二氢月桂烯合成香茅醇的研究
|
摘要
本文研究了以二氢月桂烯为原料来制取香茅醇。该过程包括4个步骤：2号位加上一摩尔氯化氢分子得到2-氯-2，6-二甲基-7-辛烯；7号位加上1摩尔溴化氢分子得到2-氯-8-溴-2，6-二甲基辛烷；消去氯化氢分子还原2号位双键；碱性水溶液中水解得到香茅醇。
在氯化氢加成反应中，向反应体系中添加活性炭可以大大加快反应的进行，因此我们研究了在加入活性碳情况下的最佳反应条件。
溴化氢加成反应采用无水溴化氢鼓泡间歇式反应器时，存在着转化率低、溴化氢气体浪费严重、反应时间长和副反应多等问题，采用垂直管降膜反应器取得了很好的效果，使产物2-氯-8-溴-2，6-二甲基辛烷的收率和转化率大大增加。文中论述了各种降膜吸收反应模型，由此建立了降膜吸收反应的数学模型，通过对该模型和实验数据的计算机模拟，得出了反应管中的温度和浓度等的分布曲线。
This work mainly focuses on the synthesis of citronellol from dihydromyrcene which comprises four steps: (1) Adding one mole of hydrogen chloride to the 2-position to produce 2-chloro-2,6-dimethyl-7-octene. (2) Treating 2-chloro-2,6-dimethyl-7-octene with hydrogen bromide in the presence of a peroxide catalyst to give 2-chloro-8-bromo-2,6-dimethyl octane. (3) Remove hydrogen chloride from the 2-position to reform the double bond involving the number 2 carbon atom. (4) Replacing the bromide atom with a hydroxyl group by hydrolysis with an aqueous base.
In the first step, the reaction conversion has been greatly increased by adding activated carbon in the reaction system. Consequently, the optimal reaction conditions have been investigated.
In the second step, when a HBr-bubbled batch reactor is employed, there is a lot of trouble in the conversion of 2-chloro-2,6-dimethyl-7-octene, consumption of hydrogen bromide, reaction time and side reactions etc.. But, a desired result can be obtained via the reaction of 2-chloro-2,6-dimethyl-7-octene with hydrogen bromide in a vertical falling film reactor. The absorption reaction has been investigated by the experiments. The mathematical models of the reaction in the vertical falling film absorber have been discussed and built. The temperature and concentration distributions in the absorber have been obtained by the computer simulation, respectively.
在氯化氢加成反应中，向反应体系中添加活性炭可以大大加快反应的进行，因此我们研究了在加入活性碳情况下的最佳反应条件。
溴化氢加成反应采用无水溴化氢鼓泡间歇式反应器时，存在着转化率低、溴化氢气体浪费严重、反应时间长和副反应多等问题，采用垂直管降膜反应器取得了很好的效果，使产物2-氯-8-溴-2，6-二甲基辛烷的收率和转化率大大增加。文中论述了各种降膜吸收反应模型，由此建立了降膜吸收反应的数学模型，通过对该模型和实验数据的计算机模拟，得出了反应管中的温度和浓度等的分布曲线。
This work mainly focuses on the synthesis of citronellol from dihydromyrcene which comprises four steps: (1) Adding one mole of hydrogen chloride to the 2-position to produce 2-chloro-2,6-dimethyl-7-octene. (2) Treating 2-chloro-2,6-dimethyl-7-octene with hydrogen bromide in the presence of a peroxide catalyst to give 2-chloro-8-bromo-2,6-dimethyl octane. (3) Remove hydrogen chloride from the 2-position to reform the double bond involving the number 2 carbon atom. (4) Replacing the bromide atom with a hydroxyl group by hydrolysis with an aqueous base.
In the first step, the reaction conversion has been greatly increased by adding activated carbon in the reaction system. Consequently, the optimal reaction conditions have been investigated.
