤维素酶用量,还可延缓副产物乳酸的形成,减小甘油生产波动。     

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%。     

基因重组酵母发酵木糖产酒精的研究

以一株基因重组酵母为研究对象,探讨了厌氧条件下pH值、底物浓度、接种量、乙酸质量分数和葡萄糖添加量等关键因子对木糖发酵的影响。结果表明,重组酵母Saccharomyces cerevisiae ZU-10有较强的发酵木糖产乙醇的能力,在80g/L(相对木糖)、初始pH值5.5、接种量1.2g/L(细胞干质量,相对培养液)、30℃下发酵72h,发酵液中乙醇质量浓度达到28.9g/L。发酵液中的乙酸质量分数低于0.05%时对发酵木糖影响不大。添加适量的葡萄糖可促进木糖发酵,在30g/L木糖培养液中添加40g/L葡萄糖,36h内木糖利用率从79.0%增加到85.7%。     

树干毕赤酵母戊糖发酵影响因素的研究

研究了树干毕赤酵母(Pichia stipitis)CBS 5776以木糖为单一碳源发酵生成乙醇的影响因素.结果表明,树干毕赤酵母发酵体系的初始酵母质量浓度、pH值和通风条件对其发酵性能有很大影响,发酵的最佳初始酵母质量浓度为5～7 g/L,最佳pH值范围是4.7～5.5,250 mL摇瓶发酵的最佳持液量为75 mL,最佳摇床转速为150 r/min.在2L发酵罐中,通风量为0.075 L/min,即0.05L/(L·min)时,发酵时间为32 h,最高乙醇质量浓度18.29 g/L,乙醇得率83.2％;厌氧发酵的最高乙醇质量浓度19.09 g/L,乙醇得率86.5％.因此,最优通风量为0～0.075 L/min.pH值的提高和通风条件的改善可以使酵母对乙酸的耐受能力得到提高,在150 r/min的转速、pH值为5时,提高通风量后,酵母乙醇得率比厌氧时提高了166.6％.纯糖实验得到的结果用以玉米秸秆酸性爆破模拟水解液定向驯化的酵母在含有乙酸的模拟糖液中发酵得到验证.     

玉米秸秆乙酰基水解产物对乙醇发酵的影响及去除策略

研究了木质纤维原料在预处理过程中半纤维素上乙酰基水解产生的乙酸对酿酒酵母、树干毕赤酵母乙醇发酵的影响,结果表明乙酸对戊糖、己糖酵母乙醇发酵均产生很大的影响。根据乙酸产生的特点,采用氢氧化钠法去除乙酸而尽量不降解纤维素和半纤维素,从源头上将乙酸与"糖"分开。在单因素(氢氧化钠质量浓度、温度、液固比和时间)试验的基础上,采用响应面分析进一步优化试验,结果表明,上述4个因素的影响从大到小依次为:氢氧化钠质量浓度、液固比、温度和时间。最佳条件为:NaOH 5.45 g/L,液固比13∶1(mL∶g),温度62℃,时间45 min。在此条件下乙酸去除率和木聚糖残留率分别为95.19%和87.80%。     

稀酸预处理玉米秸秆共发酵产乙醇抑制物的来源探究

针对己糖(葡萄糖)、戊糖(木糖)共发酵产纤维素乙醇抑制物控制的关键性瓶颈,分别以玉米秸秆及玉米秸秆中非木质素的4类组分纤维素、半纤维素、热水提取物和乙醇提取物为原料,并以0.75%稀硫酸和180℃预处理40 min得到5种稀酸预处理液。以60 g/L葡萄糖和30 g/L木糖为碳源,分别添加上述稀酸预处理液,比较了5种预处理液对休哈塔假丝酵母(Candida shehatae)共发酵产乙醇的影响,并探究主要抑制物来源。结果表明:133 g/L全玉米秸秆稀酸预处理的降解物会完全抑制C.shehatae糖代谢和共发酵。在玉米秸秆稀酸预处理过程中,4类非木质素组分降解物均会导致乙醇得率下降,其中100 g/L纤维素降解物完全抑制木糖的发酵,半纤维素降解物同时抑制葡萄糖和木糖的发酵,甚至对酵母产生致死毒性,热水提取物和乙醇提取物降解物延滞糖利用和酵母生长。玉米秸秆共发酵产乙醇抑制物主要来自于纤维素和半纤维素在稀酸预处理中的降解反应,主要为甲酸、乙酸、乙酰丙酸、5-羟甲基糠醛和糠醛,同时还存在着其他降解产物的毒性或协同毒性。     

