| Deacon reaction is an effective way to solve a large amount of by-product hydrogen chloride with low energy consumption,high efficiency,and environmental friendliness,in which Ru-based catalyst is the only commercial catalyst for catalytic oxidation of hydrogen chloride to chlorine because of its high activity and excellent stability.However,its expensive price restricts the application promotion of this technology,so how to reduce the cost of this catalyst is still one of the urgent problems to be solved.In this paper,rutile Ti O2 carriers were used to study the effect of modified carriers loaded with Ru O2 on the Deacon reaction by introducing metal ions.The main results obtained are as follows:Firstly,Ce4+was successfully doped into the carrier Ti O2 by the method of excess impregnation,and the use of Ce4+changed the lattice parameters of Ti O2.1.0wt.%Ru O2/Ce-Ti O2 catalyst was produced by adsorption and filtration impregnation.Compared with the undoped 1.0 wt.%Ru O2/Ti O2 catalyst,The 1.0 wt.%Ru O2/Ce-Ti O2-0.5 catalyst exhibits more excellent HCl catalytic oxidation performance,among which,when the doping amount of Ce4+in the carrier was 0.5wt.%,1.0 wt.%Ru O2/Ce-Ti O2-0.5 catalyzed the oxidation of HCl with the best activity（61.79%）,and its Cl2 yield was as high as 108 mol Cl2 min-1 mol Ru-1.Compared with the undoped 1.0 wt.%Ru O2/Ti O2 catalyst,its performance improved by 22%.Combined with various characterization techniques,the Ce4+doped Ti O2 carrier can effectively improve the dispersion of the active component Ru O2 and enhance the interaction between Ru O2 and the carrier,while the oxygen vacancies brought by Ce4+will make the O2 easier to adsorb and dissociate,thus improving its activity of HCl oxidation under oxygen-poor conditions.Secondly,Nb-Ti O2 carriers with different Nb loadings were prepared by sol-gel method,and then 1.wt.%Ru O2/Nb-Ti O2 catalysts were produced by adsorption and filtration impregnation method loaded with the active ingredient Ru O2.When the amount of n（Nb/（Nb+Ti））was 0.05,its temporal yield of Cl2 was 38.3 g Cl2 gcat.-1 h-1,compared with the undoped Ru O2/Ti O2 catalyst which improved the conversion of HCl by 15%.Combined with all the characterizations,the introduction of the appropriate amount of Nb can influence the chemical environment of the active component Ru O2,improve the sintering resistance of the catalyst,and increase the performance of the catalyst.The doping of metal ions can effectively change the lattice parameters of the carrier Ti O2,which can not only affect the dispersion of the loaded active component Ru O2,but also improve its utilization rate and reduce the negative loading of Ru,enhance the interaction between Ru O2 and the carrier and improve the anti-sintering ability of the catalyst.In addition,the oxygen vacancies brought by the doped ions may facilitate the adsorption and dissociation of O2,improving its catalytic performance under oxygen-poor conditions.In this thesis,the high activity and low loading Ru-based catalysts prepared largely reduce the industrial cost of the Deacon reaction and provide a favorable scientific basis and technical support for the efficient recovery and utilization of chlorine resources. |
