Catalytic Co-cracking Of Reduced Pressure Distillation Of Bio-oil And Ethanol Over Metal Loaded Micro-mesoporous Molecular Sieves Rearch

Bio-oil is the liquid product of biomass fast pyrolysis in anaerobic and medium temperature,and is expected to be the alternative new fuel of traditional fossil fuels. But bio-oil has the disadvantage of high moisture, strong acid, high oxygen content, low heating value, and poor stability. Thus, it cannot be used as a fuel and upgrading process is necessary.Catalytic cracking is a very important bio-oil upgrading method, it can achieve totally change in the composition of bio-oil. Catalytic cracking with the advantage of atmospheric reaction conditions and without reducing gas has to be the concern of the experts and scholars. Microporous molecular sieves and ordered mesoporous materials, which were used to catalytic cracking reaction, are due to their own defects in application are restricted.This paper adopted composite molecular sieves with micro-mesoporous hierarchical pore structure to improve the catalytic activity of and the performance of resistance to coke formation. About the issue of high moisture of crude bio-oil, obtained bio-oil high boiling point fractions by reduced pressure distillation in this paper. Adding ethanol with reduced pressure distillation of bio-oil co-catalytic cracking due to bio-oil has lower（H/C）eff, aiming at reducing the acid content in upgrading bio-oil and analysing the distribulation of gas, liquid and solid products.The reduced pressure distillation of bio-oil and ethanol with the mixting radio of 2:3 by weight were subjected to catalytic co-cracking over ZSM-5/MCM-41 and Ni-ZSM-5/MCM-41 molecular sieves in a fixed-bed in this paper. The effects of reaction temperature, WHSV and metal loading on cracking products were investigated. The catalysts are characterized by NH₃-TPD, H₂-TPD, BET and N₂ adsorption and desorption. The gaseous products were analyzed by gas chromatograph, and reduced pressure distillation of bio-oil and the upgraded bio-oil were quantified by gas chromatograph-mass spectrometry. It was found that:There are 11.7% ester and 4.6% aromatic hydrocarbon in upgrading bio-oil, and acid substances is markedly reduced from 25.6% in reduced pressure distillation of bio-oil to 0.1%after reacted at 500℃ of the reaction temperature and 3.75 h-1 of the WHSV. Meanwhile, the yield of upgraded bio-oil is 46.8%. In the study of adopting different Ni loading of support catalysts, it was found that acid dropped to 0.1%, and the concentration of CO₂ and CO of the gas products is 36.8% when Ni loading of support is 6wt.% at 500℃, WHSV 3.75 h-1.Therefore, 6wt.% Ni-ZSM-5/MCM-41 has a superior deoxygenation effect.By catalytic co-cracking of reduced pressure distillation of bio-oil and ethanol over metal loaded micro-mesoporous molecular sieves can effectively reduce the content of acid andoxygen in bio-oil. The catalytic co-cracking process improve the quality of bio-oil, and providing basic data for subsequent bio-oil industrial application.