不饱和脂肪酸氢转移和脱羧反应耦合过程研究

High hydrogen consumption is the major disadvantage of catalytic hydrodeoxygenation of oils to produce second generation biodiesel, in which long-chain alkanes are the main components. More and more attentions are payed on technology of decarboxylation of oil to long-chain alkanes without added hydrogen. With the technology, very good results are got for saturated fatty acids. But for unsaturated fatty acids, the issues such as more side reactions, low yields of long-chain alkanes, catalyst deactivation exsit. In order to solve the above problems, coupled processes of hydrogen transfer and decarboxylation reactions of unsaturated fatty acids are proposed in this project. Based on the study of hydrogen transfer reactions of unsaturated fatty acids, the design, preparation, characterization and evaluation of catalysts for the coupled processes of hydrogen transfer and decarboxylation reactions of unsaturated fatty acids will be conducted. Combining optimization of reaction process, exploration of reaction mechanism with studies of process coupling，a new method on coupled processes of hydrogen transfer and decarboxylation reactions of unsaturated fatty acids will be finally established. The research work will provide a new approach for preparation of long-chain alkanes from oil with zero hydrogen consumption, and greatly facilitate the progress of low-cost, environmentally benign and efficient preparation of second generation biodiesel.

高氢耗是油脂催化加氢脱氧制备第二代生物柴油（主要成分为长链烷烃）的主要缺陷。近年来提出的油脂非临氢催化脱羧制备长链烷烃技术由于氢耗低备受关注，该技术对于饱和脂肪酸取得了非常好的效果，但对于不饱和脂肪酸非临氢催化脱羧却存在副反应多、长链烷烃收率低、催化剂易失活等问题，为此本项目提出了将氢转移反应应用于不饱和脂肪酸碳碳双键选择性加氢并与脱羧反应耦合来制备长链烷烃的新途径。拟在不饱和脂肪酸氢转移反应研究的基础上，开展不饱和脂肪酸氢转移-脱羧耦合过程催化体系的设计、制备、表征与评价研究，结合反应工艺的优化、反应机理的探索以及过程耦合的研究，建立不饱和脂肪酸氢转移-脱羧耦合制备长链烷烃的新方法。研究工作将为油脂零氢耗制备长链烷烃提供新途径，进而推动我国第二代生物柴油的低成本、绿色高效制备的工业化进程。

高氢耗是油脂催化加氢脱氧制备第二代生物柴油（主要成分为长链烷烃）的主要瓶颈之一。近年来提出的油脂非临氢催化脱羧制备长链烷烃技术由于氢耗低备受关注，该技术对于饱和脂肪酸取得了非常好的效果，但对于不饱和脂肪酸非临氢催化脱羧却存在副反应多、长链烷烃收率低、催化剂易失活等问题。为此本项目提出了将氢转移/原位加氢应用于不饱和脂肪酸碳-碳双键选择性还原，并与脱羧反应耦合来制备长链烷烃的新途径。在不饱和脂肪酸催化转移氢化/原位加氢反应和脂肪酸催化脱羧反应分别研究的基础上，构建了四个不饱和脂肪酸转移氢化/原位加氢和脱羧耦合反应催化体系，进而拓展了催化转移氢化/原位加氢反应的底物。对于不饱和脂肪酸催化转移氢化/原位加氢反应，研究内容包括近临界异丙醇中油酸催化转移氢化制备十八醇、甲醇水体系中铜基催化剂催化脂肪酸原位加氢制备脂肪醇；对于脂肪酸催化脱羧反应，研究内容包括硬脂酸催化脱羧制备烷烃活性炭负载镍催化体系的构建、水对Pt/C催化下油酸非临氢脱羧制备十七烷反应的促进作用；对于不饱和脂肪酸转移氢化/原位加氢和脱羧耦合反应催化体系的构建，研究内容包括近临界异丙醇中油酸转移氢化和脱羧耦合反应CuNi/CoOx催化体系的构建、甲醇供氢下油酸原位加氢和脱羧耦合反应Cu-Ni合金催化体系的构建、甲醇供氢下油酸原位加氢和脱羧耦合反应Cu-Ni/ZrO2催化体系的构建、无供氢剂存在下油酸芳构化-原位加氢和脱羧反应耦合Ni/AC催化体系的构建、溶剂对油酸原位加氢和脱羧耦合反应的影响；最后将催化转移氢化/原位加氢反应的底物拓展到糠醛、5-HMF和木糖等。共培养博士生7人、硕士生9人。发表标注期刊论文41篇（其中SCI收录37篇、EI收录4篇）；发表标注国内外会议论文7篇；授权发明专利30件。研究工作将为油脂零氢耗制备长链烷烃提供新途径，进而推动我国第二代生物柴油的低成本、绿色高效制备的工业化进程。