Department of Material Process Engineering, Graduate School of Engineering, Kyushu University, Motooka 744, Fukuoka 819-0395, Japan.
J Colloid Interface Sci. 2012 Apr 15;372(1):121-9. doi: 10.1016/j.jcis.2012.01.019. Epub 2012 Jan 18.
Unsupported nanosized MoS(2) and CoMo-sulfide catalysts were synthesized, and their catalytic performances for the deep hydrodesulfurization (HDS) of treated gas oil were investigated as compared with that of a CoMo/Al(2)O(3) catalyst. The HDS reactions were carried out in a batch autoclave reactor at 340 °C and 3 MPa H(2). The CoMo-sulfide catalyst shows the highest activity and can reduce the sulfur content to less than 10 ppm. The decrease in total sulfur content as a function of reaction time was found to follow pseudo-second order kinetics (empirical form). The change in the concentration of some individual representative sulfur-containing species in gas oil as a function of time was found to follow pseudo-first-order kinetics. However, the change in combined concentration of these species in the gas oil during HDS with the reaction time was found to corroborate pseudo-second-order kinetics. A kinetic model approach was proposed from which an estimation of the intrinsic kinetic data can be achieved. The model fitted the obtained data reasonably well, suggesting its potential for better assessment of the catalytic activity in the HDS of real feedstock. The study reveals that ranking of catalyst activities using model refractory sulfur-containing compounds does not necessarily imply a typical rank in case of investigating the real feedstocks.
未经支持的纳米 MoS(2) 和 CoMo-硫化物催化剂被合成，并将其用于处理过的瓦斯油的深度加氢脱硫 (HDS) 的催化性能与 CoMo/Al(2)O(3) 催化剂进行了比较。HDS 反应在 340°C 和 3 MPa H(2) 的间歇式高压釜反应器中进行。CoMo-硫化物催化剂表现出最高的活性，可将硫含量降低到 10 ppm 以下。发现总硫含量随反应时间的变化遵循拟二级动力学（经验形式）。发现瓦斯油中一些代表性含硫物种的浓度随时间的变化遵循拟一级动力学。然而，在 HDS 过程中，这些物种在瓦斯油中的总浓度随反应时间的变化与拟二级动力学相符。提出了一种动力学模型方法，可以从中获得对内在动力学数据的估计。该模型很好地拟合了所得数据，表明其在评估真实原料 HDS 中的催化活性方面具有潜力。研究表明，使用模型难处理含硫化合物对催化剂活性进行排序，在研究真实原料时并不一定意味着典型的排序。
