生物質(zhì)高效水解制取生物汽油和丁醇新技術(shù)研究報(bào)告

馬隆龍 王鐵軍 陳新德 章青 張素平

摘 要：該報(bào)告通過(guò)開(kāi)展木質(zhì)纖維素高溫液態(tài)水-超低酸與酶高效水解技術(shù)、丙酮丁醇發(fā)酵技術(shù)及烷烴水相重整制備技術(shù)的研究，探索了不同工藝條件對(duì)纖維素轉(zhuǎn)化率、糖產(chǎn)率、發(fā)酵抑制物生成量等影響，并建立了相應(yīng)的數(shù)學(xué)模型。采用紫外誘變和化學(xué)誘變法研究和選育出具有較高耐受性、高轉(zhuǎn)化率的己糖和戊糖共發(fā)酵丙酮丁醇梭菌，確定丙酮丁醇梭菌發(fā)酵的工藝條件。開(kāi)發(fā)研制出高性能復(fù)合分子篩負(fù)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(zhuǎn)化工藝，并對(duì)水相重整的關(guān)鍵參數(shù)進(jìn)行優(yōu)化；設(shè)計(jì)建成了年產(chǎn)450t/年生物汽油和燃料丁醇的生產(chǎn)示范中試系統(tǒng)，探索了水解裝置、丁醇丙酮發(fā)酵裝置與生物汽油生產(chǎn)裝置之間的偶聯(lián)集成，并對(duì)系統(tǒng)進(jìn)行了調(diào)試運(yùn)行。在水解和發(fā)酵中試系統(tǒng)的運(yùn)行階段，半纖維素水解率達(dá)到90%以上，纖維素水解率達(dá)到80%以上，水解液中總糖濃度達(dá)3%～10%；戊糖、己糖轉(zhuǎn)化率均大于86%，總糖轉(zhuǎn)化率為87%。對(duì)水解液經(jīng)復(fù)合吸附劑脫毒和丙酮丁醇梭菌發(fā)酵后，產(chǎn)品中丁醇比例大于65%，最終總產(chǎn)品濃度達(dá)到2.2 wt.%，丁醇濃度達(dá)到1.4 wt.%。而在水相重整制取生物汽油系統(tǒng)運(yùn)行階段，總碳轉(zhuǎn)化率維持在85%左右；產(chǎn)物中C5、C6的選擇性在80-90%之間，其中異構(gòu)烷烴所占比例約為20%，催化劑連續(xù)使用72 h活性未見(jiàn)下降。

關(guān)鍵詞：木質(zhì)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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