合成五氟乙烷催化剂的再生研究
|
摘要
研究了五氟乙烷生产过程中催化剂三正丁胺的失活与再生行为,分别探讨了上、中、下3层失活催化剂的失活机理,针对失活机理不同的失活催化剂采用了不同的再生方法。结果表明:上层失活催化剂的失活形态主要为三正丁胺、HF与四氟乙烯的络合物,采用先在氮气氛围加热分解络合物再减压精馏的方式再生,三正丁胺的收率达83.8%;中层失活催化剂的失活形态主要为络合物与四氟乙烯的低聚物,采用失活催化剂与CaCl_2水溶液反应再加碱分相的方式再生,三正丁胺的收率达69.4%;下层失活催化剂的失活形态主要为聚合物、二正丁胺和季铵盐,不再具有回收价值。
Deactivation and regeneration of tri-n-butylamine catalysts in pentafluoroethane production was studied, and the inactivation mechanism of the deactivated catalysts in the upper, middle and lower layers was discussed. Moreover, different regeneration methods were used for the deactivated catalysts. The deactivated catalysts from the upper layer was mainly composed by complex salts of tri-n-butylamine, hydrogen fluoride and tetrafluoroethylene, which were regenerated by heating and decomposing the complex salts in nitrogen atmosphere followed by vacuum distillation, and the yield of tri-n-butylamine was 83.8%. The deactivated catalyst from the intermediate lay contained oligomers of the complex salt and tetrafluoroethylene, which could be regenerated by the reaction with CaCl_2 aqueous solution and then separated in alkali solution, and the yield of tri-n-butylamine was 69.4%. For the lower layer, the deactivated catalyst contained oligomers,di-n-butylamine and quaternary ammonium salts with no recovery value.
Deactivation and regeneration of tri-n-butylamine catalysts in pentafluoroethane production was studied, and the inactivation mechanism of the deactivated catalysts in the upper, middle and lower layers was discussed. Moreover, different regeneration methods were used for the deactivated catalysts. The deactivated catalysts from the upper layer was mainly composed by complex salts of tri-n-butylamine, hydrogen fluoride and tetrafluoroethylene, which were regenerated by heating and decomposing the complex salts in nitrogen atmosphere followed by vacuum distillation, and the yield of tri-n-butylamine was 83.8%. The deactivated catalyst from the intermediate lay contained oligomers of the complex salt and tetrafluoroethylene, which could be regenerated by the reaction with CaCl_2 aqueous solution and then separated in alkali solution, and the yield of tri-n-butylamine was 69.4%. For the lower layer, the deactivated catalyst contained oligomers,di-n-butylamine and quaternary ammonium salts with no recovery value.
引文
[1]陈军.氟代乙烷及其衍生产物的制备[J].有机氟工业,2010(2):58-64.CHEN J.Preparation fluoroethane and derived products[J].Organic Fluorine Industry,2010(2):58-64.
[2]陈军.五氟乙烷的制备方法[J].有机氟工业,2007(3):61-64.CHEN J.Preparation of pentafluoroethane[J].Organic Fluorine Industry,2007(3):61-64.
[3]任常兴,张琰,幕洋洋,等.氢氟烃类物质对丙烷抑爆特性实验研究[J].消防科学与技术,2018(2):229-231.REN C X,ZHANG Y,MU Y Y,et al.Experimental study on propane explosion suppression characteristics by hydrofluorocarbons[J].Fire Science and Technology,2018(2):229-231.
[4]文永强.五氟乙烷(R125)的制备及应用[J].科技经济导刊,2016(8):109-109.WEN Y Q.Preparation and application of pentafluoroethane[J].Science and Technology Economic Guide,2016(8):109-109.
[5]闫怡,段琦.五氟乙烷与一氯五氟乙烷萃取分离方法的研究[J].化工生产与技术,2015,22(4):7,9-11.YAN Y,DUAN Q.Study on extraction and separation of pentafluoroethane and monochloropentafluoroethane[J].Chemical Production and Technology,2015,22(4):7,9-11.
