苯胺烷基化合成对异丙基苯胺的研究
摘要
对异丙基苯胺是一种重要的有机合成中间体,其最主要用途是用作合成高效化学除草剂异丙隆的中间体,还可用于合成医药、染料、涂料及其它化工产品,因此开发对异丙基苯胺新的合成工艺前景广阔。
传统对异丙基苯胺的合成方法环境污染和设备腐蚀严重。采用分子筛为催化剂合成对异丙基苯胺,可以避免环境污染和设备腐蚀,并适合于连续化生产,具有很好的实用价值。
本文采用改进HWC-6型分子筛为催化剂进行苯胺-丙烯气液固三相烷基化反应。将苯胺-丙烯分子筛催化烷基化分别与苯-丙烯和苯酚-丙烯分子筛催化烷基化合成异丙苯和异丙基苯酚进行了对比,用估算方法得到苯胺与丙烯烷基化的反应热和反应物系临界参数等基础数据,采用Aspen软件确定了不同原料配比下反应物系的相图,由此确定烷基化反应的实验条件,在此基础上设计出等温积分式烷基化反应器。
研究了不同反应条件对改进HWC-6型分子筛催化性能的影响,并对各因素的影响作了理论探讨,确定了最佳的反应条件。苯胺单程转化率达到66%,对位选择性75%。
该工艺技术很好的解决了设备腐蚀、“三废”污染、生产成本高及无法实现大规模连续化生产等问题,为合成对异丙基苯胺开辟了一条新途径。
p-Isopropylaniline is an important intermediate in organic synthesis. One of its main uses is to prepare high efficiency herbicide isoproturon. It can also be used in synthesizing medicine, dyestuff, coating and other chemical products. So there is a broad perspective to develop the synthesis process of p-isopropylaniline.
Traditional processes for preparing p-isopropylaniline often lead to serious environmental problems and equipment corrosion. Preparing p-isopropylaniline over molecular sieve catalyst can provide a new way to avoid environmental pollution and equipment corrosion and also can be operated for continuous production. This technology has great practical application value.
Alkylation of aniline by propylene was studied. Reaction was carried under gaseous and liquid mixed phase on modified HWC-6 zeolite molecular sieve. After comparison between alkylation of benzene and phenol by propylene and alkylation of aniline by propylene, some related data such as reaction heat and critical parameters were obtained by estimation methods, and a VLE chart within experimental condition was drawn according to calculation by Aspen software. Based on former comparison and calculation, appropriate experiment conditions were given and a continuous fixed-bed tubular reactor was designed for alkylation.
The effects of different reaction conditions on modified HWC-6 have been inspected. The theoretical discusses according to the effects of different factors has been made, the favorite reaction condition has been determined. The converstion of aninline is up to 66%, selectivity of p-isopropylaniline is 75%.
This technology could solve many existed problems, such as: the pollution of the three wastes, high production cost, equipment corrosion, difficulty in realization of series mass production. So it can be concluded that this technology developed a new path for the synthesizing of p-isopropylaniline.
传统对异丙基苯胺的合成方法环境污染和设备腐蚀严重。采用分子筛为催化剂合成对异丙基苯胺,可以避免环境污染和设备腐蚀,并适合于连续化生产,具有很好的实用价值。
本文采用改进HWC-6型分子筛为催化剂进行苯胺-丙烯气液固三相烷基化反应。将苯胺-丙烯分子筛催化烷基化分别与苯-丙烯和苯酚-丙烯分子筛催化烷基化合成异丙苯和异丙基苯酚进行了对比,用估算方法得到苯胺与丙烯烷基化的反应热和反应物系临界参数等基础数据,采用Aspen软件确定了不同原料配比下反应物系的相图,由此确定烷基化反应的实验条件,在此基础上设计出等温积分式烷基化反应器。
研究了不同反应条件对改进HWC-6型分子筛催化性能的影响,并对各因素的影响作了理论探讨,确定了最佳的反应条件。苯胺单程转化率达到66%,对位选择性75%。
该工艺技术很好的解决了设备腐蚀、“三废”污染、生产成本高及无法实现大规模连续化生产等问题,为合成对异丙基苯胺开辟了一条新途径。
p-Isopropylaniline is an important intermediate in organic synthesis. One of its main uses is to prepare high efficiency herbicide isoproturon. It can also be used in synthesizing medicine, dyestuff, coating and other chemical products. So there is a broad perspective to develop the synthesis process of p-isopropylaniline.
