木质纤维素类生物质高温液态水预处理技术

木质纤维素燃料乙醇是可再生能源的重要组成部分,其中可发酵糖的制取技术是木质纤维素乙醇化的关键技术之一。原料经过预处理后再进行酶解被认为是最有前景的糖化方式。高温液态水预处理技术与其它方法相比显示了独特的优势,如不需添加化学试剂、降解产物少等。本文在总结了高温液态水性质的基础上,对它在生物质预处理过程中各组分(半纤维素和木质素)的水解过程及机理进行了较详细的综述和分析。最后对高温液态水预处理技术在木质纤维素糖化领域中的研究和应用前景进行了展望。     

高温液态水预处理木质纤维素

介绍了高温液态水的物化性质,对木质纤维素在高温液态水预处理过程中的溶解情况及半纤维素水解的影响因素、机理进行了较详细的综述和分析,简述了纤维素的水解过程,指出选择高温液态水预处理工艺应综合考虑木质纤维素的种类与酶水解效果,进一步探讨了半纤维素的高温液态水水解机理,以指导和控制预处理过程。     

木质纤维原料蒸汽爆破-生物联合预处理及其生物脱毒研究进展

在木质纤维素类生物质结构中,木质素是生物质中纤维素与半纤维素进行生物降解的天然抗性屏障,预处理是打破木质纤维素抗性结构这一阻碍生物转化与利用瓶颈的最主要途径。本文分别概述了木质纤维素蒸汽爆破预处理技术与生物预处理技术的研究现状,介绍了蒸汽爆破-生物联合预处理的研究进展,分析了蒸汽爆破预处理过程中抑制物产生的机理和主要抑制物的种类,并提出了具有脱毒效果的蒸汽爆破-生物联合预处理技术,以及木质纤维素高效预处理技术研究发展方向。     

Hydrolysis of sweet sorghum bagasse hemiceilulose with liquid hot water and its mechanism

引 言木质纤维素类生物质的生化转化过程包括预处理过程、水解液发酵过程和产物分离过程,而预处理过程是减少整个生化转化成本和提高生化转化效率的关键[1-3].与其他预处理方法相比,高温液态水处理(liquid hot water)(温度在170～250℃,压力高于饱和蒸气压)是一种绿色处理方法,它可以将木质纤维素类生物质中的半纤维素转化为木糖及其低聚糖,同时提高了残渣的纤维素酶解效率[4-7].该糖化工艺由于产生发酵毒性副产物少、不需要添加任何化学试剂、设备成本低等优点而受到广泛关注[8-12].就目前国内外相关报道来看,高温液态水预处理研究大都采用间歇(batch)搅拌反应器,该反应器的缺陷是反应中生成的糖类不能被及时排出从而被进一步降解.浙江大学吕秀阳等[13-16]主要针对葡萄糖、木糖、果糖和纤维素等在高温液态水中的水解动力学进行了深入研究,而针对真实生物质中的半纤维素水解机理报道比较少.     

木质纤维素乙醇原料预处理技术的研究进展

近十年来,随着石油价格的上涨以及化石燃料使用对全球变暖的影响,利用木质素纤维素制取燃料乙醇日益成为国内外研究的热点。木质纤维素制取乙醇的主要步骤包括:原料的预处理、纤维素的糖化、发酵、产品分离。木质纤维素的组成包括木质素、半纤维素和纤维素,其中木质素和半纤维素对纤维素的水解具有阻碍作用。因此,在木质纤维素制取乙醇的工艺过程中,原料的预处理是非常关键的步骤,影响整个木质纤维素乙醇的生产过程。文章回顾了木质纤维素原料主要的预处理技术的最新进展,并结合后续的水解与发酵工序,对各种预处理技术的优缺点进行了对比。     

