摘要
国内外生产微晶纤维素主要以棉花和木材为原料，经制浆工艺分离出纤维素纤维，再进一步提纯得到精制纤维素，即棉浆粕和木浆粕，最后通过酸水解、干燥、粉碎等一系列工艺制得微晶纤维素。由于我国棉花和木材资源匮乏，极大地限制了微晶纤维素的生产规模，且成本较高；另外，目前的生产工艺中半纤维素和纤维素无定形区降解后均被作为废弃物而排放，既污染了环境，又浪费了资源。本课题以资源丰富、成本廉价的小麦秸秆为原料，利用麦草中纤维素和木素化学性质的不同，采用可回收利用的有机溶剂体系热分解麦草，溶解木素，分离出粗纤维素；再经低污染的全无氯精制技术分离残余木素和半纤维素，得到高纯度纤维素；利用纤维素结晶区和无定形区天然聚集态结构的差异，采取了区别利用的思路，通过降解分离高纯度纤维素的无定形区，保留其结晶区用于制备高附加值产品合成革用微晶纤维素，降解的纤维素无定形区转化为葡萄糖可用于发酵制备纤维素乙醇，有效避开了目前生物质利用研究中结晶区可及度低、酶解困难的技术壁垒，实现了纤维素的资源化和能源化共利用。溶解分离出的木素用于改性制备水泥减水剂。从而初步形成农秸秆的多组分、多结构和多产品联产的高值化利用技术体系。既解决了棉花资源的紧缺问题，又充分利用了农业废弃物―小麦秸秆，因此，具有较大的潜在经济价值和社会效益。
本课题研究过程中，采用易回收再利用的乙醇乙酸二元有机溶剂体系热分解麦草，溶解木素，分离获取粗纤维素。乙醇/乙酸溶剂热分解分离麦草的最佳工艺为：乙醇水溶液浓度（v/v）55%，乙酸用量以2%（相对乙醇，v/v）为宜。液比1∶8，最高温度195℃，保温时间为60min；获得的粗纤维素得率和α-纤维素分别为49.84%和83.77%，卡伯值为20.3。
为了提高纤维素纯度，本课题采用臭氧、过氧化氢和木聚糖酶等化学处理和生物技术相结合的全无氯工艺技术进行无污染精制，以获得高纯度的精制纤维素。结果表明，该技术路线对麦草粗纤维素精制效果明显，O3处理有助于残余木素的脱除，H2O2精制段有利于产品白度的提高，而木聚糖酶处理则有效地降低了半纤维素含量，最终达到了精制的要求。其中，O3处理段的最佳工艺为：浆浓为45%，pH为2时，O3处理的最佳用量为1.2%；H2O2精制段的最佳处理条件为：浆浓12%，柠檬酸三钠用量1.0%，H2O2用量为3%，NaOH用量为1.8%，精制温度70℃，处理时间120min。木聚糖酶最佳用量为1.5IU·g-1；精制后纤维素产品的指标为：α-纤维素含量为94.67％,聚戊糖含量为4.29%，白度为86.1％ISO，聚合度为628，结晶度为27.36%，灰分为2.07%。精制纤维素的最终得率为87.31%。
利用纤维素结晶区和无定形区天然结构的差异，研究了盐酸水解技术分离精制纤维素的结晶区。盐酸水解的最佳水解工艺参数为：盐酸浓度2mol/L、最佳固液比1:15、水解温度70℃、水解时间90min。水解纤维素得率为79.68%。为了进一步提高酸水解过程对纤维素无定形区的选择性，本课题探索了过渡金属离子助催化酸水解技术和机理，以获得更高结晶度的水解纤维素。结果表明，Fe3+比Cu2+具有更佳的酸水解催化选择性。其对应的最佳工艺条件为：Fe3+浓度0.4mol/L，盐酸浓度2.5mol/L，反应温度80℃，反应时间55min，固液比1:15。该条件下水解纤维素结晶度可达到81.94%，比无金属离子催化下提高了31.04%，而得率可达到86.89%。其机理为：金属离子催化提高了酸水解速率，促使无定形区更快地被水解，使体系中更多的酸作用在无定形区降解上，作用于结晶区的酸用量则相对减少，使结晶区得到了一定保护。
鉴于麦草原料灰分较大，尤其是SiO2含量较高，本课题采用碱处理除硅技术降低灰分含量，并研究了后续的粉碎工艺。结果表明，此工艺下微晶纤维素灰分含量由2.05%降为0.32%，下降率达84.39%。碱处理最佳工艺条件为：碱用量15%，温度80℃，微晶纤维素浓度10%，处理时间30min。粉碎工艺研究发现，采用行星式球磨机对微晶纤维素的粒度控制较好，在料球比为1:1条件下，最佳粉碎时间为100min，所得微晶纤维素的平均粒径为23.33μm。
采用IR、XRD、SEM-EDS、TGA、激光粒度仪等技术手段对合成革用麦草微晶纤维素的结构和性能进行了表征，并与相关国家行业标准进行比较，完全达到标准的要求。经核工业二〇三所分析检测中心分析鉴定，其各项检测指标均符合中华人民共和国合成革用微晶纤维素林业行业标准（LY/T1333-1999）。对产品进行了实验室应用试验，结果表明，自制麦草微晶纤维素作为PU合成革移膜填料，其透气性、抗张强度和撕裂强度较国产合成革微晶纤维素的使用效果更佳。经昆山华富合成革有限公司生产应用试验证明，自制合成革用微晶纤维素与进口木质微晶纤维素对比，除膨胀率、拉伸负荷（横向）和断裂伸长率（横向）稍低外，其余各项指标均达到甚至超过了进口德国的木质微晶纤维素，较国内中高档合成革用微晶纤维素具有更好的应用效果。
分析相应的PU合成革产品微观结构发现，添加两种国产微晶纤维素的合成革产品断面结构中表层孔隙粗大且数量较多，尤其是国产木质微晶纤维素Ⅱ，但凝聚层中间部分微孔数量很少，结构较致密；添加德国微晶纤维素和麦草微晶纤维素的PU合成革表层部分孔隙较小，但在PU凝聚层中间部位，分布着更多的微孔。对比而言，德国微晶纤维素和自制麦草微晶纤维素添加后更有利于改善PU合成革凝聚层的微观结构，提高了产品的强度和透气性能。
通过蒸馏回收麦草热分解废液中的乙醇后，将析出的木素先进行羟甲基化活化，然后进行了磺化改性，制备出了改性乙醇木素水泥减水剂，并对产品的结构和应用性能进行表征和研究。结果表明，改性乙醇木素水泥减水剂使用效果较佳，水泥减水剂掺量为5%时，水泥净浆流动度可达208mm，减水率为14.9%，比市售木素磺酸钠减水剂高出30.7%；掺加改性乙醇木素的砂浆抗压强度随龄期的增长而下降；其3天抗压强度比比木素磺酸钠高13.8%，7天抗压强度比比木素磺酸钠高9.9%。磺化改性的最佳条件为：磺化剂/木素质量比为1:3，温度为95℃，pH为11，时间3h。