In the second step, when a HBr-bubbled batch reactor is employed, there is a lot of trouble in the conversion of 2-chloro-2,6-dimethyl-7-octene, consumption of hydrogen bromide, reaction time and side reactions etc.. But, a desired result can be obtained via the reaction of 2-chloro-2,6-dimethyl-7-octene with hydrogen bromide in a vertical falling film reactor. The absorption reaction has been investigated by the experiments. The mathematical models of the reaction in the vertical falling film absorber have been discussed and built. The temperature and concentration distributions in the absorber have been obtained by the computer simulation, respectively.
引文
[1]文瑞明主编，香料香精手册，湖南科学技术出版社，1999
[2]赵振东，刘先章，松节油的精细化学应用(Ⅲ)—松节油合成日化香料(中)，林产化工通讯，2001
[3]何间，季儒英编著，香料概论，中国石化出版社，1993
[4]U.S. Patent, 5633236(1997)
[5]U.S.Patent, 6143288(2000)
[6]实用精细化学品手册编写组编，实用精细化学品手册有机卷(上)，化学工业出版社，1996
[7]唐松云编著，香料生产技术与应用，广东科技出版社，2000
[8]Bauer.k. Garbe.D. Common Fragrance and Flavor Material[M]. VCH Weinheim.1985.22-23
[9]黄致喜，王慧辰编著，萜类香料化学，中国轻工业出版社，1999
[10]B.B.A.,Ger.Offen, 2,015,965(1971)
[11]世界精细化工手册(续编)，化学工业部科学技术情报研究所编辑出版，1986
[12]邹勇飞等，香料香精化妆品，1991(3)：1
[13]钟国清，松节油合成香料研究的进展，云南化工，1996，2
[14]邓淑华等，广东化工，1991，(1)16～18
[15]林耀红，谈變峰，萧树德，香茅醛气相加氢制香茅醇反应的研究，林产化学与工业1999年3月第19卷第一期
[16]Lewinsohn, P.E.O.R., 14,369(1923)
[17]Meerwein Schmidt, Ann, 444,221(1925)
[18]Ponndorf, Angew.Chem., 38,138(1926)
[19]H.Rupe and R.Rindkerknecht. Helvetica Chim.Acta 7,541-6(1924)
[20]Marcel Delepine and Charles Hanegraaf, Compt.Rend. 205, 185-8(1937)
[21]Izv Akad Nauk Gruz. SSR.Ser.khim.,1990.16(4):281-292
[22]丁德生，龚隽芳编著，实用合成香料，上海科学技术出版社，1991
[23] 高永方，肖树德等，在改性骨架镍催化剂上柠檬桉叶油选择加氢制备香茅醇，林产化工通讯，1999年33卷第六期
[24] 林耀红，谈燮峰，萧树德，香茅醛气相加氢制香茅醇反应的研究，林产化学与工业1999年第19卷第一期
[25] U.S. Patent, 3275696(1966)
[26] O'Dounell et al., Aust.J.Chem. 19,525(1966)
[27] jp patent, 57024320(1982)
[28] U.S. Patent, 3346650(1967)
[29] Journal of the American Chemical Society, 76,4412(1954)
[30] G.Ohloff, Angew.Chem., 73,240(1961)
[31] Brit. 910,879(1963)
[32] Fr patent, 1349980(1964)
[33] U.S. Patent, 3487118(1969)
[34] U.S. Patent, 3277206(1966)
[35] 刘旦初等，精细化工，5，1，27(1988)
[36] Ohloff, G.,et al., Angew. Chem., 73,240(1961)
[37] J.J.Eisch and W.C.Kaska,Am.Soc.88,2213(1966)
[38] G.B. Patent, 874164(1961)
[39] G.B. Patent, 948662(1964)
[40] U.S. Patent, 2902510(1959)
[41] U.S. Patent, 3005845(1961)
[42] G.B. Patent, 947766(1964)
[43] P.Hazra et al.,Res.Ind, 35,(2). 118(1990)
[44] M.M.Paulose et al., Res.Ind., 17,(1), 11 (1972)
[45] L.Cerveny et al., Czech.252,922(1989)
[46] U.S. Patent, 4029709(1977), (Rhodia)
[47] D.V.Sokol'ski et al.,Izv.Akad.Nauk,Kza.SSR,Ser.Khim.,26,(6),26,(1976)