[6]王军祥,刘建鹏,袁剑.1,1,1,2,2-五氟乙烷制备工艺研究进展[J].化工生产与技术,2011,18(1):10-12.WANG J X,LIU J P,YUAN J.Progress in preparation of 1,1,1,2,2-pentafluoroethane[J].Chemical Production and Technology,2011,18(1):10-12.
[7]刘坤峰,杨会娥,张文庆,气相法合成五氟乙烷(HFC-125)的研究进展[J].有机氟工业,2009(1):55-58.LIU K F,YANG H E,ZHANG W Q.Research progress on gas-phase synthesis of pentafluoroethane(HFC-125)[J].Organic Fluorine Industry,2009(1):55-58.
[8]王军祥,刘建鹏,袁剑.1,1,1,2,2-五氟乙烷应用研究现状[J].浙江化工,2011,42(7):1-4.WANG J X,LIU J P,YUAN J.Application of 1,1,1,2,2-pentafluoroethane research status[J].Zhejiang Chemical Industry,2011,42(7):1-4.
[9]何建明,何甫长,金崇献.一种制备五氟乙烷的氟化催化剂、制备方法及应用:CN 102 671 680 A[P].2012-09-19.HE J M,HE F C,JIN C X.A pentafluoroethane fluorination catalyst preparation,preparation method and application:CN 102 671680 A[P].2012-09-19.
[10]Vollmueller H,Franz R,Siegemund G.Process for the preparation of 2H-heptafluoropropane:US 5 912 392 A[P].1999-06-15.
[11]司林旭,张平忠,顾和祥.一种五氟乙烷制备方法:CN 102 617 270 A[P].2012-08-01.SI L X,ZHANG P Z,GU H X.A preparation method of pentafluoroethane:CN 102 617 270 A[P].2012-08-01.
[12]叶光武,王平.五氟乙烷的制备方法:CN 1 840 516[P].2006-10-04.YE G W,WANG P.A preparation method of pentafluoroethane:CN 1 840 516[P].2006-10-0.4
[13]大野博基,大井敏夫.五氟乙烷的纯化方法、其制备方法及其用途:CN 1 551 860[P].2004-12-01.OHNO B,OII T.Pentafluoroethane purification method,preparation and use:CN 1 551 860[P].2004-12-01.
[14]苗国详,应明明,钱建庆,等.五氟乙烷的制备方法:CN 1 793 094[P].2006-06-28.MIAO G X,YING M M,QIAN J Q,et al.Preparation of pentafluoroethane:CN 1 793 094[P].2006-06-28.
[15]司林旭,张平忠,徐建林,等.一种五氟乙烷制备方法:CN 101 265 154[P].2008-09-17SI L X,ZHANG P Z,XU J L,et al.A preparation method of pentafluoroethane:CN 101 265 154[P].2008-09-17.
[16]鲍怡法.四丁基碘化铵的合成工艺研究[D].南京:东南大学,2017.BAO Y F.Synthesis of tetrabutylammonium[D].Nanjing:Southeast University,2017.
[17]张志刚.四氟乙烯单体生产过程中氧含量和水含量的综合控制[J].有机氟工业,2006(2):29-31.ZHANG Z G.Integrated control of oxygen content and water content in tetrafluoroethylene monomer production process[J].Organic Fluorine Industry,2006(2):29-31.
[18]程毅丽,康国栋,贾静璇.聚四氟乙烯中空纤维膜的多巴胺自聚表面改性及性能研究[J].高校化学工程学报,2015,29(5):1259-1264.CHENG Y L,KANG G D,JIA J X.Preparation and performance of surface modified PTFE hollow fiber membranes by self-polymerization of dopamine[J].Journal of Chemical Engineering of Chinese Universities,2015,29(5):1259-1264.