最后，本课题初步探索了酸水解废液和碱处理废液的混合中和发酵技术，以转化其中的葡萄糖为生物质乙醇。酸性废液和碱性废液混合至pH为5.0（酿酒酵母最适宜pH）时，所需酸、碱废液的体积比为2.83：1，此时混合废液中还原糖含量约为20.60g/L。结果表明，还原糖初始浓度越高，乙醇产量越高。混合废液发酵制备乙醇的最佳工艺条件为：酿酒酵母接种量10%，发酵温度34℃，发酵时间72h，pH为5.0。
The major resources for microcrystalline cellulose products are cotton andwood. Cellulose fibers are isolated from the biomass through the pulping process.After purification, refined cellulose is obtained in the form of cotton pulp andwood pulp. Microcrystalline cellulose is produced after acid hydrolysis, drying,grinding, and other process. Due to the shortage of cotton and wood resources inour country, the production scale of microcrystalline cellulose is limitedextremely, and the cost is very high. Besides, the degradation products of theamorphous regions of hemicellulose and cellulose generated in producing processare emitted as litters currently, which are a pollution of environment and a wasteof resources. Wheat straw is a plentiful and cheap resource, is employed as theraw material in this dissertation study. Considered the differences on chemicalproperties of cellulose and lignin of wheat straw, the crude cellulose is firstseparated from lignin using recyclable organic solvent system. The organicsolvent thermally decompose the wheat straw and lignin is dissolved. The highpurity cellulose is obtained using low-pollution TCF refining technology toseparate residual lignin and hemi cellulose. The amorphous regions of high puritycellulose are separated from crystal regions by degradation by considering t thedifferences on the natural aggregation structures of crystal and amorphousregions. The crystal regions from high purity cellulose are used in producesynthetic leather, microcrystalline cellulose, which is a high value-added product.The amorphous regions from high purity cellulose are converted into glucose,which can be used in producing cellulose ethanol by fermentation. The wholeprocess employed in this study fulfills the use of cellulose as and in energy fields.This can be achieved by avoiding current technical barriers of biomass utilization,including low accessibility to crystalline regions and difficulty in enzymatichydrolysis. Lignin separated by dissolving is used in preparation of modifiedcement water reducer. This study helps utilization agricultural wheat straw,including multi-component, multi-structure, and multi-product cogeneration. By this not only the problem of cotton shortage is solved, but the wheat straw, whichis a kind of agriculture waste, is made to full use. Therefore, the process in thestudy has great potential in both economic value and social benefits.
