钒磷氧催化剂在水蒸气/空气/氮气活化气氛下的演变规律  

Evolution Law of Vanadium Phosphorus Oxide Catalyst in H_(2)O/Air/N_(2)Activation Atmosphere

作　　者：谢成思 王海波[2] 于越 蒋斌波[1] 杨遥[1] 黄正梁[1] 王靖岱[1] 阳永荣[1] XIE Chengsi;WANG Haibo;YU Yue;JIANG Binbo;YANG Yao;HUANG Zhengliang;WANG Jingdai;YANG Yongrong(College of Chemical and Biochemical Engineering,State Key Laboratory of Chemical Engineering,Zhejiang University,Hangzhou 310027,China;Dalian Research Institute of Petroleum and Petrochemicals,SINOPEC,Dalian 116041,China)

机构地区：[1]浙江大学化学工程联合国家重点实验室化学工程与生物工程学院,浙江杭州310027 [2]中国石化大连石油化工研究院,辽宁大连116041

出　　处：《石油学报（石油加工）》2022年第5期1021-1031,共11页Acta Petrolei Sinica(Petroleum Processing Section)

摘　　要：钒磷氧(VPO)催化剂的活化过程对催化剂的正丁烷转化率、顺酐选择性具有重要影响,目前对非原位活化过程中活化条件对催化剂结构性能的影响还所知甚少。研究了非原位活化过程中水蒸气体积分数、空气体积分数、活化温度及活化时间对催化剂性能的影响规律。结合XRD、SEM、BET和XPS等表征手段研究了水蒸气对催化剂结构的影响,证明了水蒸气/空气/氮气(H_(2)O/Air/N_(2))活化气氛中水蒸气对VPO催化剂中(VO)_(2)P_( 2)O _(7)晶体的形成及V^(4+)氧化为V^(5+)的促进作用。根据不同活化时间催化剂的XRD和Raman分析结果,提出了H_(2)O/Air/N_(2)活化气氛下VPO催化剂的晶相演变过程。最后,提出了一种获取高稳态性能VPO催化剂的非原位活化方法,正丁烷氧化生成顺酐的长周期考评结果表明,该方法活化的催化剂稳态性能达到了与原位活化催化剂相同的水平,而活化时间由原位活化的超过100 h缩短至10 h。The activation process of vanadium phosphorus oxide(VPO)catalyst has a major impact on the n-butane conversion and maleic anhydride(MA)selectivity of the catalyst.At present,less is known about the impact of activation conditions on the structural performance of the catalyst in the ex situ activation process.Hence,the influence laws of vapor volume fraction,air volume fraction,activation temperature and activation time on the catalyst performance during the ex situ activation were investigated.Further,the impact of vapor on catalyst structure was studied by means of XRD,SEM,BET,XPS and other characterization means,proving that the vapor in H_(2)O/Air/N_(2)activation atmosphere played a role in promoting the formation of(VO)P_(2)O_(7)crystals and the oxidation of V^(4+)to V^(5+).Based on the XRD and Raman analysis results of the catalyst with different activation time,this paper proposes the evolution process of crystal phase for the VPO catalyst in H_(2)O/Air/N_(2)atmosphere,and finally puts forwards an ex situ activation method for obtaining VPO catalyst with high steady-state performance.The long-term evaluation results of oxidation from n-butane to maleic anhydride shows that the steady-state performance of the catalyst activated by this method has reached the same level as in situ activation method,and the activation time has been shortened from more than 100 h to 10 h.

关 键 词：正丁烷 钒磷氧催化剂 顺酐 活化方法 水蒸气 晶相演变 

分 类 号：TQ139.1[化学工程—无机化工]