[48] H.Yagi et al., Yukagaku, 26,232,(1977)
[49] Neilan,J.P.,Laine,R.M.,Cortese.N.,and heck,R.F.J.Org.Chem, 1976;41,3455-60
[50] Shell Int.Res.My.,Ger.Offen.2,652,202(1977)
[51] Shell Int.ress.My.Ger.Offen.;2,704,547(1977)
[52] Akiyama,T.Sekiyu Gakkaishi 17(2),95-104(1974)
[53] H.R.Ansari et al.,Ger.Offen.2,224,136(1973)
[54] Brit. 1,389,837(1975)
[55] B.N.Joshi et al., Tetrahe dron,20,2911(1964)
[56] W.Daniewski et al., Tluszcze, srodki piorace, Kosmet, 13,229(1969)
[57] T.Shono et al.,Tetrahedron Lett.,1974,1295
[58] T.Shono et al., Japan. Kokai 50 69,008(1975)
[59] I.Z.Siemion,Roczn.Chim.33,(4-5), 1183(1959)
[60] 司杭主编，有机化工原料，化学工业出版社，1999年1月第三版
[61] 梁世懿编，加成反应，人民教育出版社，1980
[62] 马怀柱编著，基础有机化学反应，安徽教育出版社，1987
[63] 日本化学会编，无机化合物合成手册，曹惠民 包文滁 安家驹译，化学工业出版社，1983年10月第一版
[64] 何泽人编译，无机制备化学手册(上册)，燃料化学工业出版社，1972
[65] M.L.李，F.J.杨，KD.巴特尔著，王其昌等译，毛细管柱气相色谱法，化学工业出版社，1988
[66] 詹益兴，实用气相色谱分析，湖南科技出版社，1983
[67] 化学工程手册编写委员会编．化学工程手册：第12篇气体吸收．化学工业出版社，1982
[68] 天津大学物理化学教研室编，物理化学．高等教育出版社，1992，5
[69] 程文龙，贾磊，陈则韶，风冷垂直管降膜吸收器及其传热传质问题的研究，太阳能学报，2002,23(2)
[70] Fujita T., Fallingfilms in absorption machinese, Int. J. refrig., 1993, 16(4):282～294
[71] 杨景昌，党洁修，热管式溶液吸收器传热传质过程的数值模拟，四川联合大学学报(工程科学版)，1997，1(1)：63～67
[72] 杨景昌，张国喜，党洁修，热管式降膜吸收器的传热传质，高校化学工程学报，
1997，11、(2)：126～139
[73] 廖运文，杨景昌，党洁修，热管式降膜吸收器波动降膜传热传质过程研究，四川联合大学学报(工程科学版)，1999，3(6)：63～68
[74] Ru Yang, Derrming Jou, Heat and mass transfer on the wave film absorption process, Can. J. Chem. Eng., 1993, 71(4): 533～538
[75] Grossman G., Heat and mass transfer in film absorption, Handbook of heat and mass transfer, New York: Gulf Rublishing, 1986
[76] Ru Yang, Byard D., Wood A., A numerical solution of the wave motion on a film, Can.J. Chem. Eng., 1991, 69(6): 723～728
[77] Johnson G. R., Crynes B. L., Modelling of a thin-film sulfur trioxide sulfonation reactor,Ind. Eng. Chem. Process Des. Dev., 1974, 13.6～14
[78] Hurlbert R. C., Knott R. F., Cheney H. A., Apparatus for small scale sulfonation with SO_3, Soap Chemi. Specialties, 1967, 100:88～94
[79] Gilliland E. R., Sherwood T. K., Diffusion of vapors into air streams, Ind. Eng. Chem.,1934, 26:516～523
[80] Davis E. J., Van Ouwerkerk M., Venkatesh S., An Analysis of the falling film gas-liquid reactor, Chem. Eng Sci., 1979, 34:539～550
[81] Gutiérrez J., Mans C., Costa J., Improved mathematical model for a falling film sulfonation reactor, Ind. Eng. Chem. Res., 27:1701～1707
[82] Dabir B., Riazi M. R., Davoudired H. R., Modelling of falling film reactors, Chem. Eng Sci., 1996, 51:2553～2338