固定化混合菌利用戊糖和己糖共发酵制备乙醇

为研究固定化混合菌种对戊糖和己糖同步发酵生产燃料乙醇的影响,以海藻酸钙为固定化载体,采用包埋法固定化休哈塔假丝酵母(Candida shehatae)和酿酒酵母(Saccharomyces cerevisiae)混合菌发酵生产燃料乙醇,并对固定化混合菌种的发酵条件进行优化。结果表明:固定化混合菌种发酵可以快速利用葡萄糖,解除葡萄糖代谢对木糖代谢的抑制作用,提高发酵效率,发酵时间从固定化单菌发酵的24 h缩短至20 h,发酵时间缩短16.67%。乙醇产量从13.28 g/L增加至14.89 g/L,升高了12.12%。固定化混合菌种的优化条件为:混合糖(葡萄糖和木糖)质量浓度为45 g/L,发酵温度为30℃,摇床转速为170 r/min,休哈塔假丝酵母和酿酒酵母菌体的比例为4∶1。在此条件下得到最佳乙醇产量为15.21 g/L,较优化前(13.74 g/L)提高了10.70%。本研究结果可为固定化混合菌发酵生产燃料乙醇的工业化提供理论依据。     

玉米秸秆蒸汽爆破降解产物的分析

采用高效液相色谱(HPLC)和气质联用(GC-MS)色谱技术对玉米秸秆蒸汽爆破降解产物进行分析.玉米秸秆经蒸汽爆破预处理后,其纤维素、半纤维素和木质素降解损失分别为9.60%、47.98%和17.55%.采用HPLC对碳水化合物降解和分解产物定量分析,100g玉米秸秆预处理后,产生甲酸2.10g、乙酸2.00g、乙酰丙酸0.10g、5-羟甲基糠醛0.08g和糠醛0.13g.采用GC-MS对木质素和提取物降解产物定性分析,共检测出14种芳香类化合物、22种脂肪酸类化合物和5种呋喃化合物.     

糠醛生产废水废渣的资源化利用研究进展

糠醛生产废水温度达95~99℃,醋酸高达1.43%~2.84%,化学耗氧量(COD)10 000~20 000 mg/L,生物耗氧量(BOD)2 500~3 000 mg/L,BOD/COD=0.20~0.25,生物处理困难,长期以来严重困扰着糠醛生产行业的可持续发展。近年开发出多种萃取剂,回收了糠醛生产废水中90%以上的醋酸,采用的多级逆流萃取,萃取效率高达97%~99%。新开发的氧化钙中和-双效蒸发-精馏工艺技术,中和了废水的酸度,利用了废水的热能,废水中大量醋酸得到资源化利用,制成环保型醋酸钙镁(CMA)融雪剂,大大降低了传统CMA融雪剂生产成本,解决了数十年来氯化钠融雪剂腐蚀公路设施的难题,废水基本做到零排放。将糠醛生产废渣高温发酵后制取环保有机肥,或在制糠醛时联产制取木质素和乙醇,也已展示出良好的产业化前景。     

蒸汽爆破木质纤维原料的乙醇脱毒研究

以乙醇为溶剂,采用抽提的方法去除蒸汽爆破玉米秸秆中的甲酸、乙酸、糠醛及羟甲基糠醛等抑制物,比较了动态和静态两种不同的抽提方法对抑制物和糖的抽提效果,考察了温度、固液比和时间等因素对不同条件下乙醇静态抽提效果的影响。以总抑制物抽提率/总糖抽提率为评价指标,通过正交试验,对温度、固液比、时间3个因素在不同水平下的乙醇静态抽提效果进行直观分析和方差分析,确定了乙醇静态抽提的最佳试验条件为:温度80℃,固液比1∶10(g∶mL),抽提时间60 min。在最佳试验条件下,两种最重要的抑制物甲酸和乙酸的抽提率分别达到84%和98%。     

催化木糖制备 呋喃甲醛的研究

为了使呋喃甲醛的制备过程绿色化,以ZrOCl2为原料,利用沉淀-浸渍法初步制备了SO42-/ZrO2固体酸,并应用于催化木糖制备呋喃甲醛的反应。采用L9(34)正交试验确定了适宜的反应条件:木糖质量浓度10 g/L、催化剂用量20 g/L、反应温度220℃、反应时间3 h。之后采用单因素试验考察了催化剂制备条件对呋喃甲醛产率的影响。得到的催化剂最佳制备条件为:H2SO4浸渍浓度1.0 mol/L、焙烧温度550℃、焙烧时间5 h,呋喃甲醛产率达最大值47%。实验结果表明:SO42-/ZrO2固体酸在催化木糖制备呋喃甲醛方面,具有较大发展潜力。     

Effect of acetylation on the chemical composition of hornbeam (Carpinus betulus L.) in relation with the physical and mechanical properties

Common hornbeam (Carpinus betulus L.) is a highly underused wood species despite its great hardness, strength, wear-resistance and toughness. It is mainly used as firewood in Hungary because of its wood defects, irregular shape and low-dimensional stability. These wood defects and small breast height diameter result in a low yield. It is non-durable outdoors as it tends to turn grey, crack and be attacked by wood-decaying organisms. Indoors it lasts for hundreds of years. One technology that could improve the stability and durability properties is acetylation. Hornbeam was acetylated with the Accoya® method under industrial conditions. The aim of this research was the assessment of acetylation affecting the chemical properties of hornbeam wood and how these are related to the change in physical and mechanical properties. Main wood constituents (cellulose, hemicellulose, Klason lignin, extractives and ash content) were determined and compared. Chemical parameters related to the degradation of structural polymers were also evaluated (total phenolic and soluble carbohydrate contents, pH and buffering capacity, furfural, levulinic acid, formic acid, acetic acid). Structural changes in acetylated wood and in the Klason lignin fraction were also assessed using FTIR spectroscopy.     