Traditional processes for preparing p-isopropylaniline often lead to serious environmental problems and equipment corrosion. Preparing p-isopropylaniline over molecular sieve catalyst can provide a new way to avoid environmental pollution and equipment corrosion and also can be operated for continuous production. This technology has great practical application value.
Alkylation of aniline by propylene was studied. Reaction was carried under gaseous and liquid mixed phase on modified HWC-6 zeolite molecular sieve. After comparison between alkylation of benzene and phenol by propylene and alkylation of aniline by propylene, some related data such as reaction heat and critical parameters were obtained by estimation methods, and a VLE chart within experimental condition was drawn according to calculation by Aspen software. Based on former comparison and calculation, appropriate experiment conditions were given and a continuous fixed-bed tubular reactor was designed for alkylation.
The effects of different reaction conditions on modified HWC-6 have been inspected. The theoretical discusses according to the effects of different factors has been made, the favorite reaction condition has been determined. The converstion of aninline is up to 66%, selectivity of p-isopropylaniline is 75%.
This technology could solve many existed problems, such as: the pollution of the three wastes, high production cost, equipment corrosion, difficulty in realization of series mass production. So it can be concluded that this technology developed a new path for the synthesizing of p-isopropylaniline.
引文
[1] 徐克勋,精细有机化工原料及中间体手册,北京:化学工业出版社, 1998,3-403
[2] 吴建兰,周启栋,急性对异丙基苯胺中毒5例报告,中国工业医学杂志,2001, l4(3):157
[3] 汪小兰,有机化学,北京:高等教育出版社,2001, 186~189
[4] 黄天守,化学化工药学大词典,大学图书公司,1982, 239
[5] 郭佃顺,黄汝骐,等,非光气工艺合成除草剂异丙隆,农药,1994, 33(5):13
[6] 1000t/a 异丙隆原药项目可行性研究,化工开发与设计,2000, 7:35~37
[7] 善大喜,陈萍,除草剂异丙隆的合成研究,江苏石油化工学院学报,2001, 13(2):23~25
[8] Tamura, 1,2-Disubstituted 1,4-Dihedro-4-oxoquinoline compounds and their antiviral activity, EP 1, 081, 138, 2001
[9] Champman, Derek David, et al., Mixtures of Symmetrical and Symmetrical Nickel Formzan dyes, EP 832, 938, 1996
[10] New dyestuff of the Perylene Tetracarboxylic Avid Series, GB852, 202, 1957
[11] Gaughan, roger G., et al., Unleaded Aviation Gasoline, US 5, 470, 358, 1995
[12] 王良芥,罗和安,段正康,对异丙基苯胺的合成,化学世界,1997,11:581~583
[13] Fediriva,P.I. et al., Amination of Aromatic Compounds by Hydroxylamine Hydrochloride, Zh.Prikl.klim. (leningrad) 1973,46(5):1079~82(Russ)
[14] Baardman, Frank, et al. Process for the Selective Alkylation of an Aniline, EP 79 093, 1982
[15] D.D.Dixon, W.F.Burgoyne, European Patent EP334, 332(1989); Chem, Abstr, 113(1990) 171653
[16] Weisz, P.B., and Frilette, V.J., J. Phys.Chem., 1960, 680
[17] Csicsery, S. M. ACS Monograph 171 (J. A. Rabo, ed.), Washington, D.C.
