Study On Non-precious Metal Catalysts For The Hydrogenolysis Of Methyl Laurate

Biomass is currently the most abundant renewable energy source on earth.Among them,bio-oils can be converted into long-chain alkane based bio-fuel and various high-value fine chemicals through processes such as hydrogenolysis and thermal cracking.The development of low-cost and efficient catalytic systems for hydrogenolysis of bio-oils and fats has long been a hot research area.In this thesis,a series of non-precious metal catalyst systems are designed and synthesized.The hydrogenolysis reaction of methyl laurate is used as a model reaction to study the catalytic effects of the as-obtained catalysts.Breakthroughs in this research can open up a green,low-cost path to utilize biomass.The specific research content includes the following two aspects more specifically:A series of cobalt catalysts were designed and synthesized and their catalytic effects on the hydrogenolysis of methyl laurate were studied.Two highly efficient and highly selective cobalt catalysts were obtained.Interestingly,the hydrogenolysis pathway of methyl laurate can be regulated by these catalysts.Synthesized from cobalt metal-organic framework(Co-MOF:[Co(tia^2-)（H₂O）₂]_￥(tia^2-=5-（1H-1,2,3-triazolyl）isophthalate)),the Co-MOF-700 catalyst obtained by calcination at 700^oC under nitrogen atmosphere can efficiently and selectively catalyze the hydrogenolysis decarboxylation/decarbonylation（DCO_x）process of methyl laurate.The conversion of methyl laurate can reach 100%.The total selectivity for long-chain alkanes can reach 85%,of which the selectivity of undecane is 67.6%and the selectivity of dodecane is 17.7%.In addition,we have synthesized a series of cobalt-supported catalysts using the traditional impregnation method.The catalytic performance tests show that the cobalt catalyst（Co/ZSM-5）supported by mesoporous molecular sieve can efficiently and selectively catalyze the hydrogenolysis deoxygenation（HDO）process of methyl laurate.The conversion of methyl laurate can reach 100%,and the total selectivity of long-chain alkanes can reach 81.7%,of which the selectivity of dodecane is 64.94%and the selectivity of undecane is16.72%.In addition,the Co-MOF-700 catalyst showed excellent cycle performance.After 5 cycles,the conversion of the substrate and the selectivity of the product remained almost unchanged.A series of copper catalysts were designed,synthesized and their catalytic effects on the hydrogenolysis of methyl laurate were studied.It was found the Cu-MOF-700catalyst derived from copper metal-organic framework(Cu-MOF:[Cu(tia^2-)（H₂O）₂]_￥(tia^2-=5-（1H-1,2,3-triazolyl）isophthalate))could efficiently and selectively catalyze the conversion of methyl laurate to lauryl alcohol.Cu-MOF-700 catalyst can promote the conversion of methyl laurate to with 81.29%conversion,and 85.46%selectivity of dodecanol.