This study take advantage of ethanol-acetic solvent system, which is arecyclable binary organic solvent, to have wheat straw thermally decomposed andlignin is dissolved to get crude cellulose. The optimum process conditions ofethanol-acetic solvent thermal decomposition of wheat straw is that ethanolaqueous concentration is55%(v/v), acetic acid dosage is2%v/v of ethanol,liquid ratio is1:8, the highest temperature is195°C，holing time is60min. Thecrude cellulose yield and α-cellulose content are49.84%and83.77%, and theKappa number is20.3after the treatment.
In order to increase the purity of cellulose, this study uses the Chlorine-freeand non-polluting process, which is a combination of ozone, hydrogen peroxide,and xylanase treatment, to obtain high purity cellulose. The results show that theprocessing of wheat straw to refine crude cellulose is excellent by following thistechnology. O3treatment is helpful in removing of residual lignin. H2O2refiningis useful in enhancement of whiteness. The xylanase treatment reduces thecontents of hemi cellulose efficiently. The final result of refining meets therequirement. The optimum process conditions of O3treatment are that pulpconcentration is45%, pH is2, and O3dosage is1.2%. The optimum processconditions of H2O2treatment are that pulp concentration is12%, tri-sodiumcitrate dosage is1.0%, H2O2dosage is3%, NaOH dosage is1.8%, refiningtemperature is70°C, and treatment time is120min. The optimum xylanasedosage is1.5IU·g-1. The parameter of refined cellulose are that α-cellulosecontent is94.67%, Pentosan content is4.29%，whiteness is86.1%ISO, degree ofpolymerization is628, crystallinity is27.36%, ash content is2.07%. The yield ofrefined cellulose is87.31%.
The study on separation and refining of cellulose amorphous region usinghydrochloric acid hydrolysis technology is carried out based on the differences onthe natural structures of crystal and amorphous regions of cellulose. The optimumprocess conditions of hydrochloric acid hydrolysis are that HCl concentration of2mol/L, solid and liquid ratio is1:15, hydrolysis temperature is70°C, and hydrolysis time is90min. The cellulose yield after hydrolysis is79.68%. In orderto enhance the selectivity of acid hydrolysis to cellulose amorphous regions, thisstudy explore the technology and mechanism of transition metal ion assistedcatalytic acid hydrolysis with the purpose of getting hydrolyzed cellulose withhigher crystallinity. The results show that Fe3+has higher selectivity of acidhydrolysis than Cu2+. The optimum process conditions are that Fe3+concentrationis0.4mol/L, HCl concentration is2.5mol/L，reaction temperature is80°C,reaction time is55min, solid and liquid ratio is1:15. In this condition, thecrystallinity of hydrolyzed cellulose can reach81.94%, which is31.04%higherthan acid hydrolysis without the co catalysis of metal ions. The yield is86.89%.The mechanism is that metal ion catalysts increase the rate of acid hydrolysis,and promote the hydrolysis of amorphous regions. It results in most of the acid inthe system is consumed by degradation of the amorphous regions rather than onthe crystal regions, which protect the crystal regions to some extent.