[19]彭洪祥,于志家,孙晓哲.新型聚四氟乙烯微孔膜的油水分离特性研究[J].高校化学工程学报,2013,27(6):1084-1088.PENG H X,YU Z J,SUN X Z.Oil-water separation characteristics of a new type of PTFE microporous membrane[J].Journal of Chemical Engineering of Chinese Universities,2013,27(6):1084-1088.
[20]胡子江.四氟乙烯生产中氧含量的控制[J].有机氟工业,2003(1):3-4.HU Z J.Control of oxygen content in tetrafluoroethylene production[J].Organic Fluorine Industry,2003(1):3-4.
[21]宋学章,孙百开,赵永晓.一种五氟乙烷生产中废催化剂的处理方法:CN 1 962 064[P].2007-05-16.SONG X Z,SUN B K,ZHAO Y X.A method for treating spent catalyst in pentafluoroethane production:CN 1 962 064[P].2007-05-16.
[22]陈新志,应振洲,葛濯非.五氟乙烷生产中含催化剂废液的处理方法:CN 101 934 239 A[P].2011-01-05.CHEN X Z,YING Z Z,GE Z F.Treatment of waste liquid containing catalyst in pentafluoroethane production:CN 101 934 239 A[P].2011-01-05.
[23]NAWROT E,ANDRZEJ A.Difluoromethyltrialkylammonium salts--their expeditious synthesis from chlorodifluoromethane and tertiary amines in the presence of concentrated aqueous sodium hydroxide.The catalytic process[J].Journal of Organic Chemistry,2007,72(26):10258-10260.
[2]陈军.五氟乙烷的制备方法[J].有机氟工业,2007(3):61-64.CHEN J.Preparation of pentafluoroethane[J].Organic Fluorine Industry,2007(3):61-64.
[3]任常兴,张琰,幕洋洋,等.氢氟烃类物质对丙烷抑爆特性实验研究[J].消防科学与技术,2018(2):229-231.REN C X,ZHANG Y,MU Y Y,et al.Experimental study on propane explosion suppression characteristics by hydrofluorocarbons[J].Fire Science and Technology,2018(2):229-231.
[4]文永强.五氟乙烷(R125)的制备及应用[J].科技经济导刊,2016(8):109-109.WEN Y Q.Preparation and application of pentafluoroethane[J].Science and Technology Economic Guide,2016(8):109-109.
[5]闫怡,段琦.五氟乙烷与一氯五氟乙烷萃取分离方法的研究[J].化工生产与技术,2015,22(4):7,9-11.YAN Y,DUAN Q.Study on extraction and separation of pentafluoroethane and monochloropentafluoroethane[J].Chemical Production and Technology,2015,22(4):7,9-11.
[6]王军祥,刘建鹏,袁剑.1,1,1,2,2-五氟乙烷制备工艺研究进展[J].化工生产与技术,2011,18(1):10-12.WANG J X,LIU J P,YUAN J.Progress in preparation of 1,1,1,2,2-pentafluoroethane[J].Chemical Production and Technology,2011,18(1):10-12.
[7]刘坤峰,杨会娥,张文庆,气相法合成五氟乙烷(HFC-125)的研究进展[J].有机氟工业,2009(1):55-58.LIU K F,YANG H E,ZHANG W Q.Research progress on gas-phase synthesis of pentafluoroethane(HFC-125)[J].Organic Fluorine Industry,2009(1):55-58.
[8]王军祥,刘建鹏,袁剑.1,1,1,2,2-五氟乙烷应用研究现状[J].浙江化工,2011,42(7):1-4.WANG J X,LIU J P,YUAN J.Application of 1,1,1,2,2-pentafluoroethane research status[J].Zhejiang Chemical Industry,2011,42(7):1-4.
[9]何建明,何甫长,金崇献.一种制备五氟乙烷的氟化催化剂、制备方法及应用:CN 102 671 680 A[P].2012-09-19.HE J M,HE F C,JIN C X.A pentafluoroethane fluorination catalyst preparation,preparation method and application:CN 102 671680 A[P].2012-09-19.
