Catalytic Oxidative Desulfurization Of Loaded Phosphotungstic Acid Modified HMS Molecular Sieve

In order to achieve the sustainable development of man and nature,all countries in the world have strengthened the research and development efforts of the clean fuel.Oxidative desulfurization has become current research focus of fuel oil desulfurization because of its advantages,such as mild reaction conditions,simple operation,low investment costs and having a good removal effect to benzothiophene and its ramification.Choosing suitable catalysts is a key of Oxidative desulfurization.With high catalytic activity,high reaction selectivity and multi-functional catalytic characteristics,heteropolyacid is a good performance of the oxidative desulfurization catalyst.Among heteropolyacid catalysts,supported heteropolyacid catalyst has been widely concerned by people because of its good catalytic performance and stability.In this paper,with hydrogen peroxide as the oxidant,amino-modified and metal Cu,Ni,Zn modified HMS molecular sieve load phosphotungstic acid as catalysts,BT/petroleum ether model oil as the research object,study the catalyst desulfurization reaction performance,it investigated phosphotungstic acid load,modifier usage,catalyst activation temperature for the effect on catalyst desulfurization performance.Screening the best performance of the catalyst,and using it for catalytic cracking gasoline and hydrogasoline catalytic oxidative desulfurization.It investigated the oxidation reaction temperature,amount of catalyst,the amount of hydrogen peroxide and the oxidation reaction time for the effect on oil desulfurization rate.It also investigated extractant type,amount of extractant and extraction times on the yield of gasoline and the desulfurization rate,and then screening extractant and determining the best conditions of desulfurization process.Amino-modified and metals Cu,Ni,Zn modified HMS carrier have large specific surface area,after loading phosphotungstic acid,the specific surface area of catalyst can reach around 300m2/g.According to the catalyst characterization results,modified carriers can be well dispersed phosphotungstic acid and do not destroy the Keggin structure of phosphotungstic acid.The catalytic oxidation research results show that:The metal Ni modified HMS load phosphotungstic acid is the best catalyst,Ni/Si molar ratio of 0.02,the phosphotungstic acid load of 30%,in the 110? for 2h activation,under the conditions of the amount of catalyst 0.45%,hydrogen peroxide and the oil volume ratio of 0.022,the oxidation reaction temperature of 60 ?,reaction time 60min,and using volume fraction of 90%1,4-butyrolactone aqueous solution as extractant,the extractant and gasoline volume ratio of 1,separated oil after extraction 10min,FCC gasoline desulfurization rate is 88.75%,and oil yield of 80.50%,sulfur content is reduced by the initial 249?g/g to 28?g/g.hydrogenation gasoline desulfurization rate is 92.51%,the oil yield of 87.50%,sulfur content from the initial 292?g/g to 22?g/g.After extracted three times,the FCC gasoline desulfurization rate can reach 92.20%,the hydrogenated gasoline desulfurization rate can reach 95.21%,but the oil yield below 80%.