Study On The Suspension Bed Hydro-upgrading Of Residue With The Oil-soluble Catalyst

With the diminishing of petroleum resources and the growing maturity of heavy oil extraction technology,crude oil production showed a heavy trend,inferior trend,in addition,the environmental regulations are increasingly stringent and light oil demand greatly increased.Suspension bed hydrogenation technology can process high-metal,high-carbon,high-sulfur low-quality heavy oil raw materials,and gradually become a hot spot,in which the key is high-performance hydrogenation catalyst continuous progress.In this paper,the self-vulcanized oil-soluble molybdenum-based catalyst was prepared by quaternary ammonium salt or organic amine and molybdenum salt in one step.The reaction conditions of the catalyst were optimized by using Qingdao vacuum residue as raw material,initially formed low cost preparation and application strategy.The self-vulcanized oil-soluble molybdenum-based catalyst precursors were prepared by the reaction of quaternary ammonium salts and ammonium tetramethalumate.The effects of aqueous phase method,organic solvent-water two-phase method and organic solvent-solid phase method on catalyst dispersibility and hydrocracking performance were investigated.It was found that the catalyst precursor synthesized by the aqueous phase method had good dispersibility,and the amount of the catalyst was 200ug·g-1,the reaction temperature was 420?,the initial pressure of hydrogen was 8MPa,reaction time 1h,the conversion efficiency of vacuum residue is 70%and the amount of coke is less than 3%,which shows high hydrogenation activity and inhibition of coke performance.However,when the amount of catalyst added increases,the catalyst will appear more obvious agglomeration,but reduce the yield of light oil and increase the amount of coke,indicating that the oil solubility of the catalyst is still not ideal.The preparation of oil-soluble molybdenum-based catalyst precursors by the reaction of organic amines with ammonium tetrathiate molybdate was carried out.The simple preparation method of the catalyst was studied and the reaction conditions were optimized.It was found that the oil solubility of the catalyst was greatly enhanced,and the solubility in the catalytic diesel was 6%⁷%,and the synthesis process was simple and the condition was mild,which was convenient for low-cost and large-scale industrial production.The catalyst precursor can be decomposed from sulfide to form nano-scale dispersed active metal MoS₂,the average sheet length of 6nm,the average number of layers of 2 to 4.The reaction temperature is from 380?to 430?,the initial pressure of hydrogen is more than 10MPa,the concentration of catalyst is 200²000ppm,the reaction time is 1²h,the conversion rate of vacuum residue is more than 80%,the total amount of vacuum residue is 80%Coke formation rate of 0.2%,showing excellent hydrogenation performance.