In consideration that wheat straw has high ash content, especially high SiO2content, this study try to reduce ash content using base treatment of silicon, anddoes some research on subsequent grinding process. The results show that ashcontent of microcrystalline cellulose is reduced from2.05%to0.32%, which is areduction of84.39%using this process. The optimum process conditions of basetreatment are that base dosage is15%, temperature is80°C, microcrystalcellulose is10%, and the treatment time is30min. The study of grinding processshows that the granularity of microcrystalline cellulose can be controlledefficiently by using a planetary ball mill. The optimum grinding time is100minin condition that the pellet ratio is1:1. The average particle size obtainedmicrocrystalline cellulose is23.33μm.
The characterizations of wheat straw microcrystalline cellulose are carriedout using IR, XRD, SEM-EDS, TGA, and laser particle size analyzer. The resultsare in agreement with certain national standard accurately. After the appraisalfrom analysis testing center of No.203Nuclear Industry Research Institute, allthe parameters met the requirements of Chinese forestry industry standards ofsynthetic leather microcrystalline cellulose (LY/T1333-1999). The obtainedwheat straw microcrystalline cellulose undergoes application test. The results show that the permeability, tensile strength, and shear strength of homemadewheat straw microcrystalline cellulose as shift membrane packing of PUsynthetic leather is better than other synthetic leather microcrystalline cellulosemade in China. After the test from Huafu synthetic leather Co., Ltd. in Kunshan,expansion ratio, the tensile load (transverse), and fracture elongation (transverse)of homemade synthetic leather of microcrystalline cellulose are slightly lowerthan lignin microcrystalline cellulose from imports. However, the othercharacteristics are better than the lignin microcrystalline cellulose from Germany.The homemade synthetic leather of microcrystalline cellulose has better qualityand can be used in different applications than the domestic synthetic leather ofmiddle and top grade.
The analysis of the microstructure of PU synthetic leather product showsthat sectional structure of synthetic leather, which is added with domesticmicrocrystalline cellulose, has a large number of coarse pores on the surface,especially for the domestic lignin microcrystalline cellulose II. But the middlepart of the coacervate contains a small amount of the pores, and has a densestructure. PU synthetic leathers added with microcrystalline cellulose fromGermany and wheat straw microcrystalline cellulose have smaller pores on thesurface, but more micropores in the middle part of the coacervate. Therefore,microcrystalline cellulose from Germany and homemade wheat strawmicrocrystalline cellulose are helpful with the improvement of the coacervatemicrostructure of PU synthetic leather, which results in the enhancement ofstrength and permeability.
The liquid waste solution of wheat straw thermal decomposition is distilledto collect ethanol. The precipitated lignin from the liquid waste undergoeshydroxymethyl activation and sulfonation. The structures and properties ofobtained modified ethanol lignin cement water reducer are characterized andstudied. The results show that ethanol lignin cement water reducer has goodresults. Cement paste fluidity reaches208mm when5%of cement water reduceris added. The water reduction rate is14.9%in this situation, which is30.7%higher than sodium lignosulphonate water reducer that has been used currently.The compressive strength of mortar mixed with modified ethanol lignin decreases with the growth age. The3-day and7-day compressive strength ratio of mortar is13.8%and9.9%higher than mortar mixed with sodium ligninsulfonate separately.The optimum sulfonation conditions are that weight ratio of sulfonation agent andlignin is1:3, the temperature is95°C, pH is11, and the time is3h.
At last, this study explores the conversion of glucose into biobased ethanolby using mixed-neutralizing fermentation technology from the waste liquid fromacid hydrolysis and alkaline treatment. The pH of the mixture of acid and alkalinewaste liquids reaches5.0(the most suitable pH for Saccharomyces cerevisiae),when the volume ratio of waste acid and alkaline is2.83:1. In this condition,reducing sugar content in the mixed waste liquid is around20.60g/L. It showsthat the higher the concentration of reducing sugar, the higher the ethanolproduction. The optimum process condition of ethanol producing fromfermentation of mixed waste liquid and the amount of yeast inoculation is10%,fermentation temperature is34°C, fermentation time is72h, and the pH is5.0.
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