裂解汽油中噻吩硫在Co-Mo/Al2O3上的催化加氢宏观动力学

The macro-kinetic investiqations for catalytic hydrodelsulfurization of pyrolysis gasoline over an industrial Co-Mo/Al2O3 catalyst were carried out in an adiabatic tubular fixedbed reactor under the conditions: 2.5MPa～3.9MPa, 513K～655K, H2/pyrolysisgasoline molar ratio 1.8~3.5, and the mass concentration of thiophene, methylthiophene and dimethylthiophene in the feed pyrolysisgasoline, 838×10－6, 137×10－6~723×10－6 and 192×10－6~723×10－6, respectively. By means of Powell optimal method and Merson integral method, the power-law type macrokinetic models for the catalytic hydrodelsulfurization of pyrolysis gasoline were developed. The reaction orders of thiophene, methylthiophene and dimethylthiophene are 0.721, 0.735 and 0.870, respectively, and the activation energies are 70.0kJ·mol－1, 67.9kJ·mol－1 and 59.9kJ·mol－1, respectively. The conversion of thiophenic sulfides increases with the reaction pressure, but this increase is obviously slowed down at the reaction pressure above 3.5MPa. The increase of reaction temperature is beneficial to the conversion enhancement of thiophenic sulfides, especially above 563K. When the reaction temperature increases above 593K, the correlation between the conversion of thiophenic sulfides and temperature is almost linear. Therefore, for the Co-Mo/Al2O3 catalyst used, the favorable operating pressure is about 3.5MPa, and the reaction temperature should be higher than 593K.