The Preparation Of Solid Sulfonic Acid Catalyst And Its Application In FCC Gasoline Alkylation Desulfurization

In many non-hydrodesulfurization technologies of gasoline,FCC gasoline alkylated desulfurization and S-Zorb technology are the only two non-hydrodesulfurization technologies already industrialized in the world so far.olefin alkylated thiophenic sulfur in FCC gasoline over acid catalyst to generate sulfur compounds with bigger molecular weight,higher boiling point,and the higher boiling point alkylation reaction product can be distilled and removed to avoid the loss of octane number caused by the saturation of olefins in the hydrotreating.The technology has the advantages of mild operating conditions,good desulfurization effect and small loss of octane value.In this paper,a solid acid catalyst was prepared,and the alkylation desulfurization experiments of FCC gasoline were carried out.The reasons for deactivation and regeneration methods of solid acid catalyst were also studied.Experiment of alkylation desulfurization with solid acid catalyst,it has the advantages of easy to separate from FCC gasoline,no corrosion equipment,simple post-processing,less pollutant emission and good thermal stability.Glycerol as a by-product in biodiesel production was used as carbon source,sulfonated glycerol solid acid catalyst was prepared by concentrated sulfuric acid sulfonation and carbonization directly,it was applied to FCC gasoline alkylation desulfurization reaction,the desulfurization rate of FCC gasoline alkylation reaction and acid value as the index to evaluate the preparation of sulfonated glycerol solid acid catalyst activity,the sulfonated glycerol solid acid catalyst best preparation conditions were found out,the mole ratio of raw materials n(concentrated sulfuric acid:glycerol)was 4,the sulfonation temperature was 60?,the sulfonation time was 3h,carbonization temperature was 200?,carbonation time was 15min.The preparation of sulfonated glycerol solid acid catalyst was characterized by FT-IR,BET,XRD,TG and so on.the acid value of the sulfonated glycerol solid acid catalyst is up to 4.1mmol/g by the method of ultrasonic wave concussion and acid-base titration.The alkylation reaction conditions of FCC gasoline were evaluated by single factor.The experimental results showed that the best alkylation desulfurization conditions of sulfonated glycerol solid acid catalyst were:the mass ratio of solid acid and FCC gasoline was 0.4,the reaction temperature was 90?,the reaction time was 80min,and the sulfur content was reduced from518.2?g·g-1to72.8?g·g-1,the desulfurization rate was as high as 85.95%.In addition,the deactivated sulfonated glycerol solid acid catalyst was analyzed by BET?XRD?TG characterization and acid-base titration,the results showed that carbon deposition and basic nitrogencompounds in FCC gasoline caused deactivation of sulfonated glycerol solid acid catalyst,so it is very necessary to use adsorbent to pretreat FCC gasoline.The deactivated sulfonated glycerol solid acid catalyst was regenerated by the method of resulphonating,and compared catalytic activity of alkylation with the fresh sulfonated glycerol solid acid.The alkylation catalytic activity of the regenerated sulfonated glycerol solid acid almost recovered to the activity of fresh sulfonated glycerol solid acid.