二乙醇胺催化脱氢合成亚氨基二乙酸的研究
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摘要
本文对CuMnOx催化剂稳定性、CuFeOx催化剂制备条件及二乙醇胺脱氢工艺进行了研究。
论文通过对CuMnOx催化剂的稳定性研究表明：采用分步沉淀法制备CuMnOx催化剂,经碱处理后具有更好二乙醇胺脱氢活性和碱性稳定性。
CuFeOx催化剂的制备研究表明：采用共沉淀法制备CuFeOx催化剂,当Cu/Fe摩尔比为1,盐溶液浓度为0.4mol/L,沉淀pH值为10.0,沉淀温度为70℃,550℃下焙烧4h后,在210℃、60ml/min H2还原4h制得的CuFeOx催化剂；在反应温度150℃、压力0.7Mpa反应3h后,IDA收率可达91.1%；稳定性好,连续套用10次后,IDA的收率稳定在80%以上；TPR及XRD测试表明FeOx有助于表面活性Cu的分散,促进CuO的还原；通过适当引入Mn元素,有利于提高Cu/FeMn催化剂的二乙醇胺脱氢活性,当Cu:Fe:Mn=1:0.4:0.6时,IDA收率达94.8%。
通过对二乙醇胺脱氢反应系统的分析,设计连续固定床脱氢反应器,并通过对反应过程分析,建立固定床脱氢反应工艺控制参数,在进料质量比为m(NaOH):m(DEA)=0.88,质量空速为2.0hr-1,反应温度为170℃,反应压力为0.8Mpa下连续反应60min, IDA收率达22.1%,设计固定床脱氢反应器及工艺参数可用于二乙醇胺连续脱氢反应。
This thesis includes the Mn stability of CuMnOx catalyst,the preparation methods and preparation conditions of CuFeOx catalyst, and the process conditions of the catalytic dehydrogenation of diethanolamine.
The different precipitation methods on preparing CuMnOx were compared, It is confirmed that the sequential precipitation method is better and when the CuMnOx catalyst pretreated by alkali will show more stability.
The optimum preparation conditions of CuFeOx catalyst are that, molar ratio Cu/Fe of 1, the concentration of mix solution of 0.4mol/L,the pH of solution of 10, the temperature of precipitation of 70℃, the temperature of calcinations of 550℃, and the temperature of hydrogen reduction of 210℃,under the optimum process conditions for the catalytic dehydrogenation of diethanolamine:the reaction temperature of 150℃,the reaction pressure of 0.7Mpa, the reaction time of 3 hours, iminodiacetic acid(IDA) salt yield of 91.1% was obtained. During catalyst stabilization evaluation,it showed that over 80% of IDA yield,when Cu:Fe:Mn=l:0.4:0.6,the IDA yield can be upto 94.8%.
Under the continuous Fix-bed process conditions for the catalytic dehydrogenation of diethanolamine:m(NaOH):m(DEA)=0.88, weight hourly weight velocity2.0hr-1, the reaction temperature of 170℃,the reaction pressure of 0.8Mpa,IDA yield of 22.1% was obtained,and it showed that the Fix-bed reactor and process can use for continuous catalytic dehydrogenating of diethanolamine.
论文通过对CuMnOx催化剂的稳定性研究表明：采用分步沉淀法制备CuMnOx催化剂,经碱处理后具有更好二乙醇胺脱氢活性和碱性稳定性。
CuFeOx催化剂的制备研究表明：采用共沉淀法制备CuFeOx催化剂,当Cu/Fe摩尔比为1,盐溶液浓度为0.4mol/L,沉淀pH值为10.0,沉淀温度为70℃,550℃下焙烧4h后,在210℃、60ml/min H2还原4h制得的CuFeOx催化剂；在反应温度150℃、压力0.7Mpa反应3h后,IDA收率可达91.1%；稳定性好,连续套用10次后,IDA的收率稳定在80%以上；TPR及XRD测试表明FeOx有助于表面活性Cu的分散,促进CuO的还原；通过适当引入Mn元素,有利于提高Cu/FeMn催化剂的二乙醇胺脱氢活性,当Cu:Fe:Mn=1:0.4:0.6时,IDA收率达94.8%。
通过对二乙醇胺脱氢反应系统的分析,设计连续固定床脱氢反应器,并通过对反应过程分析,建立固定床脱氢反应工艺控制参数,在进料质量比为m(NaOH):m(DEA)=0.88,质量空速为2.0hr-1,反应温度为170℃,反应压力为0.8Mpa下连续反应60min, IDA收率达22.1%,设计固定床脱氢反应器及工艺参数可用于二乙醇胺连续脱氢反应。
This thesis includes the Mn stability of CuMnOx catalyst,the preparation methods and preparation conditions of CuFeOx catalyst, and the process conditions of the catalytic dehydrogenation of diethanolamine.
