生物质高效水解制取生物汽油和丁醇新技术研究报告

马隆龙 王铁军 陈新德 章青 张素平

摘 要：该报告通过开展木质纤维素高温液态水-超低酸与酶高效水解技术、丙酮丁醇发酵技术及烷烃水相重整制备技术的研究，探索了不同工艺条件对纤维素转化率、糖产率、发酵抑制物生成量等影响，并建立了相应的数学模型。采用紫外诱变和化学诱变法研究和选育出具有较高耐受性、高转化率的己糖和戊糖共发酵丙酮丁醇梭菌，确定丙酮丁醇梭菌发酵的工艺条件。开发研制出高性能复合分子筛负载型水相重整镍基催化剂，探索出葡萄糖、木糖的水相催化转化工艺，并对水相重整的关键参数进行优化；设计建成了年产450t/年生物汽油和燃料丁醇的生产示范中试系统，探索了水解装置、丁醇丙酮发酵装置与生物汽油生产装置之间的偶联集成，并对系统进行了调试运行。在水解和发酵中试系统的运行阶段，半纤维素水解率达到90%以上，纤维素水解率达到80%以上，水解液中总糖浓度达3%～10%；戊糖、己糖转化率均大于86%，总糖转化率为87%。对水解液经复合吸附剂脱毒和丙酮丁醇梭菌发酵后，产品中丁醇比例大于65%，最终总产品浓度达到2.2 wt.%，丁醇浓度达到1.4 wt.%。而在水相重整制取生物汽油系统运行阶段，总碳转化率维持在85%左右；产物中C5、C6的选择性在80-90%之间，其中异构烷烃所占比例约为20%，催化剂连续使用72 h活性未见下降。

关键词：木质纤维素 酶高效水解 水相催化

Abstract：This report mainly covers the researches on the efficient hydrolysis technologies of biomass by hot water and ultra low acid combining with enzymes， acetone -butanol fermentation， and liquid alkanes production via aqueous phase reforming. Meanwhile， the effects of different reaction parameters on the conversion of cellulose， the yield of sugars， and the generation of fermentation inhibitors were studied in detail as well as the establishment of the relative mathematical models. A good clostridium acetobutylicum for hexose and pentose fermentation was breed by using UV mutagenesis and chemical mutagenesis， and the optimum processing conditions was also determined. In addition， supported Ni-based catalysts with high catalytic performance for aqueous phase reforming of biomass were developed， and the process for the conversion of glucose and xylose into liquid alkanes was explored， accompanying with the optimization of the key technical process. A pilot plant with annual capacity of 450 tons of bio-gasoline and butanol was designed and built well. The integrated coupling technology among the hydrolysis units， acetone - butanol fermentation devices， and bio-gasoline production equipments was investigated particularly. In the hydrolysis and fermentation test runs of the system， the hydrolysis rate of hemicelluloses and cellulose was found to be higher than 90%， and 80%， respectively， and the total concentration of sugars was obtained in the range from 3% to 10%. The conversion of pentose or xylose both exceeded 86% and the conversion of total sugars was higher than 87%. The content of butanol could be obtained above 65% by a series of detoxifcation and acetobutylicum fermentation of the hydrolysate， and the final concentration of alcohol was 1.4 wt%. In the runs of aqueous phase reforming of sugars， the total carbon conversion was achieved 85% and the selectivity of C5-C5 alkanes was remained 80-90% of which 20% was isoparaffins. The catalyst showed a good stability for bio-gasoline production and no obvious deactivation was observed even after 72 h reaction in the process.

Key Words：Lignocellulose；Enzymatic Hydrolysis；Aqueous Phase Reforming

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