CuO/ZnO/Al_(2)O_(3)改性催化剂上CH_(3)OH重整制氢的研究  

CH3OH Reforming for Hydrogen over CuO/ZnO/Al_(2)O_(3) Modified Catalyst

作　　者：王康 李涛[1] 张海涛[1] WANG Kang;LI Tao;ZHANG Haitao(Engineering Research Center of Large Scale Reactor Engineering and Technology,Ministry of Education,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学大型工业反应器工程教育部工程研究中心,上海200237

出　　处：《华东理工大学学报（自然科学版）》2022年第3期281-289,共9页Journal of East China University of Science and Technology

摘　　要：采用Langmuir-Hinshelwood型双速率动力学模型方程对CH_(3)OH水蒸气重整制氢反应本征动力学实验数据进行拟合,同时探讨了反应条件对CH_(3)OH水蒸气重整制氢反应的影响。结果表明:反应器出口气体中CO和CO_(2)摩尔流率的计算值与实验值较吻合,说明所采用的双速率动力学模型适用。考察CuO/ZnO/Al_(2)O_(3)改性催化剂在200℃和300℃下的失活现象,表征结果表明,催化剂失活的主要原因有热烧结、催化剂比表面积减小、介孔比例减少、活性组分CuO流失、CuO晶粒变大等,但高温反应产生的高含量CO对催化剂失活没有产生明显影响。The effects of reaction conditions on hydrogen production from methanol steam reforming were discussed.The experimental results showed that the optimal temperature of the reaction was about 240℃.High temperature increased the selectivity of CO,and low temperature decreased the conversion rate of CH_(3)OH.When the molar ratio of H_(2)O to CH_(3)OH increased,the conversion rate of CH_(3)OH increased and the selectivity of CO decreased.If the molar ratio of H_(2)O to CH_(3)OH was too high,more energy would be consumed.To ensure the conversion rate of CH_(3)OH,the liquid hourly space velocity of feed liquid was appropriately increased.The Langmuir-Hinshelwood tworate dynamics model equation was used to fit the experimental data of intrinsic dynamics.The calculated values of molar flow rates of CO and CO_(2) in the gas products at the reactor outlet were in good agreement with the experimental values,and the two-rate model was applicable.The deactivation of CuO/ZnO/Al_(2)O_(3) modified catalysts at 200℃and 300℃was also investigated.Using BET,XRF,XRD and CO-TPD,it was found that the main reasons for the deactivation of the catalysts were,in addition to hot sintering,the reduction of specific surface area and mesoporous ratio,the CuO loss,and the increase of CuO grain size.The high content of CO produced in the high temperature had no obvious effect on catalyst deactivation.

关 键 词：甲醇水蒸气重整 制氢 CuO-ZnO-Al_(2)O_(3)催化剂 反应动力学 催化剂失活 

分 类 号：TQ013.2[化学工程]