Metal Modified Zeolite Adsorbent Using For Adsorption Desulfurization Of Gasoline

In recent years,with the strict control of sulphide content in automotive exhaust gas and the need of fuel cells for ultra-low sulfur fuel,the deep desulphurization of fuel oil has become a research hit question and an urgent problem to be solved all over the world.A series of metal-modified zeolite adsorbents were prepared using solid-phase method,liquid-phase ion exchange method,and co-precipitation method.At the same time,the XRPD?SEM?TEM?FT-IR?XPS?N₂-adsorption desorption isotherms,NH₃-TPD?H₂-TPR and other characterization methods were used to characterize the physicochemical properties of the adsorbents.The desulfurization behavior of the organic sulfur compounds on the adsorbents are discussed.1.The metal modified Y zeolite adsorbents were prepared by solid state reaction?MY-S-1,M:Ru?Sb?Zr and Bi?.Adsorptive properties for thiophene over the adsorbents were investigated in the model gasoline.The thiophene concentration is0.624 mM?corresponding to the concentration of 20 ppmw as S?in the model gasoline.RuY-S-1 showed the highest sulfur removal among the MY-S-1 adsorbents studied.The sulfur removal reached 68%at an adsorbent/solution ratio of 0.1 g/10mL.The competitive adsorption analysis of the sulfur and coexistence toluene showed that the MY-S-1 has high selectivity for thiophene.Effect of metal ion type,metal ion loading,metal ion chemical state for thiophene removal were investigated in detail by batch method.The sulfur removal increased with an S-M bond strength of metal ion on MY-S-1.The metal ion loading dependence suggested that sulfur removal increased with Ru ion loading amount on RuY-S-X.2.RuY-L adsorbents were prepared by liquid-phase ion exchange method.Adsorption desulfurization experiments for thiophene,benzothiophene and4,6-dimethyldibenzothiophene over RuY-L adsorbents with different calcination temperatures and different loading were investigated.The experimental results showed that sulfue removal of RuY-L-12?200?was reached 99%.The XPS results indicated that Ru⁴⁺active component was present in RuY-L-12?200?adsorbent.TEM and H₂-TPR results exhibited that active component in Ru Y-L-12?200?adsorbent was RuOx cluster.After five adsorption-regeneration cycles,the sulfur removal of thiophene and benzothiophene was about 50%,and the sulfur removal for4,6-dimethyldibenzothiophene was 88%.3.A series of Ce-modified zeolites?X?L?ZSM-5?A?Mordenite?and MCM-41adsorbents were prepared by liquid-phase ion exchange and precipitation method.The adsorbents pore size,surface area and Ce loading influence for the desulfurization of thiophene were investigated.The experimental results showed that CeX and 0.05Ce/MCM-41 exhibited well desulfurization performance.The sulfur removal of thiophene and benzothiophene over CeX and 0.05Ce/MCM-41 were 83%and 76%,respectively.After five adsorption-regeneration cycles,the sulfur removal of CeX and 0.05Ce/MCM-41 were 65%and 53%,respectively.