[18] Derouane, E.G., Catalysis by Zeolites(B. Imelik, et al., eds.), Elsevier Scientific
[19] Chen, N. Y. and Garwood, W.E., Catal. Rev. Sci. Eng., 1986, 28, 185
[20] Dewing, J., Spencer. M. S., Whittmam, T. V., Synthesis, Characterization and Catalytic Properties of Nu-1, Fu-1, and related Zeolites, Catal. Rev. Sci. Eng., 1985, 27(3):461
[21] 陈吉祥,潘履让,合成异丙基苯胺催化剂研究进展,化工科技,2001,9(1):55~59
[22] 陈吉祥,唐祥海,朱瑞芝,等,合成对异丙基苯胺分子筛催化剂的研究,燃料化学学报,1998, 26(6):526~530
[23] 陈吉祥,唐祥海,朱瑞芝,等,不同方法合成的 HZSM-5 分子筛上苯胺与异丙醇烷基化反应规律的研究,石油学报(石油加工),1999, 15(3): 46~51
[24] Takuji N. Preparation of 4-Isopropylanilne, JP 4 069 366, 1992
[25] Agrawal, Rokesh. Alkylation of Aromatic Amines with Olefins on Partially Dealumiated Zeolites, EP 240 018, 1987
[26] 朱瑞芝,陈吉祥,唐祥海,等,HY 分子筛上合成对异丙基苯胺,石油化工,2000, 29(5):330~333
[27] Agrawal, Rakesh, Alkylation of aromatic amines with olefins on partially dealuminated zeolites, EP0240018, 1982
[28] Keith Smith, Adam Musson, et al. A novel Method for the Nitration of Simple Aromatic Compounds, J. Org. Chem.,1998,63,8448-8454
[29] R.B.C.Pillai. Synthesis of Secondary amines by reductive alkylation using copper chromite catalyst: steric effect of carbonyl compounds, J.Mol.Catal., 1993, 84:125~129
[30] Beyer, Hermann; Gerencser Marko,Anna; et al. Process for the praparation of alkylanilines by isomerization of N- alkylanilines over acidic zeolites as catalysts, DD295,338
[31] 申东明,β-分子筛催化剂在异丙苯工业中的应用研究,硕士学位论文,大连:大连理工大学,2005
[32] 高辉,史建公,曹钢,等,异丙苯合成工艺进展,化学工业与工程技术,2003, 24(6):36~38
[33] 陈小明,超临界苯烷基化反应体系在分子筛中吸附行为的分子模拟,北京:北京化工大学,2004
[34] 郭继志,近临界条件下苯与丙烯烷基化反应体系的相平衡和反应行为研究,博士学位论文,上海:华东理工大学,2000
[35] 孟祥燕,不同相态下苯丙烯烷基化反应研究,硕士学位论文,太原:中国科学院山西煤炭化学研究所,2002
[36] 孙海,刘靖,郭汝生, 超临界条件下烷基化反应的研究进展,天然气化工, 2003, 28(2):42-45
[37] 王波,多相催化体系中芳烃及其衍生物的烷基化和羟基化,博士学位论文,大连:大连理工大学,2001
[38] 高滋,沸石催化与分离技术,北京:中国石化出版社,1999,3~4
[39] 郝素娥,强亮生,精细合成单元反应与合成设计,哈尔滨:哈哈尔滨工业大学出版社,2001, 69