甘蔗渣木质素的结构及其对纤维素酶解的影响

对甘蔗渣有机酸预处理、碱处理和氧化预处理过程中得到的5种木质素[乙酸木质素(AAL)、Acetosolv木质素(As L)、Milox木质素(ML)、过氧乙酸木质素(PAAL)和碱木质素(AL)]进行了结构表征,通过元素、官能团和化学组分分析、分子量测定及光谱特性分析,验证了甘蔗渣木质素为典型的H-S-G型木质素,除PAAL外其余4种木质素具有类似的结构特性,而PAAL由于过氧乙酸的氧化作用使木质素结构显著变化,从而具有较低的分子量、较高的酸溶木质素和羰基含量.将5种木质素添加至纤维素酶催化水解体系中,纤维素转化率均有不同程度降低,PAAL的抑制作用最强.结合添加木质素单体模型化合物的实验表明,酚羟基是木质素抑制纤维素酶作用的关键官能团,对羟苯基中酚羟基的抑制作用比愈创木基和紫丁香基更强.木质素对纤维素酶解的抑制作用不只是通过无效吸附纤维素酶实现,小分子的酚类降解产物也会降低纤维素的酶解转化效率.     

有机酸及多元醇类低共熔溶剂预处理木质纤维素研究进展

综述了一种新型绿色低共熔溶剂(Deep Eutectic Solvents, DES)预处理木质纤维素的研究进展。DES具有价格低廉、毒性小、易生物降解和易合成等优势,用于木质纤维素预处理可以在保留纤维素的同时,选择性去除木质素和半纤维素,极大提高后续纤维素酶解过程中的糖化率。重点介绍了有机酸和多元醇类DES预处理木质纤维素、不同DES预处理效果比较以及这两大类DES组合其他预处理等方面取得的研究进展,并对DES预处理机理及构效关系、DES循环使用、DES木质素的分离及高值化利用做了展望。     

蒸汽爆破预处理对沙柳组成及纤维结构性能影响研究

研究了蒸汽爆破维压时间对沙柳茎杆化学组成和酶解糖化率的影响,并采用扫描电镜(SEM)、X射线衍射仪和红外光谱(IR)对沙柳纤维物理形态、结构和性能进行了表征.结果表明蒸汽爆破处理对纤维素、木质素含量影响小显著,而半纤维素含量人幅度降低.蒸汽爆破预处理后沙柳纤维表面和细胞壁受到不同程度的破裂,蒸汽爆破纤维素表观结晶度比原料纤维素有所提高,但其绝埘结晶度降低.酶解糖化反应温度46℃、反应时问72 h、酶用最20 FPU/(g纤维素)和底物浓度为2.0%时,沙柳攀杆原料酶解糖化率为14.5%,蒸汽爆破维压4 min处理的沙柳物料糖化率达到69.81%,纤维素糖化率提高4.4倍,蒸汽爆破是一种有效的木质纤维预处理方法.     

低共熔溶剂预处理杨木水解渣拆解木质素

为高效去除木质纤维素中的木质素,获得富含纤维素的底物,实现木质纤维素组分的单一分离与组分全利用,制备合成了6种三元低共熔溶剂（deep eutectic solvent, DES）,利用DES预处理已去除半纤维素的杨木水解渣,研究了6种低共熔溶剂对木质素去除和纤维素保留的影响,并优化获得了最佳的预处理工艺参数。结果表明,6种DES中苄基三乙基氯化铵-乙二醇-氯化铁（T-EG-Fe）的预处理效果最优,木质素去除率为80.46%,纤维素保留率为90.81%。优化得到T-EG-Fe预处理杨木水解渣最佳工艺条件为：反应固液比为1∶15,反应温度为130℃,反应时间为5h,在最优条件下预处理得到的固体残渣中纤维素质量分数为92.78%,木质素质量分数为5.33%。T-EG-Fe具有高效拆解木质素的潜力,在木质纤维素预处理过程中具有一定的应用价值。     

过氧甲酸预处理对甘蔗渣酶解和发酵的影响

以甘蔗渣(SCB)为原料, 经过氧甲酸(PAP)预处理后加入酶进行水解, 并以水解液发酵产乙醇, 考察预处理时过氧化氢(HPP)浓度变化对甘蔗渣酶解和乙醇得率的影响。实验结果表明: 在甘蔗渣PAP预处理过程中, HPP与甲酸(FAP)体积比为1∶1时, 预处理甘蔗渣(PAP-SCB-1)的木质素脱除率达84.30%;在纤维素酶用量为10 FPIU/g(以预处理后的甘蔗渣质量计)时, PAP-SCB-1水解72 h葡萄糖得率为98.71%, 较单独过氧化氢预处理甘蔗渣(HPP-SCB, 葡萄糖得率9.11%)和单独甲酸预处理甘蔗渣(FAP-SCB, 葡萄糖得率7.06%), 分别提高了9.84和12.98倍; PAP-SCB-1水解液经24 h发酵后, 乙醇得率为84.06%, 比HPP-SCB(76.20%)和FAP-SCB(75.15%)均有增加。对预处理前后物料的化学成分变化、比表面积和结晶度进行测定, 结果显示: 经PAP预处理后可以显著脱除甘蔗渣中的木质素, 木质素的量由未经预处理的21.27%降低到10%以下; 比表面积和结晶度都有提高, PAP-SCB-1的比表面积和结晶度分别为13.01 m²/g和54.18%, 是HPP-SCB的10.66和1.11倍, FAP-SCB的11.39和1.15倍。     

