草本能源植物培育及催化制備先進液體燃料

馬隆龍 劉琪英

摘 要：研究前兩年圍繞3個關鍵科學問題開展，取得的進展如下：（1）針對關鍵科學問題1，圍繞解析能源高粱等能源植物能源物質組成和結構，能源物質生物合成及抗逆相關基因的功能和作用機制開展研究，提出了高粱等能源植物中次生細胞壁生物合成調控網絡的解析機理；闡明了抗逆性相關基因的功能和作用機制；建立了檢測技術平臺以及種質遺傳多樣性的評價體系與方法。（2）針對關鍵科學問題2，揭示了生物質大分子水熱解聚為糖類衍生物的反應機理及產物選擇性調控規律；深入解析了酸/堿處理木質素的結構特征，構建了堿溶出木質素過程的動力學模型；提出了微波在木質素氧化與液化解聚過程中的協同促進機制，獲得較高的單酚收率。（3）針對關鍵科學問題3，圍繞解聚產物制氫、糖類衍生物制液體烴類/含氧燃料和酚類衍生物制液體烷烴燃料，進行了深入系統地研究。根據Gibbs自由能最小化原理建立了模擬流程，闡明了葡萄糖水溶液的水熱氣化模型與反應途徑。設計制備了高效的Ni/CeO2-Al2O3和Ni/TiO2催化劑，并對其結構與化學性質進行深入分析，該類催化劑在葡萄糖水熱制氫反應中的產氫率超過90%，具有較好的穩定性。首次發現了mdtB基因對細菌的抗逆性、生長速率和產氫速率具有重要的影響。創制了強化水相傳質與相轉移的微液膜反應體系，實現糖類衍生物一步高效轉化為平臺化合物HMF與C5/C6糖醇；研制了高水熱穩定的功能化納米碳及金屬酸性鹽催化體系，提高了選擇性斷鍵性能；研制了高效過渡金屬/介孔-微孔固體酸復合催化體系，揭示了糖醇水相催化合成液體烴燃料的轉化機理與產物控制規律；初步建立了糖類衍生物水相催化合成液體烴類燃料的中試驗證系統。發展了多種新型的催化劑體系，可協同轉化纖維素和半纖維素，實現了糖類衍生物到平臺分子（糠醛，HMF和乙酰丙酸）的高效轉化，揭示了上述轉化過程的反應機理與產物控制機制；設計制備了新型雙功能加氫催化劑，研究了水相平臺分子HMF加氫氫解為含氧化合物2，5-二甲基呋喃的反應機理、選擇性控制規律；制備了高效的氧化催化劑K-OMS-2，闡明了該催化劑上HMF到2，5-呋喃二甲醛的轉化規律。發展了從酸水殘渣中提取甜高粱木質素的方法，并對其結構進行了表征；在實驗室合成了木質素二聚體模型；制備了高效負載型金屬催化劑體系，研究了木質素低聚物解聚反應和酚類衍生物制備液體烷烴的反應機理；發展了含釩雜多酸在水/醇混合溶劑體系中催化氧化解聚木質素，獲得了含有芳香醛類化合物，研究了Aldol縮合、頻哪醇偶聯和傅克反應的增碳反應機理，通過催化劑加氫脫氧，實現了由木質素制取C13-C17的液態烴類燃料。

關鍵詞：能源植物 培育 化學催化 先進燃料 基礎研究

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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