[10]Vollmueller H,Franz R,Siegemund G.Process for the preparation of 2H-heptafluoropropane:US 5 912 392 A[P].1999-06-15.
[11]司林旭,张平忠,顾和祥.一种五氟乙烷制备方法:CN 102 617 270 A[P].2012-08-01.SI L X,ZHANG P Z,GU H X.A preparation method of pentafluoroethane:CN 102 617 270 A[P].2012-08-01.
[12]叶光武,王平.五氟乙烷的制备方法:CN 1 840 516[P].2006-10-04.YE G W,WANG P.A preparation method of pentafluoroethane:CN 1 840 516[P].2006-10-0.4
[13]大野博基,大井敏夫.五氟乙烷的纯化方法、其制备方法及其用途:CN 1 551 860[P].2004-12-01.OHNO B,OII T.Pentafluoroethane purification method,preparation and use:CN 1 551 860[P].2004-12-01.
[14]苗国详,应明明,钱建庆,等.五氟乙烷的制备方法:CN 1 793 094[P].2006-06-28.MIAO G X,YING M M,QIAN J Q,et al.Preparation of pentafluoroethane:CN 1 793 094[P].2006-06-28.
[15]司林旭,张平忠,徐建林,等.一种五氟乙烷制备方法:CN 101 265 154[P].2008-09-17SI L X,ZHANG P Z,XU J L,et al.A preparation method of pentafluoroethane:CN 101 265 154[P].2008-09-17.
[16]鲍怡法.四丁基碘化铵的合成工艺研究[D].南京:东南大学,2017.BAO Y F.Synthesis of tetrabutylammonium[D].Nanjing:Southeast University,2017.
[17]张志刚.四氟乙烯单体生产过程中氧含量和水含量的综合控制[J].有机氟工业,2006(2):29-31.ZHANG Z G.Integrated control of oxygen content and water content in tetrafluoroethylene monomer production process[J].Organic Fluorine Industry,2006(2):29-31.
[18]程毅丽,康国栋,贾静璇.聚四氟乙烯中空纤维膜的多巴胺自聚表面改性及性能研究[J].高校化学工程学报,2015,29(5):1259-1264.CHENG Y L,KANG G D,JIA J X.Preparation and performance of surface modified PTFE hollow fiber membranes by self-polymerization of dopamine[J].Journal of Chemical Engineering of Chinese Universities,2015,29(5):1259-1264.
[19]彭洪祥,于志家,孙晓哲.新型聚四氟乙烯微孔膜的油水分离特性研究[J].高校化学工程学报,2013,27(6):1084-1088.PENG H X,YU Z J,SUN X Z.Oil-water separation characteristics of a new type of PTFE microporous membrane[J].Journal of Chemical Engineering of Chinese Universities,2013,27(6):1084-1088.
[20]胡子江.四氟乙烯生产中氧含量的控制[J].有机氟工业,2003(1):3-4.HU Z J.Control of oxygen content in tetrafluoroethylene production[J].Organic Fluorine Industry,2003(1):3-4.
[21]宋学章,孙百开,赵永晓.一种五氟乙烷生产中废催化剂的处理方法:CN 1 962 064[P].2007-05-16.SONG X Z,SUN B K,ZHAO Y X.A method for treating spent catalyst in pentafluoroethane production:CN 1 962 064[P].2007-05-16.
[22]陈新志,应振洲,葛濯非.五氟乙烷生产中含催化剂废液的处理方法:CN 101 934 239 A[P].2011-01-05.CHEN X Z,YING Z Z,GE Z F.Treatment of waste liquid containing catalyst in pentafluoroethane production:CN 101 934 239 A[P].2011-01-05.
[23]NAWROT E,ANDRZEJ A.Difluoromethyltrialkylammonium salts--their expeditious synthesis from chlorodifluoromethane and tertiary amines in the presence of concentrated aqueous sodium hydroxide.The catalytic process[J].Journal of Organic Chemistry,2007,72(26):10258-10260.