掺Zr短大孔硅基无硫Ni-M双金属催化油脂同碳转化碳氢燃料的反应机制

The same carbon conversion of biomass oil through hydrodeoxygenation is a direction for developing high quality green clean hydrocarbon fuel. It is a key scientific problem to promot C-O bonds cleavage and inhibit C-C bonds broken (usually including decarboxylation/carbonyl and long-chain alkane cleavage) in the hydrodeoxygenation of biomass oil converted to same hydrocarbon fuel. A strategy of the solvent evaporation induced polymerization assembly for adjusting double template agents structure and carrier surface modification is adopted. This project intends to do the following works: (1) Using a strategy of solvent evaporation induced polymerization assembly to control bi-template structure for design and synthesis of a Zr-doped with C and the oxyphilic Zr/Zn modified short-large-pore silica carriers, it is beneficial for reducing diffusion resistance and fracture of long-chain grease molecules into small molecular in carrier channels,where doping-Zr can enhance Brønsted acid sites to promote C-O bonds cleavage and facilitate the formation of short large pores to inhibite C-C bonds cleavage, and carbon-modifying pore structure can enhance wall thickness with both facilitating the loading of Ni-M bimetallic and improving the hydrothermal stability. (2) Using a method of ultrasonic wet impregnating Ni-M(Co/Mo) bimetallic followed by two-segmented calcination to remove the double-template agent, realize crystal transformation and to provide bimetallic active sites for hydrodeoxygenation, with the regulation of Ni/M to reduce nickel d band holes to increase the mobility of active hydrogen and bimetallic activites for inhibiting C=O bonds adsorption and promoting C-O bonds cleavage. (3) Based on the catalyst structure-activity and reaction mechanism analysis, combined with the DFT theoretical simulation, the reaction mechanism of the same carbon conversion of biomass oil to hydrocarbon fuel through hydrodeoxygenation over the Zr-doped short-large-pore silica Ni-M bimetallic catalysts will be disclosed, and a new method for preparing the Zr-doped short-large-pore silica sulfur-free Ni-M bimetallic catalysts and for the same-carbon converting of biomass oil to high quality green clean hydrocarbon fuel over will be developed.

生物质油酯加氢脱氧是发展高品质绿色洁净碳氢燃料的方向。针对催化油脂加氢脱氧中如何促进C-O键裂解抑制C-C键断裂实现同碳转化碳氢燃料的科学问题，采用溶剂蒸发诱导聚合组装调控双模板剂结构与改性载体表面策略，设计制备碳修饰掺杂亲氧性Zr/Zn短大孔硅基载体，适合长链油脂分子在孔内扩散避免C-C键碰撞断裂与堵塞；载体掺Zr增强B酸促进C-O键裂解又有利短大孔形成，碳修饰孔结构增强孔壁厚提高水热稳定性；超声湿法浸渍Ni-M(Co/Mo)分段焙烧，形成促进C-O裂解抑制C-C断裂的加氢脱氧活性位；调控Ni/M降低镍d带空穴提升H迁移率，抑制Ni对C=O羰基C的强吸附，促进C-O裂解；在催化剂构效关系与反应机理分析基础上，运用密度泛函理论与分子模拟计算，揭示催化油脂加氢脱氧同碳转化的反应机制，提供一种制备掺Zr短大孔硅基无硫非贵金属Ni-M催化剂催化油脂加氢脱氧同碳转化高品质绿色洁净碳氢燃料的新方法。

针对催化生物油脂加氢脱氧同碳转化碳氢燃料、合成航空煤油及脂肪醇研究工作如下：（1）研制非贵金属无硫镍基催化剂：浸渍法制备Ni/CeO2-Al2O3在280℃、2.5MPa氢压催化油酸乙酯加氢脱氧n-C17收率95%；共沉淀法制备Ni/La2O3-SiO2催化棕榈酸甲酯加氢脱氧n-C15收率99%，催化剂循环10次收率95%；溶胶凝胶法制备Ni/CeO2-Al2O3催化油酸甲酯加氢脱氧n-C17收率97%，催化实际油脂（麻疯树油、废弃烹饪油）加氢脱氧C13-18收率94%；溶剂蒸发诱导聚合组装制备Ni/CeO2-Al2O3催化脂肪酸甲酯加氢脱氧收率93~99%，催化剂循环11次收率90%，催化实际油脂C13-18收率95%。（2）催化脂肪酸甲酯加氢脱氧同碳转化：NiMo/TiO2-SiO2催化月桂酸甲酯加氢脱氧n-C12收率96%；掺杂亲氧性助剂Mo制备Ni/MxOy-Al2O3催化棕榈酸甲酯n-C16收率95%，发现B酸Mo亲氧性吸附促进加氢脱氧同碳转化；CoMo/ZrO2-Al2O3催化实际油脂n-C13-18收率90%。（3）生物质衍生物制备航空燃料：MoO3/TiO2在60℃催化糠醛、2-甲基呋喃反应得呋喃偶联产物收率95%，Ni/Mo2C@CQDs在250℃、4MPa氢压催化呋喃偶联产物加氢脱氧得航空燃料主组分6-丁基十一烷收率86%、总烷烃收率97%；NiMo/ZrO2催化糠醛加氢脱氧得2-甲基呋喃收率94%；TiO2−ZrO2催化环戊酮缩合二聚物收率76%。（4）催化脂肪酸甲酯选择性加氢制备脂肪醇：碳量子点原位Ni掺杂制备Ni/Mo2C@CQDs在180℃、4MPaH2催化脂肪酸甲酯选择性加氢得脂肪醇收率82~96%，催化实际油脂加氢得C14+16+18混合脂肪醇收率87%。本研究揭示催化油脂加氢脱氧反应机制，提供催化油脂加氢脱氧同碳转化碳氢燃料及脂肪醇新方法。