Applied Basic Study On Catalytic Oxidation Of Phosphine With Ionic Liquid/Water Dual Liquid Phase

Tail gas from phosphorus furnace contains a large amount of CO resource that can be used as important C1 chemical raw materials after purification.But phosphine acts as one of difficult to deal with industrial waste gas in the yellow phosphorus tail gas,it not only causes serious environmental pollution and endangers human health,but also severely restricts the product deep processing and utilization of yellow phosphorus tail gas.In view of liquid phase catalytic oxidation purification PH3 possessing the advantages of mild reaction conditions,good selectivity and high activity,so in the homogeneous metal complexes catalyze reaction system,ionic liquids and catalysts can be effectively integrated together by complexation to achieve catalysts liquid immobilization.Dual liquid phase catalytic system can be composed by water and hydrophobic ionic liquids immobilized catalysts,and it can be used both as solvent and catalyst for the reaction in gas absorbing separation purification applications.Considering the study of catalytic oxidation products separation and the mass transfer kinetics of liquid phase not sufficient,the lack of data on ionic liquids absorption equilibrium for PH3,having few studies about the distribution coefficient of catalytic component and catalytic oxidation products in ILs/Water,etc.In this study,PH3 from phosphorus furnace tail gas is acted as purified target.We investigate the physical parameters of ionic liquids,the solubility of oxygen and phosphine in ionic liquids,the influence of reaction temperature,oxygen content and catalytic component content on ILs/Water dual phase catalytic system purification efficiency,the distribution coefficient of catalytic component and catalytic oxidation products in ILs/Water.Moreover,on the basis of the FT-IR characterization of transition metal-based ionic liquids before and after reaction,and the Ion chromatographic analysis of products,We explore the mechanism of ILs/Water dual phase catalytic system purification for PH3.Through experiments,the experimental results are as follows:(1)Preparation of a variety of room temperature hydrophobic ionic liquids were characterized by 1H NMR,13C NMR and MS.Meanwhile we got corresponding transition metal-based ionic liquids with room temperature hydrophobic ionic liquids and transition metal salts,and built transition metal ionic liquids/water dual phase catalytic systems.(2)The results indicate that the viscosity and conductivity of[Bmim]PF6,[Hmim]PF6 and[Omim]PF6 is affected by temperature and the alkyl chain length.At the same temperature,the order of viscosity:[Bmim]PF6?[Hmim]PF6<[Omim]PF6,the order of conductivity:[Bmim]PF6>[Hmim]PF6>[Omim]PF6.The solubility of O2 and PH3 in[Bmim]PF6,[Hmim]PF6 and[Omim]PF6 are also closely related to temperature and alkyl chain length,the solubility of O2 and PH3 in ionic liquids is higher than the solubility in water.(3)Studies have shown that CuCl is a good catalyst component.The Cu+-[Bmim][PF6]/Water dual phase catalytic system has high purification efficiency for PH3,and Cu+-[Bmim][PF6]has good thermal stability.In addition,Cu+-[Bmim][PF6]/Water dual phase catalytic system purification efficiency for PH3 is much better than[Bmim][PF6]/Water and pure[Bmim][PF6].(4)In terms of Cu+-[Bmim][PF6]/Water dual phase catalytic system purification for PH3,the results show that the optimum reaction temperature is 45?,the optimal oxygen content is 3%,the best mole ratio of[Bmim][PF6]and CuCl is 2:1.The dual phase catalytic system can be reused by drum oxygen regeneration.(5)The distribution coefficient of CuCl and H3PO4 in ionic liquids/water dual phase were obtained respectively.Meanwhile according to the Ion chromatographic analysis of products,and the FT-IR characterization of Cu+-[Bmim][PF6]ionic liquids before and after reaction.Through the research on Cu+-[Bmim][PF6]/water dual phase system purification PH3 reaction mechanism and the ionic liquid/water dual phase system structure,the Cu+-[Bmim][PF6]/Water dual phase catalytic system purification process for PH3 is a liquid-phase catalytic oxidation process,and the product is H3PO4 that can be automatically separated.