The different precipitation methods on preparing CuMnOx were compared, It is confirmed that the sequential precipitation method is better and when the CuMnOx catalyst pretreated by alkali will show more stability.
The optimum preparation conditions of CuFeOx catalyst are that, molar ratio Cu/Fe of 1, the concentration of mix solution of 0.4mol/L,the pH of solution of 10, the temperature of precipitation of 70℃, the temperature of calcinations of 550℃, and the temperature of hydrogen reduction of 210℃,under the optimum process conditions for the catalytic dehydrogenation of diethanolamine:the reaction temperature of 150℃,the reaction pressure of 0.7Mpa, the reaction time of 3 hours, iminodiacetic acid(IDA) salt yield of 91.1% was obtained. During catalyst stabilization evaluation,it showed that over 80% of IDA yield,when Cu:Fe:Mn=l:0.4:0.6,the IDA yield can be upto 94.8%.
Under the continuous Fix-bed process conditions for the catalytic dehydrogenation of diethanolamine:m(NaOH):m(DEA)=0.88, weight hourly weight velocity2.0hr-1, the reaction temperature of 170℃,the reaction pressure of 0.8Mpa,IDA yield of 22.1% was obtained,and it showed that the Fix-bed reactor and process can use for continuous catalytic dehydrogenating of diethanolamine.
引文
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[38]赵乐平,庞宏,尤百玲,房莹.新型CuO/ZnO催化剂的制备及其对醛加氢／醇脱氢反应的催化性能.石油化工.2004,33(3)：209-211.
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[43]刘玉娟,金杏妹.用于二乙醇胺脱氢反应的铜锰系催化剂制备条件的研究.工业催化.2008,16(10)：165-168.
[44]王嵩,毛东森,吴贵升,郭晓明,卢冠忠,铜／氧化锆催化剂的制备及应用研究进展.化工进展.2008,27(6)：837-843.
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[2]汪家铭.亚氨基二乙酸发展概况与市场前景.化工科技市场.2009,32(9)：38-42.
[3]颜守保.亚氨基二乙酸的生产技术及其应用.安徽化工.2008,34(2)：20-22.
[4]钱伯章.亚氨基二乙酸的市场前景.精细化工原料及中间体.2005,3：39.
[5]John C., Moore. Iminodiacetic and aminotriaceticacids. US2239617.1941.
[6]Kozak Wladyslaw, Debowski Zygmunt. Synthesis of iminodiacetic acid by the cleavage of nitrilotriacetic acid. Chem,1963,16(85):47-55.
[7]Tsirulnikova, Rykov. S. V. Iminodiacetic acid. US.598884.1978.
[8]Gaudette Roger, R. Philbrook. Iminodiacetonitrile. US3988360.1976.
[9]Kozak Wladyslaw, Debowski Zygmunt. Synthesis of iminodiacetic acid by the cleavage of nitrilotriacetic acid. Chem.1963,16(85):47-55.
[10]Ochoa Gomez. Method for obtaining acetic acid derivatives namely glycine, iminodiacetic and nitrolotriacetic acid by dehydrogenation of ethan olamines using regenerated Raney copper catalysis. W09206069.1992.
[11]曾庆友,谢荣锦,王任蟠.亚氨基二乙酸的合成与分离纯化技术进展.精细石油化工进展.2001,2(10)：24.
[12]吴越.催化化学.北京科学出版社.1990,957.
[13]尾崎萃,田丸谦二,田部浩三,西村重夫.催化剂手册.化学工业出版社.1982,103.
[14]洪盈,叶凤阁等.有机化学辞典.高等教育出版社.1989,380.
[15]Jackisch, Philip F. Preparation of amino carboxylic acid salts. US3535373.1970.
[16]Bishop, John J.;Jache, Albert W. Catalytic preparation of alkali metal salts of nitrilotriacetic acid. US3578709,1971.
[17]Heinz Schulze, Edward Thomas Marquis. Preparation of aminocarboxylic acids from aminoalcohols. US3842081.1974.
[18]周杰,彭立煌等.二乙醇胺脱氢氧化法合成草甘膦的制备工艺.CN 1563021A.2005.
[19]彭彩云,盛文兵,王福东,方渡.二乙醇胺化清洁氧化合成亚氨基二乙酸.中国实用医药.2006(4)：32-33.
[20]Chitwood, Henry C. Catalytic alkaline oxidation of alcohols. US2384817.1945.
[21]Goto, Takakiyo, Yokoyama, et al. Method for manufacture of amino-carboxylic acid salts. US4782183.1988.
[22]储伟.催化剂工程.四川大学出版社.2006.9.
[23]Franczyk, Thaddeus S. Process to prepare amino carboxylic acid salts. US5292936.1994.
[24]Franczyk, Thaddeus Stephen, Kadon, et al. Process to prepare amino carboxylic acid salts. US5739390.1998.
