• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to aliphatic alcohols, in particular lower aliphatic alcohols I, which are widely used as raw materials and solvents in mainly organic and petrochemical syntheses. Increasing the yield of the target product is achieved by using a different catalyst and water for treatment. The process is carried out by treating an ether of the formula RI-OR, where R and is lower alkyl, with water at their molar ratio of 1: (1.37-6.49), 110-180 s and pressure 15-100 atm in the presence of a sulfonic acid ion-exchange resin type The resulting organic phase, containing alcohol and unreacted ether, is recycled and recovered from the aqueous phase by distillation. The recycled organic phase is preferably extracted with water. Output I 69-98% vs. 25%. 1 hp formulas. 2 na. § JV о о о с / 1
    公开号:SU1301307A3
    申请号:SU843796141
    申请日:1984-10-03
    公开日:1987-03-30
    发明作者:Нейер Вильгельм；Веберс Вернер；Деттмер Михаэль
    申请人:Дейче Тексако Аг (Фирма)；
    IPC主号:
    专利说明:

    1,130
    The invention relates to an improved process for the preparation of lower aliphatic alcohols, widely used as raw materials and solvents in basic organic and petrochemical synthesis.
    The purpose of the invention is to increase the yield of the target products, achieved by treating a simple ether with water in
    3072
    According to FIG. 2, the organic phase is withdrawn through conduit 6 in the heat exchanger 7 and then fed to extractor 8, where at a lower temperature (at 100 ° C) by washing it is supplied with water through the conduit 9, the alcohol still contained in the recycle stream is separated. Alcohol Free Stream
    the liquid phase at a molar ratio of 0, then through conduit 10 again naked 1: (1.37-6.49) at a temperature of 110-180 ° C and a pressure of 15-100 atm in the presence of a sulfonic acid type ion exchange resin as an acid catalyst .
    FIG. 1 and 2 show the schemes for implementing the proposed method.
    According to FIG. 1, a simple ether is continuously supplied through pipe 1, and water is fed through pipe 2. These components are fed through reactor 3 together to reactor 4. As a result of the liquid phase reaction at 155–180 ° C and 15–100 bar in the presence of an acidic catalyst, the ether is hydrolyzed. The alcohol formed and the starting ester with water are distributed in two immiscible liquid phases: alcohol – water and ether – alcohol. The alcohol is much more soluble in the aqueous phase than the ether. Thus, after separation of the phases through the pipeline 5, along with a small amount of ether with an excess of water, a product can be withdrawn from which the alcohol is recovered by distillation.
    are recycled and recycled to the splitting reactor. Aqueous alcohol is discharged through line 11.
    The method is illustrated by the following.
     5 examples (all percentage data are given in wt.%).
    Example 1. In the reactor (figure 1) with a diameter in the light of 26 mm and a length of 5 m, filled with 2.5 liters of highly acidic
    0 Amberlite 252 ionite (sulfonated copolymer of styrene and divinylbenzene) as catalyst, 254 g (2.5 mol) of diisopropyl ether and 2225 g (123.5 mol) of demineralized water are served hourly. Taking into account the indicated quantities ftJx quantities, the molar ratio of ether and water is 1: 1.37,
    ABOUT
    The reaction is carried out at 155 ° C under 30 at a pressure of 50 atm. At the same time, 23 l (17365 g / h) of the upper organic phase formed in the reactor consisting of 72% (122.4 mol) of unreacted 35 simple E (mra, 20% isopropyl alcohol, 5% (48.2 mol)) are obtained hourly. water and 3% propylene, which is recycled along with the initial simple oe (4 ore to the bottom of the reactor, as well as 2455 g of an aqueous liquid phase consisting of 88% water, 11.0% isopropyl alcohol and 1% diisopropyl ether. Per liter of catalyst in 108 g (1.8 mol) of isopropyl alcohol are formed.
