Study Of Performance Of Macroporous Sulfonic Resin Catalysts On Alkylation Desulfurization Of FCC Gasoline

Macroporous sulfonic resin,a kind of non-corrosive and non-polluting solid acid catalyst,is widely used in alkylation,etherization,esterification,hydrolysis and other organic reaction.The advantages are high activity,high selectivity,and simple operation conditions.Macroporous sulfonic resin has a very good absorption performance for basic nitrogen in the FCC gasoline,and also can be used as catalyst for alkylation of thiophenic sulfur compounds with olefins.This paper first discussed the adsorption performance of macroporous sulfonic resin NKC-9,CT-175,LSI-600,D005-â…¡and 13X zeolite for the basic nitrogen compounds in FCC gasoline,through the investigation of the ratio of gasoline and catalyst,adsorption time,absorption capacity,selective absorption and adsorbent costs. The results indicated that LSI-600 was the best absorbent.The adsorption conditions were:the ratio of FCC gasoline and adsorbent 35:1,adsorption temperature about 25℃,absorption time 15 min,with a certain mechanical agitation rate.LSI-600 regenerated by ethylamide-ethanol,had a slight increase in the basic nitrogen absorption capacity.FCC gasoline was cut into several fractions,through a simple way.This paper studied the alkylation desulfurization of fractions in accordance with the characteristics.The results showed that 40℃,120℃were the appropriate distillation cutting points.The boiling potints of products in 40～120℃distillate were higher than the products's in＜40℃,＞120℃mixed fraction.C₄,C₅-olefins were the main reagents in alkylation reaction.The sulfonic resin for the alkylation of olefins and thiophenic sulfur compounds had good activity,but poor stability in the batch reactor.Based on patent CN1986746A,Ion-exchange resins were modified by AlCl₃ and ZnCl₂.But the activity and stability of modified AlCl₃-ion resins and ZnCl₂-ion resins were both reduced.IR analysis showed that the metal ions and resin formed chemical bond,but not formed super acid structure.The resin modified by AlCl₃ and ZnCl₂ reduced B acid,increased L acid,it was bad for alkylation of thiophenic sulfur and olefins.Ion resin industrialization will be the reaction distillation tower installations.So, the stability of NKC-9 resin was inspected in distillation columns.NKC-9 reacted in the distillation tower about 30h maintained the alkylation desulfurization activity, compared with the fresh NKC-9.However,the alkylation performance of NKC-9 after twice deactivity was poor.It was indicated that the stability of resin was significantly improved in reaction distillation tower.