生物質高效水解制取生物汽油和丁醇新技術研究報告

馬隆龍 王鐵軍 陳新德 章青 張素平

摘 要：該報告通過開展木質纖維素高溫液態水-超低酸與酶高效水解技術、丙酮丁醇發酵技術及烷烴水相重整制備技術的研究，探索了不同工藝條件對纖維素轉化率、糖產率、發酵抑制物生成量等影響，并建立了相應的數學模型。采用紫外誘變和化學誘變法研究和選育出具有較高耐受性、高轉化率的己糖和戊糖共發酵丙酮丁醇梭菌，確定丙酮丁醇梭菌發酵的工藝條件。開發研制出高性能復合分子篩負載型水相重整鎳基催化劑，探索出葡萄糖、木糖的水相催化轉化工藝，并對水相重整的關鍵參數進行優化；設計建成了年產450t/年生物汽油和燃料丁醇的生產示范中試系統，探索了水解裝置、丁醇丙酮發酵裝置與生物汽油生產裝置之間的偶聯集成，并對系統進行了調試運行。在水解和發酵中試系統的運行階段，半纖維素水解率達到90%以上，纖維素水解率達到80%以上，水解液中總糖濃度達3%～10%；戊糖、己糖轉化率均大于86%，總糖轉化率為87%。對水解液經復合吸附劑脫毒和丙酮丁醇梭菌發酵后，產品中丁醇比例大于65%，最終總產品濃度達到2.2 wt.%，丁醇濃度達到1.4 wt.%。而在水相重整制取生物汽油系統運行階段，總碳轉化率維持在85%左右；產物中C5、C6的選擇性在80-90%之間，其中異構烷烴所占比例約為20%，催化劑連續使用72 h活性未見下降。

關鍵詞：木質纖維素 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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