[83] Van Dam M. H. H., Lamine A. S., Roizard D., Lochon P., Roizard C., Selective sulfur dioxide absorption using organic solvents, Ind. Eng. Chem. Res., 1997, 36:4628～4637
[84] Van Dam M. H. H., Corriou J. P., Lamine A. S., Roizard C., Modelling and measurement of sulfur dioxide absorption rate in a laminar film reactor, Chem. Eng. Sci., 1999, 54:5311～5318
[85] Bird R. B., Steward W. E., Lightfoot E. N., Transport Phenomena, (7~(éme)éd.), 1966, New York: John
[86] Federico I., Talens-Alesson, The modeling of film chemical reactors, Chem. Eng. Sci.,
1999,54:1871～1881
[87] Lide D. R., CRC handbook of chemistry and physics (74~(éme)éd.), Boca Raton: CRC Press, 1993—1994
[88] Barker B. J., Rosenfarb J., Caruso J. A., Ureas as solvents for chemical investigations, Angewandte Chemie international Edition in English, 1979, 18:503～507
[89] Hikita H., Ishimi K., Mass transfer into laminar gas streams in wetted-wall columns with cocurrent gas-liquid flow, J. Chem. Eng., 1976, 9:362～367
[90] Reid R. C., Prausnitz J. M., Sherwood T. K., The properties of gases and liquids, (3~(éme)éd.), New York: McGraw-Hill, 1977
[91] Reid R. C., Prausnitz J. M., Poling B. E., The properties of gases and liquids, (4~(éme)éd.), New York: McGraw-Hill, 1987
[92] 徐士鸣，袁一，垂直管内降膜吸收过程热—质传递数值计算问题的研究，大连理工大学学报，1997，37(4)：414～419
[93] Riazi M. R., Faghri A., Effect of the interfacial grag on gas absorption with chemical reaction in a vertical tube, AIChE J., 1986, 32(4): 696～699
[94] Riazi M. R., Estimation of rates and enhancement factors in gas absorption with chemical reaction and phase mass transfer resistances, Chem. Eng. Sci., 41(11):2925～2929
[95] Lapidus L., Digital computation for chemical engineering, McGraw-Hill: New York,1962
[2]赵振东，刘先章，松节油的精细化学应用(Ⅲ)—松节油合成日化香料(中)，林产化工通讯，2001
[3]何间，季儒英编著，香料概论，中国石化出版社，1993
[4]U.S. Patent, 5633236(1997)
[5]U.S.Patent, 6143288(2000)
[6]实用精细化学品手册编写组编，实用精细化学品手册有机卷(上)，化学工业出版社，1996
[7]唐松云编著，香料生产技术与应用，广东科技出版社，2000
[8]Bauer.k. Garbe.D. Common Fragrance and Flavor Material[M]. VCH Weinheim.1985.22-23
[9]黄致喜，王慧辰编著，萜类香料化学，中国轻工业出版社，1999
[10]B.B.A.,Ger.Offen, 2,015,965(1971)
[11]世界精细化工手册(续编)，化学工业部科学技术情报研究所编辑出版，1986
[12]邹勇飞等，香料香精化妆品，1991(3)：1
[13]钟国清，松节油合成香料研究的进展，云南化工，1996，2
[14]邓淑华等，广东化工，1991，(1)16～18
[15]林耀红，谈變峰，萧树德，香茅醛气相加氢制香茅醇反应的研究，林产化学与工业1999年3月第19卷第一期
[16]Lewinsohn, P.E.O.R., 14,369(1923)
[17]Meerwein Schmidt, Ann, 444,221(1925)
[18]Ponndorf, Angew.Chem., 38,138(1926)
[19]H.Rupe and R.Rindkerknecht. Helvetica Chim.Acta 7,541-6(1924)
[20]Marcel Delepine and Charles Hanegraaf, Compt.Rend. 205, 185-8(1937)
[21]Izv Akad Nauk Gruz. SSR.Ser.khim.,1990.16(4):281-292
[22]丁德生，龚隽芳编著，实用合成香料，上海科学技术出版社，1991
[23] 高永方，肖树德等，在改性骨架镍催化剂上柠檬桉叶油选择加氢制备香茅醇，林产化工通讯，1999年33卷第六期