[25]Ebner, Jerry R., Franczyk, Thaddeus S. Catalytic process for preparing carboxylic acid salts. US5689000.1997.
[26]Ebner, Jerry R., Franczyk, Thaddeus S. Preparation of carboxylic acid salts and catalysts useful in the preparation. US5627125.1997.
[27]Urano, Yoshiaki, Kadono, et al. Process for producing amino carboxylic acid salts. US5220055.1993.
[28]Urano, Yoshiaki, Kadono, Yukio, Goto, Takakiyo. Process for producing amino carboxylic acid salts by selective oxidative dehydrogenation of amino alcohols. W09209559A1.1992.
[29]Ochoa Gomez, Jose Ramon, Martin Ramon, Juan Luis. Method for obtaining acetic acid derivatives, namely glycine, iminodiacetic acid and nitrilotriacetic acid, by dehydrogenation of ethanolamines using regenerated Raney copper catalysts [P]. WO 9206069A1.1992.
[30]Franczyk, Thaddeus Stephan, Kadono, Yukio, Miyagawa, Norikazu, Takasaki, Seiji, Wakayama, Hiroki. Process to prepare amino carboxylic acid salts[P]. W09424091A1.1994.
[31]Thaddeus Stephen Franczyk, Yukio Kadono, Kawasaki, Norikazu Miyagawa, Seji Takasaki, Hiroki Wakayama. process to prepare amino carboxylic acid salts. US5739390.1994.
[32]Jorge Gustavo Vigil, Marta Del Carmen Ruiz, Method of preparing amino-imino-, and nitrilocarboxylic acids and silver-promoted copper catalyst for use in said method. U. S.6414188.2002.
[33]金杏妹.工业应用催化剂.华东理工大学出版社.
[34]David A. Morgenstern, Juan P. Arhancet, Howard C. Berk, William L. Moench, James C.Peterson, Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts. US7329778B2.2008.
[35]Thaddeus S. Franczyk, Maryland Heights, Process to prepare anlinocarboxylic acid salts [P]. US5292936.1994.
[36]曾庆友.硕士学位论文.二乙醇胺催化脱氢制亚氨基二乙酸催化剂及工艺研究.浙江大学,2001,11-12.
[37]段正康,杨运泉等.一乙醇胺碱水催化氧化合成甘氨酸工艺研究.精细化工.2000,17(6)：345-347.
[38]赵乐平,庞宏,尤百玲,房莹.新型CuO/ZnO催化剂的制备及其对醛加氢／醇脱氢反应的催化性能.石油化工.2004,33(3)：209-211.
[39]陈冬梅.硕士学位论文.用于二乙醇胺脱氢反应的Cu/ZrO2催化剂研究.华东理工大学.2008.
[40]蒯尉.硕士学位论文.用于合成亚氨基二乙酸盐的Cu/ZrO2催化剂制备及改性研究.华东理工大学.2008.
[41]叶洪平,段正康,杨运泉,吴俊,余剑.二乙醇胺脱氢催化剂Cu/ZrO2的制备条件研究[J].工业催化.2004,12(1)：48-52.
[42]杜朝军,李金辉.高活性铜／玻璃纤维催化剂的制备及其性能研究.材料保护.2004,37(10)：52-53.
[43]刘玉娟,金杏妹.用于二乙醇胺脱氢反应的铜锰系催化剂制备条件的研究.工业催化.2008,16(10)：165-168.
[44]王嵩,毛东森,吴贵升,郭晓明,卢冠忠,铜／氧化锆催化剂的制备及应用研究进展.化工进展.2008,27(6)：837-843.
[45]徐六兴.硕士学位论文.亚氨基二乙酸及草甘膦合成新工艺研究.浙江大学.2006.
[46]Dongsheng Liu, Noel W. Cant, Andrew J. Smith*, Mark S. Wainwright, The activity of chromia-promoted skeletal copper catalysts for the oxidative dehydrogenation of ethanolamine to sodium glycinate based on measurements in a modified autoclave. Applied Catalysis A:General 297 (2006) 18-23.
[47]Urano, Yoshiaki, etc. Process for produing salt of anlinocarboxylic acid. CA2071999.1992.
[48]Villanti, Alberto, Conti, Gianna. Method for the preparation of salts of carboxylic acids using copper catalyzed dehydrogenation. US6239312.2001.
[49]杨福卫,曾云.连续化合成亚氨基二乙酸钠清洁工艺方法.CN 101186581A.2008.
[50]曾云.连续化合成亚氨基二乙酸(盐)环保清洁工艺方法.CN 101544574A.2009.9.
[51]H.斯科特.福格勒著.化学反应工程.化学工业出版社.2005.1.
[52]高鸿顺等.催化蒸镏技术在石油化工过程中的应用.化工进展.1999.
[53]王龙延.催化蒸镏技术.现代化工.1990.
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