糠醇非均相自身缩合扩链及加氢脱氧制运输燃料的反应规律研究

Furfuryl alcohol is abundant biorefinery platform chemical resources in our country which original from straws, wood branches and other agricultural or forestry waste resources. It is important for energy security and environmental protection to search new technologies for the conversion of the lignocellulosic biomass to diesel and/or jet fuels. But Furfuryl alcohol only five carbon, oxygen containing 33%, A novel strategy is development in this application for lignocellulosic biomass catalytic conversion into alkanes: Alkanes with the number of carbon atoms ranging from C5 and C25 are selectively produced from biomass-derived furfuryl alcohol by acid-catalyzed dehydration condensation in heterogeneous systems, which is followed by hydrogenation/ deoxygenation reaction to transfer the multi-furan rings compounds to transportation alkanes. This application project is focus on studying the relevant carbon-carbon bond formation and subsequent hydrogenation /deoxygenation reaction problems of this catalytic process route mentioned above.Through the studying of the main effecting options of self-condensation reaction of furfuryl alcohol in aqueous phase, the relationship between water-furfuryl alcohol-acid reactive system and carbon number distribution of hydrophobic condensation product could be identificated. Then the kinetics model of furfuryl alcohol self-condensation process will be established to describe the condensation product distribution, which could be used to control the distribution and proportion of C5-C25 condensation product. Further, the subsequent hydrogenation reaction conditions of condensation intermediates would be studied, the furan ring double bond hydrogenation, the open-loop, catalytic hydrogenation /deoxygenation reaction mechanism will be explored, as well as the efficient, non-precious metal hydrogenation catalysts will be synthesized for the condensate product upgraded to produce C5-C25 alkanes. On this basis, the whole process pathways could be gotten through initially by integrating the upstream and downstream of this process of biomass via furfuryl alcohol to produce C5+ hydrocarbons.

糠醇是我国优势的生物基化合物，源于秸秆和林木枝杈等农林废弃物，用它生产柴油和喷气燃料对我国能源安全和环境保护具有重要意义。但是糠醇只有5个碳，含氧33%，我们提出创新的思路扩链，并通过创新的非均相缩合反应控制分子量，得到C5-C25多呋喃环化合物、经加氢脱氧后获得碳数分布符合传统运输燃料要求的烷烃。 本申请主要研究这条催化工艺路线糠醇扩链和脱氧问题。研究水相/有机相糠醇缩合扩链的反应规律和主要影响因素，建立水-糠醇-酸反应体系与疏水缩合产物碳数分布的关联，构建描述缩合产物分布的动力学模型，控制糠醇缩合物中C5-C25的分布与比例；并研制高效、非贵金属加氢脱氧催化剂,研究缩合物催化加氢制烷烃反应规律，探索呋喃环双键加氢、开环、并进一步脱氧催化作用机理；在此基础上，整合生物质糠醇法生产C5+烷烃这条路线上下游工艺，初步打通木质生物质经糠醇生产第二代生物柴油的工艺流程。

有机小分子C-C链的高效延长方法是化学合成和化学工业关键的科学问题，尤其是以纤维素和半纤维素为主体的木制生物质，解聚以后的单体碳数只有5或6，需要高选择性的延长碳链到8-25的范围，才能符合传统运输燃料汽柴油的需要。.针对这一具有普遍意义和应用前景的科学问题，本项目开发了廉价、常用的无机质子酸催化糠醇的自身缩合扩链的技术方法，建立了复杂反应体系中较大分子量有机产物的结构表征和定量分析方法，测定了反应级数和速率常数、活化能等参数，建立了动力学方程，探索了缩合反应机理，实现了可控缩合反应， C5-C25产物的选择性从研究初期的30%左右，提升到75%。.含氧有机物的加氢脱氧也是具有普遍意义的科学问题，温度过高分子链容易断裂，温度过低影响氧的脱除率。关键是开发高效催化剂和相应的工艺路线。本项目开发了镍基负载β型分子筛催化剂，可以达到贵金属Pd的催化效果。在研究对比二步法和一步法加氢脱氧工艺的基础上，最终确定固定床一步法加氢脱氧工艺，采用雷尼镍和M/HZSM-5复合型催化剂，实现了缩合物固定床一步法加氢生产运输燃料所需的烃类成分，脱氧率95%。初步打通了由木质生物质经糠醛、糠醇平台化合物，化学催化法生产汽柴油和喷气燃料的技术路线。.上述两项重点工作都以论文形式发表，并获得了国家授权发明专利。这些研究成果不仅丰富了碳氢氧有机物C-C扩链方法，也初步打通了拥有自主知识产权的秸秆生物质化学催化法生产运输燃料的技术路线，为生物质资源高效利用和能源安全提供支撑。