[24] 林耀红，谈燮峰，萧树德，香茅醛气相加氢制香茅醇反应的研究，林产化学与工业1999年第19卷第一期
[25] U.S. Patent, 3275696(1966)
[26] O'Dounell et al., Aust.J.Chem. 19,525(1966)
[27] jp patent, 57024320(1982)
[28] U.S. Patent, 3346650(1967)
[29] Journal of the American Chemical Society, 76,4412(1954)
[30] G.Ohloff, Angew.Chem., 73,240(1961)
[31] Brit. 910,879(1963)
[32] Fr patent, 1349980(1964)
[33] U.S. Patent, 3487118(1969)
[34] U.S. Patent, 3277206(1966)
[35] 刘旦初等，精细化工，5，1，27(1988)
[36] Ohloff, G.,et al., Angew. Chem., 73,240(1961)
[37] J.J.Eisch and W.C.Kaska,Am.Soc.88,2213(1966)
[38] G.B. Patent, 874164(1961)
[39] G.B. Patent, 948662(1964)
[40] U.S. Patent, 2902510(1959)
[41] U.S. Patent, 3005845(1961)
[42] G.B. Patent, 947766(1964)
[43] P.Hazra et al.,Res.Ind, 35,(2). 118(1990)
[44] M.M.Paulose et al., Res.Ind., 17,(1), 11 (1972)
[45] L.Cerveny et al., Czech.252,922(1989)
[46] U.S. Patent, 4029709(1977), (Rhodia)
[47] D.V.Sokol'ski et al.,Izv.Akad.Nauk,Kza.SSR,Ser.Khim.,26,(6),26,(1976)
[48] H.Yagi et al., Yukagaku, 26,232,(1977)
[49] Neilan,J.P.,Laine,R.M.,Cortese.N.,and heck,R.F.J.Org.Chem, 1976;41,3455-60
[50] Shell Int.Res.My.,Ger.Offen.2,652,202(1977)
[51] Shell Int.ress.My.Ger.Offen.;2,704,547(1977)
[52] Akiyama,T.Sekiyu Gakkaishi 17(2),95-104(1974)
[53] H.R.Ansari et al.,Ger.Offen.2,224,136(1973)
[54] Brit. 1,389,837(1975)
[55] B.N.Joshi et al., Tetrahe dron,20,2911(1964)
[56] W.Daniewski et al., Tluszcze, srodki piorace, Kosmet, 13,229(1969)
[57] T.Shono et al.,Tetrahedron Lett.,1974,1295
[58] T.Shono et al., Japan. Kokai 50 69,008(1975)
[59] I.Z.Siemion,Roczn.Chim.33,(4-5), 1183(1959)
[60] 司杭主编，有机化工原料，化学工业出版社，1999年1月第三版
[61] 梁世懿编，加成反应，人民教育出版社，1980
[62] 马怀柱编著，基础有机化学反应，安徽教育出版社，1987
[63] 日本化学会编，无机化合物合成手册，曹惠民 包文滁 安家驹译，化学工业出版社，1983年10月第一版
[64] 何泽人编译，无机制备化学手册(上册)，燃料化学工业出版社，1972
[65] M.L.李，F.J.杨，KD.巴特尔著，王其昌等译，毛细管柱气相色谱法，化学工业出版社，1988
[66] 詹益兴，实用气相色谱分析，湖南科技出版社，1983
[67] 化学工程手册编写委员会编．化学工程手册：第12篇气体吸收．化学工业出版社，1982
[68] 天津大学物理化学教研室编，物理化学．高等教育出版社，1992，5
[69] 程文龙，贾磊，陈则韶，风冷垂直管降膜吸收器及其传热传质问题的研究，太阳能学报，2002,23(2)
[70] Fujita T., Fallingfilms in absorption machinese, Int. J. refrig., 1993, 16(4):282～294
[71] 杨景昌，党洁修，热管式溶液吸收器传热传质过程的数值模拟，四川联合大学学报(工程科学版)，1997，1(1)：63～67
[72] 杨景昌，张国喜，党洁修，热管式降膜吸收器的传热传质，高校化学工程学报，
1997，11、(2)：126～139
[73] 廖运文，杨景昌，党洁修，热管式降膜吸收器波动降膜传热传质过程研究，四川联合大学学报(工程科学版)，1999，3(6)：63～68
[74] Ru Yang, Derrming Jou, Heat and mass transfer on the wave film absorption process, Can. J. Chem. Eng., 1993, 71(4): 533～538
[75] Grossman G., Heat and mass transfer in film absorption, Handbook of heat and mass transfer, New York: Gulf Rublishing, 1986
