Preparation And Oxidative Desulfurization Performance Of Supported Metal Phthalocyanine Catalysts

With the increasing of using motor vehicles,the problem of environmental pollution is becoming more and more serious.The removal of sulfur-containing compounds from liquid fuel has become an important problem.Oxidative desulfurization technology has been demonstrated to be an effectively method for the removal of sulfur-containing compounds in petroleum refining.Metalophthalocyanines(MPcs)have been widely used as oxidized desulfurization catalysts because of the stable planar structure.In this paper,a series of non-substituted metalophthalocyanines,tetracarboxylic-substituted metalophthalocyanines and carboxyl-substituted polymeric metal phthalocyanines were synthesized.Metalophthalocyanines were supported on semiconductors SnO2,Zn2Sn4a and graphene oxide by hydrothermal method.The oxidized desulfurization performance was evaluated by the degradation of thiophene.The main work of this paper is as follows:1.A series of non-substituted metal phthalocyanines,tetracarboxylic-substituted metal phthalocyanines and polymerized metal phthalocyanines with different conjugated structures were prepared by the solid-state melting method.The structures were characterized by IR and UV-Vis spectra.The desulfurization performance of different kinds of metal phthalocyanines was studied by the degradation of thiophene taking oxygen molecular as oxidant under normal temperature and pressure.The results showed that the order of desulfurization is MPc<MTcPc<MPPcTc.The conjugated system of metal phthalocyanine molecule is the main factor affecting its oxidative desulfurization performance.2.Metallophthalocyanines were loaded on the semiconductors SnO2 and Zn2SnO4 respectively by hydrothermal method and characterized by Infrared spectroscopy(IR),Scanning electron microsceopy(SEM),X-ray diffraction(XRD)and X-ray Photoelectron spectroscopy(XPS).The desulfurization performance of different kinds of metal phthalocyanines was studied by the degradation of thiophene taking oxygen molecular as oxidant under normal temperature and pressure.The results showed that the desulfurization conversion rate of ZnTcPc/SnO2 composites reached 98.42%,and the desulfurization conversion rate of ZnTcPc/Zn2SnO4 composites reached 97.95%,which achieved deep desulfurization.3.A series of Metal phthalocyanine/Graphene oxide(MPc/GO)and Ploymerized metal phthalocyanine/Graphene oxide(MPPc/GO)composites were prepared by in-situ hydrothermal method and characterized by IR spectra,XRD,SEM and XPS.The desulfurization performance of different kinds of metal phthalocyanines was studied by the degradation of thiophene taking oxygen molecular as oxidant under normal temperature and pressure.The results showed that the electron mobility of the metal phthalocyanine was greatly increased and the catalytic efficiency was obviously improved after the metal phthalocyanine was supported on the graphene oxide.The catalytic efficiency of CoPc/GO was 9.80%higher than that of the CoPc.The desulfurization efficiency of NiPPc/GO reached 96.98%after 180min.According to a series of experimental results,the catalytic mechanism of"adsorption-catalytic oxidation" was proposed,which provided theoretical guidance for the practical application of desulfurization catalyst.