化学学报 ›› 2002, Vol. 60 ›› Issue (10): 1806-1810. 上一篇    下一篇

研究论文

金属氧化物脱硫/固硫反应动力学中的补偿效应

郭汉贤;樊惠玲;李彦旭   

  1. 太原理工大学煤化工研究所,太原(030024)
  • 发布日期:2002-10-15

Compensation Effect in Kinetics of Desulfurization and SO_2 Fixing by Metal Oxides

Guo Hanxian;Fan Huiling;Li Yanxu   

  1. Institute for Chemical Engineering of Cool, Taiyuan University of Technology,Taiyuan(030024)
  • Published:2002-10-15

讨论了氧化锌中温脱硫、氧化钙高温固硫的补偿效应。实验发现,脱除硫化氢 和二氧化硫在反应过程中均先后在动力学控制区和粒子扩散控制区进行。改变非硫 气氛或添加催化组分,所得热重数据均可有效粒子模型处理。lnk_0-E_a及lnD_0- E_D呈线性关系。给出了补偿效应的理论解释。指出晶粒表面及内部缺陷等的随机 指数分布是出现该效应的主要原因。计算了两反应体系的等动力学温度。讨论了高 于和低于该温度时,反应活性与活化能不同的变化规律。并对粒子扩散化学反应性 质进行了探讨。

关键词: 脱硫, 氧化锌, 硫化氢, 二氧化硫, 活化能

Compensation effect of ZnO desulfurization and SO_2 fixing by CaO at high temperatures is discussed. Experiments showed that both the H_2S removal and SO_2 fixing were first under surface reaction control before the eventual grain diffusion control. The thermal gravimetric data were obtained during change of reaction atmosphere or additive used for a series of samples and were well simulated by using equivalent grain model. There were linear relationships between logarithms of the pre-exponential factor lnk_0, lnD_0 and activation energies E_a, E_D, respectively. Furthermore, the compensation effect could be explained based on assumption of exponential energy distribution function over crystal surface and its inner as well. There existed different kinetic behavior when operating temperature was above or below the isokinetic temperature T_S. Above the isokinetic temperature T_S, the greater the activation energy, the higher activity the desulfurizer/SO_2 fixer had. It appeared that the grain diffusion of sulfur contained ion was very different from the molecule diffusion in pore.

Key words: DESULFURIZATION, ZINC OXIDE, HYDROGEN SULFIDE, SULFUR DIOXIDE, ACTIVATION ENERGY

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