[40] Wojciechowski B W, Corma A. Catalytic Cracking, Catalysts, Chemistry and Kinetics. New York: Marcel Dekker, 1986, 9
[41] Weisz,P.B., Pure Appl.Chem.,1980, 52, 2091
[42]马沛生,化工数据,北京:中国石化出版社,2003, 42~66, 129~181
[43] Carl L. Yaws, Chemical Properties Handbook, McGraw-Hill, 1999, 5~29, 288~313
[44] Robert H. Perry, Don W. Green, Perry’s Chemical Engineers’ Handbook (7th Edition), 北京:科学出版社,2001, 2-50, 2-52
[45] 杨少华,崔英德,等,ZSM-5 沸石分子筛的合成和表面改性研究进展,精细石油化工进展,2003, 4:47~51
[46] 李绍芬,化学与催化反应工程,北京:化学工业出版社,1986, 458~492
[47] 曾昭槐,择形催化,北京:中国石化出版社,1994, 4~6
[48] 曹声春,胡艾希,催化原理及其工业应用技术,长沙:湖南大学出版社,2001, 151~152
[49] 李栋藩,张盈珍,陶龙镶,等,水热处理对 ZSM-5 沸石的酸性、活性及烯烃选择性的影响,石油化工,1988, 17:150
[50] 杨彩虹,牛清华,卢学栋,焙烧和水热处理对 HZSM-5 沸石酸性和催化活性的影响,天然气化工,1990, 2:11~17
[2] 吴建兰,周启栋,急性对异丙基苯胺中毒5例报告,中国工业医学杂志,2001, l4(3):157
[3] 汪小兰,有机化学,北京:高等教育出版社,2001, 186~189
[4] 黄天守,化学化工药学大词典,大学图书公司,1982, 239
[5] 郭佃顺,黄汝骐,等,非光气工艺合成除草剂异丙隆,农药,1994, 33(5):13
[6] 1000t/a 异丙隆原药项目可行性研究,化工开发与设计,2000, 7:35~37
[7] 善大喜,陈萍,除草剂异丙隆的合成研究,江苏石油化工学院学报,2001, 13(2):23~25
[8] Tamura, 1,2-Disubstituted 1,4-Dihedro-4-oxoquinoline compounds and their antiviral activity, EP 1, 081, 138, 2001
[9] Champman, Derek David, et al., Mixtures of Symmetrical and Symmetrical Nickel Formzan dyes, EP 832, 938, 1996
[10] New dyestuff of the Perylene Tetracarboxylic Avid Series, GB852, 202, 1957
[11] Gaughan, roger G., et al., Unleaded Aviation Gasoline, US 5, 470, 358, 1995
[12] 王良芥,罗和安,段正康,对异丙基苯胺的合成,化学世界,1997,11:581~583
[13] Fediriva,P.I. et al., Amination of Aromatic Compounds by Hydroxylamine Hydrochloride, Zh.Prikl.klim. (leningrad) 1973,46(5):1079~82(Russ)
[14] Baardman, Frank, et al. Process for the Selective Alkylation of an Aniline, EP 79 093, 1982
[15] D.D.Dixon, W.F.Burgoyne, European Patent EP334, 332(1989); Chem, Abstr, 113(1990) 171653
[16] Weisz, P.B., and Frilette, V.J., J. Phys.Chem., 1960, 680
[17] Csicsery, S. M. ACS Monograph 171 (J. A. Rabo, ed.), Washington, D.C.
