甲醇合成铜基催化剂硫化氢中毒研究(Ⅰ)——硫化氢中毒本征失活动力学

HYDROGEN SULFIDE POISONING OF METHANOL SYNTHESIS Cu-BASED CATALYST (I) INTRINSIC DEACTIVATION KINETICS

研究了甲醇合成C207铜基催化剂硫化氢中毒本征失活动力学.研究表明,硫化氢分压增加,失活速率加快;温度升高,失活速率加快.本征失活速率方程为r_d=-da/dr=0.1474×10^(12)exp(-81128/R_gT)P_(H_2s^a)

The global reaction rates of methanol decomposition of C207 Cu-based catalyst under atmospheric pressure were determined in an internal recycle gradientless reactor and mlet. 7.19×10-4) with addition of H2S for 4 hours, 8 hours and 12 hours respectively. The pore size distribution, and the tortuosity factors of φ 5 × 5mm cyindrica catalyst pellets were also measured. Hydrogen sulfide poisoning of commerial catalyst is considered as surface poisoning. The experimental values of non-poisoned dimensionless radius xc by Auger Electron Spectroscopy were 0.038 0.916 and 0.960 with addition of H2S for 4 hours, 8 hours and 12 hours respectively, which agreed with the values calculated by intrinsic deactivation kinetics. The single component model and multicomponent model of effectiveness factor ξd of surface poisoned catalyst were presented and solved by orthogonal collocation and Broyden method. Not only surface poisoning but also center equilibrium dead zone was found in catalyst pellets. The average of absolute values of relative deviations between experimental values and calculated values lor ξd was less than 11%. The models can be used to calculate the effectiveness factor of surface poisoned catalyst.