Cu-Ni/γ-Al2O3催化剂上二甘醇催化氨化合成吗啉的本征动力学研究  

Intrinsic Kinetics of Morpholine Synthesis via Diethylene Glycol Amination Catalyzed by Cu-Ni/γ-Al_2O_3

作　　者：赵全忠 赵祯霞[1] 邹昀[1] 韦藤幼[1] 童张法[1] ZHAO Quan-zhong;ZHAO Zhen-xia;ZOU Yun;WEI Teng-you;TONG Zhang-fa(Guangxi Colleges and Universities Key Laboratory of New Chemical Application Technology in Resources,School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China)

机构地区：[1]广西大学化学化工学院,广西资源化工应用新技术高校重点实验室,广西南宁530004

出　　处：《高校化学工程学报》2018年第6期1353-1358,共6页Journal of Chemical Engineering of Chinese Universities

基　　金：广西自然科学基金重点项目(2017GXNSFDA198047);广西自然科学基金创新团队项目(2016GXNSFGA380003);广西石化资源加工及过程强化技术重点实验室主任基金(2017Z001,2017Z010).

摘　　要：在固定床反应器中研究了Cu-Ni/γ-Al_2O_3催化剂上二甘醇氨化脱水合成吗啉的本征动力学。通过增大进料气体速度和减小催化剂粒径,分别消除内、外扩散的影响;在温度483～513 K,体积空速1.73～4.32 s^(-1),压力1.7 MPa,氨醇摩尔比大于10的条件下,考察了温度与进料空速对二甘醇转化率的影响;使用幂律模型描述反应动力学过程,并拟合实验数据估算模型参数。结果表明:当体积空速大于4.32 s^(-1),催化剂粒径40～80目,内、外扩散影响均已消除;二甘醇氨化合成吗啉的反应活化能为43.97 kJ?mol^(-1),对二甘醇的反应级数为1.45。二甘醇反应速率实验值与模型计算值比较和统计检验结果表明模型是合适的。The intrinsic kinetics of morpholine synthesis via diethylene glycol amination was studied using Cu-Ni/γ-Al2O3as the catalyst in a fixed-bed reactor.The internal and external diffusion resistances were eliminated by increasing feed gas flow rate and reducing catalyst particle size.Effects of reaction temperature and space velocity on diethylene glycol conversion were studied under conditions of:reaction temperature483~513K,space velocity1.73~4.32s-1,reaction pressure1.7MPa and molar ratio of ammonia to diethylene glycol>10.The reaction kinetics was described by power-law model and parameters were obtained by experimental fitting.The results show that the internal and external diffusion resistances can be eliminated when the space velocity is over4.32s-1and the catalyst particle size is40~80mesh.The reaction activation energy is43.97kJ.mo-1and the reaction order is1.45for diethylene glycol.The modeling results are consistent with the experimental data,which together with statistical results indicate that the model is reliable.

关 键 词：吗啉 Cu-Ni/γ-Al2O3催化剂 本征动力学 固定床反应器 幂律模型 

分 类 号：TQ032.4[化学工程] O626[理学—有机化学]