[18] Derouane, E.G., Catalysis by Zeolites(B. Imelik, et al., eds.), Elsevier Scientific
[19] Chen, N. Y. and Garwood, W.E., Catal. Rev. Sci. Eng., 1986, 28, 185
[20] Dewing, J., Spencer. M. S., Whittmam, T. V., Synthesis, Characterization and Catalytic Properties of Nu-1, Fu-1, and related Zeolites, Catal. Rev. Sci. Eng., 1985, 27(3):461
[21] 陈吉祥,潘履让,合成异丙基苯胺催化剂研究进展,化工科技,2001,9(1):55~59
[22] 陈吉祥,唐祥海,朱瑞芝,等,合成对异丙基苯胺分子筛催化剂的研究,燃料化学学报,1998, 26(6):526~530
[23] 陈吉祥,唐祥海,朱瑞芝,等,不同方法合成的 HZSM-5 分子筛上苯胺与异丙醇烷基化反应规律的研究,石油学报(石油加工),1999, 15(3): 46~51
[24] Takuji N. Preparation of 4-Isopropylanilne, JP 4 069 366, 1992
[25] Agrawal, Rokesh. Alkylation of Aromatic Amines with Olefins on Partially Dealumiated Zeolites, EP 240 018, 1987
[26] 朱瑞芝,陈吉祥,唐祥海,等,HY 分子筛上合成对异丙基苯胺,石油化工,2000, 29(5):330~333
[27] Agrawal, Rakesh, Alkylation of aromatic amines with olefins on partially dealuminated zeolites, EP0240018, 1982
[28] Keith Smith, Adam Musson, et al. A novel Method for the Nitration of Simple Aromatic Compounds, J. Org. Chem.,1998,63,8448-8454
[29] R.B.C.Pillai. Synthesis of Secondary amines by reductive alkylation using copper chromite catalyst: steric effect of carbonyl compounds, J.Mol.Catal., 1993, 84:125~129
[30] Beyer, Hermann; Gerencser Marko,Anna; et al. Process for the praparation of alkylanilines by isomerization of N- alkylanilines over acidic zeolites as catalysts, DD295,338
[31] 申东明,β-分子筛催化剂在异丙苯工业中的应用研究,硕士学位论文,大连:大连理工大学,2005
[32] 高辉,史建公,曹钢,等,异丙苯合成工艺进展,化学工业与工程技术,2003, 24(6):36~38
[33] 陈小明,超临界苯烷基化反应体系在分子筛中吸附行为的分子模拟,北京:北京化工大学,2004
[34] 郭继志,近临界条件下苯与丙烯烷基化反应体系的相平衡和反应行为研究,博士学位论文,上海:华东理工大学,2000
[35] 孟祥燕,不同相态下苯丙烯烷基化反应研究,硕士学位论文,太原:中国科学院山西煤炭化学研究所,2002
[36] 孙海,刘靖,郭汝生, 超临界条件下烷基化反应的研究进展,天然气化工, 2003, 28(2):42-45
[37] 王波,多相催化体系中芳烃及其衍生物的烷基化和羟基化,博士学位论文,大连:大连理工大学,2001
[38] 高滋,沸石催化与分离技术,北京:中国石化出版社,1999,3~4
[39] 郝素娥,强亮生,精细合成单元反应与合成设计,哈尔滨:哈哈尔滨工业大学出版社,2001, 69
[40] Wojciechowski B W, Corma A. Catalytic Cracking, Catalysts, Chemistry and Kinetics. New York: Marcel Dekker, 1986, 9
[41] Weisz,P.B., Pure Appl.Chem.,1980, 52, 2091
[42]马沛生,化工数据,北京:中国石化出版社,2003, 42~66, 129~181
[43] Carl L. Yaws, Chemical Properties Handbook, McGraw-Hill, 1999, 5~29, 288~313
[44] Robert H. Perry, Don W. Green, Perry’s Chemical Engineers’ Handbook (7th Edition), 北京:科学出版社,2001, 2-50, 2-52
[45] 杨少华,崔英德,等,ZSM-5 沸石分子筛的合成和表面改性研究进展,精细石油化工进展,2003, 4:47~51
[46] 李绍芬,化学与催化反应工程,北京:化学工业出版社,1986, 458~492
[47] 曾昭槐,择形催化,北京:中国石化出版社,1994, 4~6
[48] 曹声春,胡艾希,催化原理及其工业应用技术,长沙:湖南大学出版社,2001, 151~152
[49] 李栋藩,张盈珍,陶龙镶,等,水热处理对 ZSM-5 沸石的酸性、活性及烯烃选择性的影响,石油化工,1988, 17:150
[50] 杨彩虹,牛清华,卢学栋,焙烧和水热处理对 HZSM-5 沸石酸性和催化活性的影响,天然气化工,1990, 2:11~17