蔗渣闪爆处理及其黄原酸化物的制备和应用

采用热蒸汽适度闪爆及稀碱洗涤等预处理技术对蔗渣进行纯化和活化,利用处理后的蔗渣纤维素合成纤维素基黄原酸酯,对其在水处理中的应用进行了研究。研究优化了闪爆处理的工艺条件,并采用IR、SEM和化学分析技术对闪爆前后蔗渣纤维的形态、结构、a-纤维素的含量进行了分析,对处理前后的蔗渣纤维的碱化和黄原酸化合成条件进行了优化。结果表明,闪爆预处理技术是一种便宜、迅速、无污染的技术,蔗渣纤维素基黄原酸酯对含金属离子的污水有良好的处理效果。     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 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     

Evaluation of the effects of operational parameters in the pretreatment of sugarcane bagasse with diluted sulfuric acid using analysis of variance

The pretreatment of lignocellulosic residues has been extensively studied as a method to disrupt the cellulose–hemicelluloses–lignin complex in biomass to access the sugars in their respective components. In this work, we carried out a study using sulfuric acid pretreatment of sugarcane bagasse by varying the following operational parameters: solid loading (10–30% of bagasse relative to the volume of the sulfuric acid solution), sulfuric acid concentration (0.5–2.5% relative to the dry mass of bagasse), reaction time (5–25?min), and temperature (135–195°C). The obtained solids from each pretreatment condition were submitted to enzymatic hydrolysis under the same process conditions: 0.232?g of Celluclast 1.5?L and 0.052?g of Novozym 188 per g of pretreated sugarcane bagasse, 72?h of hydrolysis, and 200?rpm of agitation at 50°C. Using central composite rotational design configuration in the experiments and analysis of variance, the results indicate that the conditions that produced larger quantities of glucose by enzymatic hydrolysis (0.35?g glucose/g pulp) with minimum amounts of degradation products were as follows: 20% solids loading, 15?min of reaction time, 1.5% sulfuric acid, and a minimum temperature of reaction of 170°C.     

Determination of Sugarcane Bagasse Lignin S/G/H Ratio by Pyrolysis GC/MS

Abstract

In this work, analytical pyrolysis (Py-GC-MS) was employed to identify lignin markers derived from H, S, and G phenylpropanoid units in sugarcane bagasse. Temperatures of 450 and 500°C allowed the detection of key products that were informative on the bagasse lignin composition. The method was validated by comparing the S/G ratio as determined by the nitrobenzene oxidation (NBO) standard method for five sugarcane varieties. The S/G ratio as determined by Py-GC-MS, taking into consideration all known lignin markers in the analysis, resulted in a correlation coefficient of 0.85 with a linear regression coefficient of 0.74. When a group of selected markers (M2) was used, the correlation coefficient between methods was improved to 0.95 and the linear regression coefficient was adjusted to 0.92. M2 markers consisted of five syringyl markers (syringol, 4-methylsyringol, 4-ethylsyringol, 4-vinylsyringol, and trans-4-propenylsyringol) and four guaiacyl markers (guaiacol, 4-vinylguaiacol, 4-methylguaiacol, and vanillin). Importantly, Py-GC-MS allowed for the study of lignin composition in sugarcane bagasse without the need to remove the extractives, minimizing the work with sample preparations.     

