Preparation And Study Of ZrO ₂/3YSZ Supported High Temperature Granular Desulfurizer

The preparation of regenerative desulfurizer capable of stabilizing reaction and removing hydrogen sulfide gas with high precision in high temperature reduction atmosphere can lay a solid foundation for integrated coal gasification combined cycling?IGCC?and solid oxide fuel cell?SOFC?power generation technologies.In this paper,the preparation and properties of high temperature regenerative desulfurizer are studied.The experimental results are composed of experimental data and characterization results.The core research contents are as follows:?1?The powder desulfurizer with different cerium zirconium content ratio was prepared by sol-gel method,and the performance of different desulfurizer was compared through 20 desulphurization regeneration cycle experiments.According to the phase formation law of Ce _0.8Zr_0.2O₂ and Ce _0.2Zr_0.8O₂,cerium-zirconium solid solution is not unique,precursor solutions were prepared by the ratio of metal cations nZr⁴⁺:nMn²⁺:nCe³⁺=12:5:3 and nZr⁴⁺:nMn²⁺:nCe³⁺=3:5:12,respectively.Finally,the sol-gel method was used to prepare powder desulfurizer.The analysis of desulfurization experimental data shows that the average desulfurization accuracy of Zr₃Mn₅Ce₁₂O_X desulfurizer with high cerium content is 0³ppm,and the performance of 20 desulfurization experiments has not decreased;the average desulfurization accuracy of Zr₁₂Mn₅Ce₃O_X desulfurizer with high zirconium content is 1⁹ppm,and the performance of 17²0 desulfurization experiments has declined significantly.It is concluded that the stability of desulfurizer decreases with the increase of zirconium content,and the desulfurization accuracy of desulfurizer improves with the increase of cerium content.?2?Zirconia carrier doped with yttrium oxide was prepared by phase inversion method,and then the carrier was vacuum impregnated to prepare desulfurizer.Gas resistance experiment shows that carrier impregnated desulfurizer has no gas resistance,and the higher the filling height of powder desulfurizer,the greater the gas resistance.The porosity of the carrier was 23%by Archimedes method and characterization shows that the carrier desulfurizer is filled with divergent pore structure.The desulfurization experiment found that the larger the carrier load,the better the desulfurization effect of desulfurizer.The four desulfurization regeneration curves of CMZm have good reproducibility,and the desulfurization accuracy is 0²ppm,respectively.However,the breakthrough sulfur capacity of CMZm is low,reaching only 499.3 mg?sulfur?/100g?desulfurizer?.?3?Combining the advantages of large sulfur penetration capacity of powder desulfurizer and small gas resistance of carrier desulfurizer,the powder desulfurizer was processed by phase inversion method.The stability of columnar desulfurizer was examined by 35 desulfurization regeneration experiments.Experiments show that columnar desulfurizer is better than spherical desulfurizer at 800?.The desulfurization effect of columnar desulfurizer is different at 400,500,600,700 and800?,the higher the temperature is,The higher the temperature is,the better the performance of desulfurizer would be.Thirty-five desulfurization regeneration experiments showed that the desulfurizer had stable performance.The desulfurization accuracy of the 16th to 35th desulfurization experiments was stable at 0¹ppm for a long time,and the breakthrough sulfur capacity could reach 2.59g?sulfur?/100g?desulfurizer?.