连续催化胺化制备四甲基乙二胺催化剂

doi:10.16085/j.issn.1000-6613.2017.04.019

化工进展 ›› 2017, Vol. 36 ›› Issue (04): 1294-1300.DOI: 10.16085/j.issn.1000-6613.2017.04.019

连续催化胺化制备四甲基乙二胺催化剂

吴军, 钱俊峰, 孙富安, 吴中, 崔爱军, 何明阳, 陈群

常州大学石油化工学院, 江苏省精细石油化工重点实验室, 江苏常州 213164

收稿日期:2016-08-25 修回日期:2016-12-14 出版日期:2017-04-05 发布日期:2017-04-05
通讯作者: 何明阳,教授,主要从事有机化学及清洁化工工艺方向的研究。E-mail:hmy@jpu.edu.cn。
作者简介:吴军(1989-),男,硕士研究生。E-mail:474614330@qq.com。
基金资助:
江苏省科技厅产学研前瞻项目（BY2015027-16）及江苏省产学研项目（BY2014037-17）。

Study on catalyst for continuous catalytic amination of TMEDA

WU Jun, QIAN Junfeng, SUN Fu'an, WU Zhong, CUI Aijun, HE Mingyang, CHEN Qun

Key Laboratory of Fine Petrochemical Engineering, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China

Received:2016-08-25 Revised:2016-12-14 Online:2017-04-05 Published:2017-04-05

摘要/Abstract

摘要： 以Cu/Ni为主活性组分，研制出适合于N，N-二甲基乙醇胺（DMEA）固定床连续催化胺化制备N，N，N’，N’-四甲基乙二胺（TMEDA）复合催化剂。考察了催化剂载体类型、铜镍摩尔比、负载量、助剂、焙烧温度和时间等因素对催化剂性能的影响。通过实验得出催化剂较佳的制备条件为：以γ-Al₂O₃球为载体，摩尔比Cu：Ni：Mn=4：1：0.2，负载量20%，500℃下焙烧6h。在反应温度240℃、常压、胺醇摩尔比1：1、空速0.12h^-1、氢气流量30mL/min反应条件下，DMEA转化率和TMEDA选择性分别达到92.8%和82.9%；通过固定床连续500h寿命测试，转化率和选择性分别稳定在90%和80%以上，显示催化剂具有较好的催化活性和稳定性。

关键词: N, N-二甲基乙醇胺, N, N, N', N'-四甲基乙二胺, 催化剂, 固定床, 加氢

Abstract: A compound catalyst with Cu/Ni as the main activate component is applied for continuous catalytic amination DMEA to TMEDA. The influences of catalyst carrier type,Cu/Ni molar ratio,loading amount,additives,roasting time and temperature on the performance of the catalyst were investigated. The best preparation conditions of the catalyst were as follows:with the γ-Al₂O₃ ball as the carrier,Cu:Ni:Mn=4:1:0.2(mole ratio),the load amount 20%,and roasting 6h at 500℃. Under the conditions of the reaction temperature of 240℃,atmospheric pressure,amine alcohol molar ratio 1:1,space velocity of 0.12h^-1,hydrogen speed of 30 mL/min,the conversion rate of DMEA and the selectivity of TMEDA could achieve 92.8% and 82.9%,respectively. Through 500h life test,the conversion rate and selectivity were stable and maintained at above 90% and 80%,respectively. The experimental results showed that the catalyst had excellent catalytic activity and stability.

Key words: DMEA, TMEDA, catalyst, fixed-bed, hydrogenation

中图分类号:

TQ032.4

吴军, 钱俊峰, 孙富安, 吴中, 崔爱军, 何明阳, 陈群. 连续催化胺化制备四甲基乙二胺催化剂[J]. 化工进展, 2017, 36(04): 1294-1300.

WU Jun, QIAN Junfeng, SUN Fu'an, WU Zhong, CUI Aijun, HE Mingyang, CHEN Qun. Study on catalyst for continuous catalytic amination of TMEDA[J]. Chemical Industry and Engineering Progress, 2017, 36(04): 1294-1300.

