Study On Desulfurization Performance Of Metal Phthalocyanine Supported With NIT Nitroxyl Radical

Sulfur-content compounds in fuel for vehicles caused a large number of SO₂ and other pollutants,which resulted in serious environmental pollution problems such as acid rain,smog?PM2.5?and others pollution problems.The production of ultra-low sulfur fuel and sulfur-free fuel has become an important measure to solve environmental and energy problems.Oxidation desulphurization technology is one of the most effective measures for deep desulphurization.Metallophthalocyanine could activate oxygen molecules and oxide the sulfur-content compounds in fuel.However,metallophthalocyanines have some disadvantages for catalytic oxidative desulphurization reaction,which limited its application in practical production.Based on the research results,this paper designed and synthesized the octachloro-substituted metallophthalocyanine and two series of NIT nitrogen-oxygen free radicals.The NIT nitrogen-oxygen free radicals were then immobilized on the octachloro-substituted metal phthalocyanine with chemical bond to prepare the metallophthalocyanine/NIT nitrogen-oxygen free radicals catalysts.The catalytic performance of composites was investigated taking thiophene and dibenzothiophene as model sulfur-content compounds.The influence of different catalyst structures on desulfurization efficiency were discussed.The results revealed the reaction mechanism of catalytic oxidation desulfurzation.The main works are as follow:Firstly,octachloro-substituted metallophthalocyanines were preparated and the desulfurization performance was investigated;Metallophthalocyanines MTc Pc Cl₈?M=Mn?II?,Fe?II?,Co?II?,Ni?II?,Cu?II?,Zn?II??were synthesized taking six different metal salts as raw materials.The catalytic performance of catalysts was investigated taking thiophene and dibenzothiophene as model sulfur-content compounds.The desulfurization efficiency of Ni Tc Pc Cl₈ for thiophene could reach to 99.46%after 3 h at room temperature under natural light;The desulfurization efficiency of Ni Tc Pc Cl₈ for dibenzothiophene could reach to 94.42%after 3 h at 60?under natural light.The results realized deep desulfurization;The research of desulfurization reaction mechanism showed that the central metal ions and the structure of phthalocyanine ring are the main factors affecting the desulfurization efficiency of phthalocyanine.Secodly,The NIT nitrogen-oxygen free radical were preparated and the desulfurization performance was investigated;The NIT nitrogen-oxygen free radicals with different substituents were synthesized taking benzoyl chloride and benzaldehyde as different substituents.The structural characteristics were determined by FT-IR,UV-Vis,MS and EPR.The catalytic performance of catalysts was investigated taking thiophene as model sulfur-content compounds under normal temperature and pressure.The results showed that the two series of NIT nitrogen-oxygen free radicals had good desulphurization effect.The catalytic performance of fluor-based L-prolinol NIT nitrogen-oxygen free radicals reached to 96.71%.Finally,the metallophthalocyanine/NIT nitrogen-oxygen free radicals catalysts were synthesized and the desulfurization performance was investigated.The NIT nitrogen-oxygen free radicals were immobilized on the octachloro-substituted metal phthalocyanine with the amidation reaction.The catalytic performance of catalysts was investigated taking thiophene as model sulfur-content compounds.The results showed that the desulfurization efficiency of the metal phthalocyanine is significantly improved when the NIT nitrogen oxide radicals were immobilized.The catalytic reaction mechanism is preliminary studied.