[76] Ru Yang, Byard D., Wood A., A numerical solution of the wave motion on a film, Can.J. Chem. Eng., 1991, 69(6): 723～728
[77] Johnson G. R., Crynes B. L., Modelling of a thin-film sulfur trioxide sulfonation reactor,Ind. Eng. Chem. Process Des. Dev., 1974, 13.6～14
[78] Hurlbert R. C., Knott R. F., Cheney H. A., Apparatus for small scale sulfonation with SO_3, Soap Chemi. Specialties, 1967, 100:88～94
[79] Gilliland E. R., Sherwood T. K., Diffusion of vapors into air streams, Ind. Eng. Chem.,1934, 26:516～523
[80] Davis E. J., Van Ouwerkerk M., Venkatesh S., An Analysis of the falling film gas-liquid reactor, Chem. Eng Sci., 1979, 34:539～550
[81] Gutiérrez J., Mans C., Costa J., Improved mathematical model for a falling film sulfonation reactor, Ind. Eng. Chem. Res., 27:1701～1707
[82] Dabir B., Riazi M. R., Davoudired H. R., Modelling of falling film reactors, Chem. Eng Sci., 1996, 51:2553～2338
[83] Van Dam M. H. H., Lamine A. S., Roizard D., Lochon P., Roizard C., Selective sulfur dioxide absorption using organic solvents, Ind. Eng. Chem. Res., 1997, 36:4628～4637
[84] Van Dam M. H. H., Corriou J. P., Lamine A. S., Roizard C., Modelling and measurement of sulfur dioxide absorption rate in a laminar film reactor, Chem. Eng. Sci., 1999, 54:5311～5318
[85] Bird R. B., Steward W. E., Lightfoot E. N., Transport Phenomena, (7~(éme)éd.), 1966, New York: John
[86] Federico I., Talens-Alesson, The modeling of film chemical reactors, Chem. Eng. Sci.,
1999,54:1871～1881
[87] Lide D. R., CRC handbook of chemistry and physics (74~(éme)éd.), Boca Raton: CRC Press, 1993—1994
[88] Barker B. J., Rosenfarb J., Caruso J. A., Ureas as solvents for chemical investigations, Angewandte Chemie international Edition in English, 1979, 18:503～507
[89] Hikita H., Ishimi K., Mass transfer into laminar gas streams in wetted-wall columns with cocurrent gas-liquid flow, J. Chem. Eng., 1976, 9:362～367
[90] Reid R. C., Prausnitz J. M., Sherwood T. K., The properties of gases and liquids, (3~(éme)éd.), New York: McGraw-Hill, 1977
[91] Reid R. C., Prausnitz J. M., Poling B. E., The properties of gases and liquids, (4~(éme)éd.), New York: McGraw-Hill, 1987
[92] 徐士鸣，袁一，垂直管内降膜吸收过程热—质传递数值计算问题的研究，大连理工大学学报，1997，37(4)：414～419
[93] Riazi M. R., Faghri A., Effect of the interfacial grag on gas absorption with chemical reaction in a vertical tube, AIChE J., 1986, 32(4): 696～699
[94] Riazi M. R., Estimation of rates and enhancement factors in gas absorption with chemical reaction and phase mass transfer resistances, Chem. Eng. Sci., 41(11):2925～2929
[95] Lapidus L., Digital computation for chemical engineering, McGraw-Hill: New York,1962