参考文献

[1] 黄健,黄志明,包永忠,等. 非离子型凝胶球在水中的溶胀行为[J]. 高校化学工程学报,2006,20(6):864-869. HUANG J,HUANG Z M,BAO Y Z,et al. Swelling behavior of nonionic spherical gels in water[J]. Journal of Chemical Engineering of Chinese Universities,2006,20(6):864-869.
[2] 黄健,黄志明,包永忠,等. 表面强化交联聚(N-异丙基丙烯酰胺)水凝胶的温敏和浓缩分离性能[J]. 化工学报,2006,57(4):948-954. HUANG J,HUANG Z M,BAO Y Z,et al. Thermo-sensitive and separation properties of poly(N-isopropylacrylamide) hydrogels with enhanced surface crosslinking[J]. Journal of Chemical Industry and Engineering,2006,57(4):948-954.
[3] 韩世岩. 松香基双子表面活性剂合成及纳米材料制备[D]. 哈尔滨:东北林业大学,2012. HAN S Y. Synthesis of rosin based gemini surfactants and preparation of nanometer materials[D]. Harbin:Northeast Forestry University,2012.
[4] 虞剑秋,张建元,王得宁,等. 改良BBS法评价聚氨酯发泡催化剂[J]. 高分子材料科学与工程,1991,7(2):105-109. YU J Q,ZHANG J Y,WANG D N,et al. Modified BBS method for evaluation of polyurethane foam catalysts polymeric[J]. Materials Science and Engineering,1991,7(2):105-109.
[5] 岳冬梅,沈曾民,徐瑞清,等. 新型双金属双配体催化剂对NBR加氢的影响[J]. 化工学报,2006,57(1):41-47. YUE D M,SHEN C M,XU R Q,et al. Performance of new homogenous bimetallic biligand catalyst for NBR hydrogenation[J]. Journal of Chemical Industry and Engineering,2006,57(1):41-47.
[6] 薛宏,王军,张春庆,等. 正丁基锂-四甲基乙二胺体系下的丁二烯-苯乙烯共聚合[J]. 大连理工大学学报,1999,39(4):514-518. XUE H,WANG J,ZHANG C Q,et al. Copolymerization of butadiene-styrene based on n-buli-TMEDA[J]. Journal of Dalian University of Technology,1999,39(4):514-518.
[7] ROSENAU T,POTTHAST A,RHRLING J,et al. A solvent-free and formalin-free eschweiler-clarke methylation for amines[J]. Synthetic Communications,2002,32(3):457-4655.
[8] 陈建国,南巍冈. 一种利用管道反应器合成N,N,N',N'-四甲基乙二胺的方法:200610154984.4[P]. 2007-05-16. CHEN J G,NAN W G. Method for synthesizing TMEDA by using pipeline reactor:200610154984.4[P]. 2007-05-16.
[9] HAMMERSTROM K,SPIELBERGER G. Process for the continuous preparation of tetramethylethylene-diamine:US4053516[P]. 1977-10-11.
[10] 张涛,陈汉庚,张旭,等. 固定床合成N,N,N',N'-四甲基乙二胺的研究[J]. 浙江大学学报,2010,44(12):2401-2405. ZHANG T,CHEN H G,ZHANG X,et al. Catalytic synthesis of TMEDA in fixed-bed reactor[J]. Journal of Zhejiang Unversity,2010,44(12):2401-2405.
[11] 李运玲. 催化胺化制三烷基叔胺的研究[D]. 太原:山西大学,2012. LI Y L. Study on the preparation of trialkylamine with catalytic amination[D]. Taiyuan:Shanxi University,2012.
[12] BAIKER A,KIJENSKI J. Catalytic synthesis of higher aliphatic amines from the corresponding alcohols[J]. Catalysis Reviews Science and Engineering,1985,27(4):653-697.
[13] 安倍裕,谷口英樹,岡部和彦,等. トリ長鎖アルキルアミンの合成に関する研究[J]. 油化学,1989,38(7):565-569. ABE M,TANIGUCHI H,OKABE K,et al. Research on the synthesis of tri(long-chain alkyl)amines[J]. Journal of Japan Oil Chemists' Society,1989,38(7):565-569.
[14] ZHANG L,LIU J,LI W,et al. Ethanol steam reforming over Ni-Cu/Al₂O₃-M_yO_z (M=Si,La,Mg,and Zn) catalysts[J]. Journal of Natural Gas Chemistry,2009,18(1):55-65.
[15] CHEN Y,REN J. Conversion of methane and carbon dioxide into synthesis gas over alumina-supported nickel catalysts. Effect of Ni-Al₂O₃ interactions[J]. Catalysis Letters,1994,29(1/2):39-48.
[16] 谭平. 脂肪醇胺化制叔胺催化剂的研究与开发[D]. 太原:中国日用化学工业研究院,2003. TAN P. Research and development of fatty alcohol amination catalyst[D]. Taiyuan:China Research Institute of Daily Chemical Industry,2003.
[17] KIM Y J,KWON H J,NAM I S,et al. High deNO_x performance of Mn/TiO₂,catalyst by NH₃[J]. Catalysis Today,2010,151(3/4):244-250.
[18] 顾立军,谢颖,刘宝生,等. 焙烧温度对CuO/γ-Al₂O₃和CeO₂-CuO/γ-Al₂O₃催化剂NO还原活性的影响[J]. 燃料化学学报,2004,32(2):235-239. GU L J,XIE Y,LIU B S,et al. Effect of roasting temperature on NO reduction activity of CuO/γ-Al₂O₃ and CeO₂-CuO/γ-Al₂O₃ catalysts[J]. Journal of Fuel Chemistry and Technology,2004,32(2):235-239.

连续催化胺化制备四甲基乙二胺催化剂

Study on catalyst for continuous catalytic amination of TMEDA

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