V-Ce复合氧化物催化间二甲苯气相氨氧化制间苯二甲腈  

Gas Phase Ammoxidation of meta-Xylene to Isophthalonitrile over V-Ce Composite Oxides

作　　者：习鹏博 冯冰 顾龙勤[2] 杨为民[1,2] XI Pengbo;FENG Bing;GU Longqin;YANG Weimin(School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;State Key Laboratory of Green Chemical Engineering and Industrial Catalysis,Shanghai Research Institute of Petrochemical Technology,SINOPEC,Shanghai 201208,China)

机构地区：[1]华东理工大学化工学院,上海200237 [2]中国石油化工股份有限公司上海石油化工研究院绿色化工与工业催化国家重点实验室,上海201208

出　　处：《化学反应工程与工艺》2020年第3期222-229,共8页Chemical Reaction Engineering and Technology

摘　　要：采用喷雾干燥成型的方法,制备了不同Ce/V比的无Cr环境友好型V-Ce复合氧化物催化剂,在流化床反应器中考察了Ce/V比及Mo助剂对催化剂反应性能的影响,并通过X射线衍射(XRD)、拉曼光谱、氢气程序升温还原(H2-TPR)、NH3程序升温脱附(NH3-TPD)和X射线光电子能谱(XPS)等方法对催化剂进行了表征。结果表明,CeVO_(4)晶相对于提高间苯二甲腈(IPN)收率具有关键作用,随着Ce/V比的提高,逐渐出现CeO_(2)晶相,主产物IPN选择性下降。V-Ce复合氧化物催化剂表面以弱酸为主。V_(1)Ce_(0.8)/SiO_(2)表现出较优的催化性能,其IPN收率为60.0%。进一步添加助剂Mo,可显著降低深度氧化产物COx选择性,当Mo/V比为0.10时,催化剂的IPN收率可提高至62.5%。Environmental friendly and Cr-free composite oxide catalysts with different Ce/V ratios were prepared through spray drying method.The effect of Ce/V ratio and the addition of Mo on the ammoxidation performance of the catalysts were investigated in a fluid bed reactor.The structure of the catalysts was characterized by X-ray diffraction(XRD),Raman spectra,H2 temperature programmed reduction(H2-TPR),NH3 temperature programmed desorption(NH3-TPD)and X-ray photoelectron spectroscopy(XPS).The characterization results showed that the catalysts consisting of CeVO_(4) crystal phase played a key role in improving the yield of isophtalonitrile(IPN).With the increase of Ce/V ratio,the CeO_(2) crystal phase appeared gradually,and the selectivity of the main product IPN decreased.The surface acid site of the V-Ce composite oxide catalysts was mainly weak site.The V_(1)Ce_(0.8)/SiO_(2) sample exhibited the best catalytic performance among the four catalysts with different Ce/V ratios,with IPN yield of 60.0%.Moreover,the addition of Mo promoter into the V_(1)Ce_(0.8)/SiO_(2) sample could suppress the COx formation and further improve the gas-phase ammoxidation performance.The IPN yield could reach 62.5% when the Mo/V ratio was 0.10.

关 键 词：流化床 气相氨氧化 V-Ce催化剂 间苯二甲腈 

分 类 号：TQ426.94[化学工程] O643.322[理学—物理化学]