草本能源植物培育及催化制备先进液体燃料

马隆龙 刘琪英

摘 要：研究前两年围绕3个关键科学问题开展，取得的进展如下：（1）针对关键科学问题1，围绕解析能源高粱等能源植物能源物质组成和结构，能源物质生物合成及抗逆相关基因的功能和作用机制开展研究，提出了高粱等能源植物中次生细胞壁生物合成调控网络的解析机理；阐明了抗逆性相关基因的功能和作用机制；建立了检测技术平台以及种质遗传多样性的评价体系与方法。（2）针对关键科学问题2，揭示了生物质大分子水热解聚为糖类衍生物的反应机理及产物选择性调控规律；深入解析了酸/碱处理木质素的结构特征，构建了碱溶出木质素过程的动力学模型；提出了微波在木质素氧化与液化解聚过程中的协同促进机制，获得较高的单酚收率。（3）针对关键科学问题3，围绕解聚产物制氢、糖类衍生物制液体烃类/含氧燃料和酚类衍生物制液体烷烃燃料，进行了深入系统地研究。根据Gibbs自由能最小化原理建立了模拟流程，阐明了葡萄糖水溶液的水热气化模型与反应途径。设计制备了高效的Ni/CeO2-Al2O3和Ni/TiO2催化剂，并对其结构与化学性质进行深入分析，该类催化剂在葡萄糖水热制氢反应中的产氢率超过90%，具有较好的稳定性。首次发现了mdtB基因对细菌的抗逆性、生长速率和产氢速率具有重要的影响。创制了强化水相传质与相转移的微液膜反应体系，实现糖类衍生物一步高效转化为平台化合物HMF与C5/C6糖醇；研制了高水热稳定的功能化纳米碳及金属酸性盐催化体系，提高了选择性断键性能；研制了高效过渡金属/介孔-微孔固体酸复合催化体系，揭示了糖醇水相催化合成液体烃燃料的转化机理与产物控制规律；初步建立了糖类衍生物水相催化合成液体烃类燃料的中试验证系统。发展了多种新型的催化剂体系，可协同转化纤维素和半纤维素，实现了糖类衍生物到平台分子（糠醛，HMF和乙酰丙酸）的高效转化，揭示了上述转化过程的反应机理与产物控制机制；设计制备了新型双功能加氢催化剂，研究了水相平台分子HMF加氢氢解为含氧化合物2，5-二甲基呋喃的反应机理、选择性控制规律；制备了高效的氧化催化剂K-OMS-2，阐明了该催化剂上HMF到2，5-呋喃二甲醛的转化规律。发展了从酸水残渣中提取甜高粱木质素的方法，并对其结构进行了表征；在实验室合成了木质素二聚体模型；制备了高效负载型金属催化剂体系，研究了木质素低聚物解聚反应和酚类衍生物制备液体烷烃的反应机理；发展了含钒杂多酸在水/醇混合溶剂体系中催化氧化解聚木质素，获得了含有芳香醛类化合物，研究了Aldol缩合、频哪醇偶联和傅克反应的增碳反应机理，通过催化剂加氢脱氧，实现了由木质素制取C13-C17的液态烃类燃料。

关键词：能源植物 培育 化学催化 先进燃料 基础研究

Abstract：With aiming to the three key scientific issues， this project conducted the production advanced liquid fuels from biomass， and the development is listed as follows： （1） So as to the first key scientific issue， this project conducted the investigation on the the component and construction， and the function and mechansim of the stress-inducible gene during biosynthesis of energy plant such as energy sorghum. The net mediation mechanism of secondary cell wall formation in energy sorghum by biosynthesis was elucidated. The measurement platform and evaluation system for the genetic diversity of plasm germ was established. （2） For the second key scientific issue， this project clarified the decompolymerization mechanism and product controlling pathway of biomass macro-molecules in hydrothermal condition. The structure properties of acid/alkali treated lignin were explained and the dynamical model of the alkali dissolved lignin was built. For obtaining the yield of high phenolic monomers， the cooperative promotion mechanism of lignin decompolymerization by oxidation and liquifaction was investigated under microwave irradiation. （3） For the third key scientific issue， the study focused on the H2 production by decomposed products of biomass， the liquid alkane fuels and oxygen contained fuels from sugar derivatives by catalysis， and the liquid alkane fuels by phenol derivatives. The stimulated process was established based on the principle of Gibbs energy minimization and the hydrothermal gasification model and conversion pathway of glucose aqueous solution. The catalysts contained Ni/CeO2-Al2O3 and Ni/TiO2 were prepared， characterized and their performance was tested in H2 production by glucose aqueous solution， which obtained the H2 yield of more than 90% and good catalytic stability. For the first time，we found that the mdtB gene significantly affects the stress resistance and growth rate of the fungus， and thus influences the H2 production rate. The mass transfer enhanced micro- liquid layer system was developed to achieve high yielded HMF and alditol by one-pot conversion of sugar derivatives and the effective catalysts included functionalized nano-carbon and metal sulfates and phosphates were designed to the selective cracking of bonds in sugar derivatives. To obtain the high yield of liquid alkanes from sorbitol conversion in aqueous phase， the highly active metal supported on micro-/meso-porous zeolite was fabricated and the detailed reaction mechanism and pathway for products formatiion were researched. The pilot scaled apparatus for liquid alkanes production from sugar derivatives has been built up on the basis of scientific investigation in lab. To achieve the simultaneous conversion of cellulose and hemi-cellulose to platform （furfural， HMF and levulinic acid， etc.）， the new catalysts were developed and the formation mechanism and product controlling pathway was clarified. The effective duel functioalized catalyst and K-OMS-2 catalyst were prepared and their performance was evaluated in hydrogenation of HMF to 2，5--dimethyl furan and partial oxidation of HMF to furan-2，5-di-aldehyde， respectively. We developed the new method for obtaining lignin from the residue produced by acid-hydrolysis of sweet sorghum. The structure of the lignin was characterized in detail. For better understanding the decomposed mechanism of real lignin， we synthesized dimer models of lignin in lab. We prepared the supported metal catalysts for hydrodeoxygenation of lignin derived oligo-mers and phenolic derivatives to liquid alkanes and the detailed mechanism was investigated. The vanadium contained heteropolyacids was prepared to achieve oxidative decomposition of lignin to aromatic aldehydes in alcohol-water system. The C-C coupling mechanism for Aldol condensation， Pinacol coupling and Friedel-Crafts alkylation of phenol derivatives was studied， followed by hydrodeoxygenation to C13-C17 alkanes by supported metal catalysts.

Key Words：Energy plant；Breeding；Chemical catalysis；Advanced fuel；Basic research

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