在Ru/C和甲酸(甲酸盐)体系中碱木质素水热解聚特性研究

在Ru/C和甲酸(甲酸盐)的共同作用下,275~350℃的亚临界水中,进行碱木质素的水热解聚反应。通过GC-MS定性分析和GC-FID定量分析,探究了供氢试剂及用量、反应温度、木质素分子级分对木质素水热解聚的影响。结果表明:在甲酸和Ru/C条件下,木质素解聚液相产物得率最高,组成较简单,具有较好催化降解效果;在甲酸添加量为0.8 mol/L,反应30 min时,木质素解聚液相产物最多,其中含量最高的单酚类物质为4-甲基愈创木酚,在主要单酚类物质中占32.77%,木质素水热解聚液相产物得率随温度升高而先增后减,并在325℃时取得峰值;L1、L2和L3是碱木质素的3个不同的分子级分,L1级分对木质素解聚液相产物得率贡献最大,达61.80%,且产物中单酚类物质总得率最高,为112.71 mg/g。其中,愈创木酚与4-甲基愈创木酚所占比例最高,可分别为35.38和35.52 mg/g;对木质素进行分级分离处理后再进行水热转化反应,有利于液相产物和单酚类物质得率的进一步提高。     

Two-step hydrolysis of Japanese beech as treated by semi-flow hot-compressed water

A two-step hydrolysis of Japanese beech (Fagus crenata) was conducted by semi-flow treatment with hot-compressed water. The first treatment stage was conducted at 230°C/10 MPa for 15 min and the second at 270°C/10 MPa for 15 min. Hemicellulose and lignin were found to be hydrolyzed in the first stage, while crystalline cellulose was hydrolyzed in the second stage. The treatment solubilized 95.6% of the Japanese beech wood flour into water with 4.4% remaining as water-insoluble residue, which was composed mainly of lignin. Hydrolysis products from the first stage were xylose and xylo-oligosaccharides, glucuronic acid and acetic acid from O-acetyl-4-O-methylglucuronoxylan, and hydrolyzed monomeric guaiacyl and syringyl units and their dimeric condensed-type units from lignin. Products from the second hydrolysis stage were glucose and cello-oligosaccharides from cellulose. The dehydrated products levoglucosan, 5-hydroxymethylfurfural (5-HMF), and furfural, as well as fragmented products glycolaldehyde, methylglyoxal, and erythrose, were recovered in the first stage from hemicellulose, and to a greater extent in the second stage from cellulose. Furthermore, organic acids such as glycolic, formic, acetic, and lactic acids were recovered in both stages. Based on these lines of evidence, decomposition pathways of O-acetyl-4-O-methylglucuronoxylan and cellulose are independently proposed.     

桉木循环强化预水解过程中有机酸变化规律

以桉木为原料,将桉木经热水预水解后,将预水解液按不同比例循环回用于桉木的预水解,在桉木粉(8 g)与不同水解介质6∶1(m L∶g)的条件下,探讨了循环强化预水解过程中,主要的有机酸(乙酸、甲酸和乙酰丙酸)及总糖的生成和变化情况。结果表明:反应温度190℃,在不同保温时间下,循环强化预水解液中的甲酸和乙酰丙酸浓度随着保温时间的延长而增加,而乙酸浓度则先增加,后期虽有波动,但是稳定在较高水平,而总糖则呈现先增加后下降的趋势;保温时间60 min,在不同预水解温度下,循环强化预水解液中的有机酸和总糖质量浓度随着预水解温度的升高呈现增加的趋势;在上述两种效应研究中,循环比的增大均对循环强化预水解液中的有机酸质量浓度提升有正面效应。循环强化预水解工艺的水解过程自产酸得以富集,利于其资源化利用,而自产酸具有催化水解进程的功能。     

Determination of formic-acid and acetic acid concentrations formed during hydrothermal treatment of birch wood and its relation to colour, strength and hardness

Formation of benzyl esters from acetic and formic acids during heat treatment of birch at 160–200°C has been studied by gas chromatography. High concentrations of formic and acetic acids formed by the wood itself during hydrothermal treatment were found. The concentrations of acids increased with both treatment time and temperature. The maximum formic- and acetic acid concentrations found at 180°C and after 4 h of treatment performed in this work were 1.1 and 7.2%, based on dry-weight wood, respectively. The treated wood material was characterised by mechanical testing [bending tests perpendicular to the grain, modulus of rupture, modulus of elasticity, Brinell hardness, impact bending and colour measurements (CIE colour space)]. The experiments, where high concentration of acids was formed, showed severe losses in mass and mechanical strength. Indications of possible enhanced mechanical properties for the treated, compared with untreated birch wood were found around 180–200°C at short treatment times. This paper discusses possible degradation reactions coupled with the colour and mechanical properties in relation to acid formation, and suggestions for process optimisations.