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-Al2O3
赵全忠,赵祯霞,邹昀,韦藤幼,童张法
摘要(Abstract):
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。
关键词(KeyWords): 吗啉;Cu-Ni/γ-Al_2O_3催化剂;本征动力学;固定床反应器;幂律模型
基金项目(Foundation): 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)
作者(Author): 赵全忠,赵祯霞,邹昀,韦藤幼,童张法
参考文献(References):
- [1]Diao P C,Li Q,Hu M J,et al.Synthesis and biological evaluation of novel indole-pyrimidine hybrids bearing morpholine and thiomorpholine moieties[J].European Journal of Medicinal Chemistry,2017,134(7):110-118.
- [2]Cebeci Y U,Ozdemir S B,Ceylan S,et al.Microwave-assisted synthesis of some hybrid molecules derived from morpholine and investigation of their antimicrobial activities[J].Chemistryselect,2017,2(35):11402-11407.
- [3]LU Qiao-sen(卢乔森),HUANG Yun-hong(黄韵弘),HUANG Chao-ming(黄超明),et al.Progress of production and application of N-acylated morpholine(酰化吗啉生产技术及其应用进展)[J].Applied Chemical Industry(应用化工),2016,45(8):1566-1570.
- [4]HOU Xue(侯雪),BAI Xiao-ying(白小莹),ZHANG Sheng-jun(张胜军).Conservation method for natural latex and ammonia-free conservant therefore(一种天然胶乳无氨保存剂及其保存方法):CN,106565862A[P].2015-10-12.
- [5]CHEN Han-geng(陈汉庚),ZHANG Tao(张涛),LUO Ming(罗明),et al.Synthesis of N-methylmorpholine over the catalyst Cu-Ni-Co/Al2O3 in the gas phase(Cu-Ni-Co/Al2O3气固相催化合成N-甲基吗啉)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2009,23(5):801-806.
- [6]Krabbe S W,Chan V S,Franczyk T S,et al.Copper-catalyzed aerobic oxidative amidation of benzyl alcohols[J].Journal of Organic Chemistry,2016,81(22):10688-10697.
- [7]Kimura H,Tsutsumi S I,Tsukada K.Reusability of the Cu/Ni-based colloidal catalysts stabilized by carboxylates of alkali-earth metals for the one-step amination of dodecyl alcohol and dimethylamine[J].Applied Catalysis A General,2005,292(1):281-286.
- [8]MA Tian-qi(马天奇),WEI Tian-yu(魏天宇),PIAN Yan-jie(骈岩杰),et al.Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline(丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能)[J].CIESC Journal(化工学报),2014,65(3):905-911.
- [9]DENG Hong(邓红),WEI Teng-you(韦藤幼),TONG Zhang-fa(童张法).Preparation of catalyst for morpholine synthesis by ultrasonic irradiation impregnation method and its catalytic behavior(超声浸渍法制备吗啉催化剂及其催化性能)[J].Chemical Industry and Engineering Progress(化工进展),2015,34(2):425-429
- [10]YUAN Shi-jian(袁诗剑),TONG Zhang-fa(童张法),ZHAO Zhen-xia(赵祯霞),et al.Preparation of Cu-NiO@Al2O3 morpholine catalysts by ethylene glycol auxiliary impregnation and its catalytic performance(乙二醇辅助浸渍法制备Cu-NiO@Al2O3吗啉催化剂及其催化性能)[J].Guangxi Science(广西科学),2016,23(3):261-265.
- [11]YANG Heng-dong(杨恒东),CUI Mi-fen(崔咪芬),LI You-lin(李有林),et al.Reaction networks and dynamics of isopropyl acetate hydrogenation to produce dual alcohols(醋酸异丙酯催化加氢制双醇反应网络及动力学研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2016,30(4):836-842.
- [12]LUO Hu(罗虎).Research on the synthesis of morpholine and its alkyl derivatives(吗啉及其烷基衍生物的合成工艺研究)[D].Hangzhou(杭州):Zhejiang University(浙江大学),2012.
- [13]Peter M,Fichtl M B,Ruland H,et al.Detailed kinetic modeling of methanol synthesis over a ternary copper catalyst[J].Chemical Engineering Journal,2012,203(5):480-491.
- [14]ZHANG Yue-cheng(张月成),ZHANG Di(张頔),ZHAO Ji-quan(赵继全).Intrinsic kinetics for amination of ethanol to acetonitrile over Co-Ni/γ-Al2O3 catalyst(Co-Ni/γ-Al2O3催化剂上乙醇催化氨化合成乙腈反应的本征动力学)[J].CIESC Journal(化工学报),2011,62(11):3156-3163.