Evaluation of technological alternatives for process integration of sugarcane bagasse for sustainable biofuels production—Part 1

Nowadays, there is a tremendous global interest in the biofuels production. However, first generation biofuels have been debated about that energy-crop compete with food crops and thus cause food deficiency and price increases. In this sense, researchers have started looking for potential feedstock for ethanol such as lignocellulosic biomass (e.g., sugarcane bagasse), which does not affect food security. In this paper, the integrated use of sugarcane bagasse is analyzed as raw material for second generation of biofuels production. This case study implements a design and process integration to compare several biorefinery topologies using the typical mass flow rate of residual biomass produced by the sugar industry (1200 ton per day). Based on evaluation of chemical composition of bagasse (cellulose, hemicellulose, and lignin) several process schemes for integral utilization of biomass were proposed. This paper is the first part of the study on the exergy, life cycle analysis (LCA) and economic analysis of sugarcane bagasse for sustainable biofuels production using Aspen Plus™ software. Part 1 presents the exergy and life cycle analysis developed while part 2 describes economic analysis and selection of an optimal configuration with minimal environmental impact, by means of the combined use of raw material and energy integration.     

Effect of LHW,HCl, and NaOH pretreatment on enzymatic hydrolysis of sugarcane bagasse: sugar recovery and fractal-like kinetics

Conversion of lignocellulose to sugars involves two main processes, namely pretreatment and enzymatic hydrolysis. Lignocellulose pretreatment leads to the degradation of enzymatic recalcitrance of substrate for achieving efficient saccharification. In this study, liquid hot water (LHW), hydrochloric acid (HCl), and sodium hydroxide (NaOH) were as reagents used to pretreat sugarcane bagasse (SB). Results showed that LHW, HCl, and NaOH pretreatment could solubilize 95.3%, 94.7% xylan and 88.7% lignin, respectively. Enzymatic hydrolysis of pretreated SB showed that the maximum glucose (26.0?g/L) and xylose (12.7?g/L) concentration were produced by NaOH pretreatment, and slightly more glucose and less xylose were produced after HCl pretreatment compared to LHW pretreatment. Addition of Tween 80 or xylanase could significantly improve both glucose and xylose production. At 48?h, the glucose increase for LHW, HC1 and NaOH pretreatment was 38.3%, 26.4% and 8.0%, respectively, and the xylose increase for them was 35.0%, 24.9% and 1.7%, respectively. Fractal-like kinetics showed that the value of rate constant increased after the addition of Tween 80 or xylanase, and the efficiency of enzymatic hydrolysis mainly depended on rate constant other than fractal dimension of substrate. Totally, substrate accessibility was dominated for efficient of lignocellulose to sugar compared to enzyme loading. The application of fractal-like theory on the heterogeneous enzymatic hydrolysis of lignocellulose was quite successful.     

甘油预处理蔗渣的木质素分离提取及结构表征

以甘油分别对甘蔗渣进行常压甘油自催化（AGO）预处理和常压甘油碱催化（al-AGO）预处理。利用酸沉法分别从预处理液中得到自催化甘油木质素（AGOL）和碱催化甘油木质素（al-AGOL）。利用单因素实验和正交实验得到最佳木质素提取工艺为转速8000r/min、离心时间15min、甘油混合液pH为3、甘油混合液浓度10%，在该条件下木质素AGOL和al-AGOL提取率分别达到72%和76%。采用扫描电镜（SEM）、元素分析、紫外光谱（UV）、凝胶色谱（GPC）、核磁共振¹H谱、热重分析以及抗氧化活性分析等技术手段对提取得到的木质素进行结构表征。结果表明：从甘蔗渣中提取的球磨甘蔗木质素（MBL）、AGOL和al-AGOL主要呈现出球形特征；AGOL和al-AGOL具有相似的活性特点，与MBL相比，AGOL和al-AGOL的分子量更小、分布更窄、均一性更好，热稳定性和抗氧化活性更高，有望成为重要的工业原料。     

蔗渣纤维素乙醇的预处理技术研究进展

从蔗渣的物化特性及预处理的必要性出发,综述了近年来国内外预处理蔗渣方面发展的不同技术途径(包括物理法、化学法、生物法和联合法)及其研究进展,对各种技术的作用效果和特点进行了总结和对比分析,并对蔗渣预处理技术的发展方向予以展望。蔗渣作为糖厂的主要副产物,具有量大、集中且纤维含量高等特点,是生产第二代生物乙醇的重要潜在原料之一,对其进行有效预处理是利用其制取生物乙醇的关键,直接影响着后续的酶解糖化和乙醇发酵效果。