草本能源植物培育及催化制備先進(jìn)液體燃料

馬隆龍 劉琪英

摘 要：研究前兩年圍繞3個關(guān)鍵科學(xué)問題開展，取得的進(jìn)展如下：（1）針對關(guān)鍵科學(xué)問題1，圍繞解析能源高粱等能源植物能源物質(zhì)組成和結(jié)構(gòu)，能源物質(zhì)生物合成及抗逆相關(guān)基因的功能和作用機(jī)制開展研究，提出了高粱等能源植物中次生細(xì)胞壁生物合成調(diào)控網(wǎng)絡(luò)的解析機(jī)理；闡明了抗逆性相關(guān)基因的功能和作用機(jī)制；建立了檢測技術(shù)平臺以及種質(zhì)遺傳多樣性的評價體系與方法。（2）針對關(guān)鍵科學(xué)問題2，揭示了生物質(zhì)大分子水熱解聚為糖類衍生物的反應(yīng)機(jī)理及產(chǎn)物選擇性調(diào)控規(guī)律；深入解析了酸/堿處理木質(zhì)素的結(jié)構(gòu)特征，構(gòu)建了堿溶出木質(zhì)素過程的動力學(xué)模型；提出了微波在木質(zhì)素氧化與液化解聚過程中的協(xié)同促進(jìn)機(jī)制，獲得較高的單酚收率。（3）針對關(guān)鍵科學(xué)問題3，圍繞解聚產(chǎn)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(jìn)行了深入系統(tǒng)地研究。根據(jù)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(yīng)途徑。設(shè)計(jì)制備了高效的Ni/CeO2-Al2O3和Ni/TiO2催化劑，并對其結(jié)構(gòu)與化學(xué)性質(zhì)進(jìn)行深入分析，該類催化劑在葡萄糖水熱制氫反應(yīng)中的產(chǎn)氫率超過90%，具有較好的穩(wěn)定性。首次發(fā)現(xiàn)了mdtB基因?qū)?xì)菌的抗逆性、生長速率和產(chǎn)氫速率具有重要的影響。創(chuàng)制了強(qiáng)化水相傳質(zhì)與相轉(zhuǎn)移的微液膜反應(yīng)體系，實(shí)現(xiàn)糖類衍生物一步高效轉(zhuǎn)化為平臺化合物HMF與C5/C6糖醇；研制了高水熱穩(wěn)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(fù)合催化體系，揭示了糖醇水相催化合成液體烴燃料的轉(zhuǎn)化機(jī)理與產(chǎn)物控制規(guī)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(yàn)證系統(tǒng)。發(fā)展了多種新型的催化劑體系，可協(xié)同轉(zhuǎn)化纖維素和半纖維素，實(shí)現(xiàn)了糖類衍生物到平臺分子（糠醛，HMF和乙酰丙酸）的高效轉(zhuǎn)化，揭示了上述轉(zhuǎn)化過程的反應(yīng)機(jī)理與產(chǎn)物控制機(jī)制；設(shè)計(jì)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(yīng)機(jī)理、選擇性控制規(guī)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(zhuǎn)化規(guī)律。發(fā)展了從酸水殘?jiān)刑崛√鸶吡荒举|(zhì)素的方法，并對其結(jié)構(gòu)進(jìn)行了表征；在實(shí)驗(yàn)室合成了木質(zhì)素二聚體模型；制備了高效負(fù)載型金屬催化劑體系，研究了木質(zhì)素低聚物解聚反應(yīng)和酚類衍生物制備液體烷烴的反應(yīng)機(jī)理；發(fā)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(zhì)素，獲得了含有芳香醛類化合物，研究了Aldol縮合、頻哪醇偶聯(lián)和傅克反應(yīng)的增碳反應(yīng)機(jī)理，通過催化劑加氫脫氧，實(shí)現(xiàn)了由木質(zhì)素制取C13-C17的液態(tài)烴類燃料。

關(guān)鍵詞：能源植物 培育 化學(xué)催化 先進(jìn)燃料 基礎(chǔ)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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