Study On Preparation Of Dinuclear Phthalocyanine - Molecular Sieve Oxidative Desulfurization Catalyst

With the development of social economy, the environmental pollution has become more severe. The occurrence of hazy weather is obvious, which mainly attributed to the oil quality. So the increasingly stringent regulations have been established worldwide to limit the sulfur level, while a near-zero sulfur content not only is the main problem we face, but also our goal. It is well known that mercaptan, sulfur ether, dibenzothiophene and its derivatives are in the petroleum. Due to the steric hindrance and low reactivity of these sulfur compounds, it is difficult to remove some alkylated aromatic S-compounds such as dibenzothiophene and its derivatives.In this paper, the dibenzothiophene, which is our focus research object, is the source of the sulfur compound and the load type catalysts were also synthesized. M2 (PcTN)2 (M=Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) was obtained by liquid phase method, while Na2S is used to get the M2 (PcAN)2 (M=Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) for the futher bonding with the molecular sieve. The synthetic product was characterized by IR and UV.M2 (PcAN)2 (M=Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) and functionalization of W-HZSM-5 were obtained. M2(PcAN)2-W-HZSM-5(M= Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) was synthesized by anchoring M2 (PcAN)2 (M= Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) onto W-HZSM-5. In addition, the M2(PcTN)2/W-HZSM-5 was prepared following doping M2(PcTN)2 into the W-HZSM-5. However, many efforts have been implemented to develop single zeolite catalysts promoted by metal ions and we firstly reported M-HZSM-5-MCM-41 (M=Fe (â…¡), Co (â…¡), Ni (â…¡), Cu (â…¡), Zn (â…¡), Mn (â…¡)) as well. Superior performance of Cu-HZSM-5-MCM-41 combined with phthalocyanine by anchoring and doping method to obtain the desulfurization catalyst. The three kinds of catalysts were characterized by IR, XRD, SEM, TEM, ICP, XPS, TG-DSC and N2 adsorption.The oxidative desulfurization experiments were carried out under the presence of oxygen. Reaction time, temperature and the amount of hydrogen peroxide were investigated as the important parameters for optimization of the reaction. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Furthermore, a possible process of oxidative desulfurization, reaction mechanism, recycling use of the catalyst and the reaction products were proposed, The main conclusion is as follows:(1)The activity of selectivity followed the order:T> BT> DBT under the same conditions.(2)The order of superior desulfurization performance:Cu2(PcAN)2-W-HZSM-5> Cu2(PcAN)2-W-HZSM-5/MCM-41> Cu2(PcTN)2/W-HZSM-5> Cu2(PcTN)2/ W-HZSM-5/MCM-41.