    The reaction is carried out at 155 ° C under 30 at a pressure of 50 atm. At the same time, 23 l (17365 g / h) of the upper organic phase formed in the reactor consisting of 72% (122.4 mol) of unreacted 35 simple E (mra, 20% isopropyl alcohol, 5% (48.2 mol)) are obtained hourly. water and 3% propylene, which is recycled along with the initial simple oe (4 ore to the bottom of the reactor, as well as 2455 g of an aqueous liquid phase consisting of 88% water, 11.0% isopropyl alcohol and 1% diisopropyl ether. Per liter of catalyst in 108 g (1.8 mol) of isopropyl alcohol are formed.
    Unreacted ether and 40 possible small amount of olefins, which is separated as an upper phase at the head of the column, without intermediate treatment are fermented through line 6 to reactor 4. To reach -45 gas phase is not observed, the high degree of cleavage of ether 90%) and to achieve a good mixing of both phases, the light phase (ether - alcohol).
    Thus, the yield of isopropyl alcohol is 90.4% in terms of the initial diisopropyl section in the upper part of the reactor, 50, served in the amount of 3-23 l / h in Example 2, Repeat example
    cube reactor. This leads (disregarding 1, with the difference that the process of simple ether, which after distillation can also be recycled at 55 reactants), leads to a high conversion of the starting ether to alcohol, since the olefins are also recycled to alcohol under the reaction conditions.
    d t at a pressure of 25 atm and 15 atm. You get the same results as in example 1,
    Example 3, Example 1 is repeated with the difference that the reaction is carried out in the device according to FIG. 2 and the upper organic phase (23 l / h
    072
    According to FIG. 2, the organic phase is withdrawn through conduit 6 in the heat exchanger 7 and then fed to extractor 8, where at a lower temperature (at 100 ° C) by washing it is supplied with water through the conduit 9, the alcohol still contained in the recycle stream is separated. Alcohol Free Stream
    then through conduit 10 is again heated and recycled to the splitting reactor. Aqueous alcohol is discharged through line 11.
    The method is illustrated by the following.
    5 examples (all percentage data are given in wt.%).
    Example 1. In the reactor (figure 1) with a diameter in the light of 26 mm and a length of 5 m, filled with 2.5 liters of highly acidic
    0 Amberlite 252 ionite (sulfonated copolymer of styrene and divinylbenzene) as catalyst, 254 g (2.5 mol) of diisopropyl ether and 2225 g (123.5 mol) of demineralized water are served hourly. Taking into account the indicated quantities ftJx quantities, the molar ratio of ether and water is 1: 1.37,
    ABOUT
    The reaction is carried out at 155 C under 0 pressure of 50 atm. In this case, 23 l (17365 g / h) of the upper organic phase formed in the reactor consisting of 72% (122.4 mol) of unreacted 5 simple E (mra, 20% isopropyl alcohol, 5% (48.2 mol)) are obtained every hour. water and 3% propylene, which is recycled along with the initial simple oe (4 ore to the bottom of the reactor, as well as 2455 g of an aqueous liquid phase consisting of 88% water, 11.0% isopropyl alcohol and 1% diisopropyl ether. Per liter of catalyst in 108 g (1.8 mol) of isopropyl alcohol are formed.
    0 5 no gas phase is observed
     1 with the difference that the process is
    d t at a pressure of 25 atm and 15 atm. You get the same results as in example 1,
    Example 3, Example 1 is repeated with the difference that the reaction is carried out in the device according to FIG. 2 and the upper organic phase (23 l / h
    -17365 g / h composition: 79% diisopropyl ether, 14.5% isopropyl alcohol, 4% water and 2.5% propylene) after cooling to 100 ° C, is fed to the extraction of isopropyl alcohol with water supplied in an amount of 2058 g / h 450 g / h (4.4 mol) of ether and 3292 g / h (182.7 mol) of water are fed to the reaction. With these recycle quantities, the molar ratio of ether to water is 1: 1, 59.
    In this case, 2361 g / h of the aqueous phase consisting of 87.2% water, 11.9% isopropyl alcohol and 0.9% isopropyl ether, and also 17062 g / h recycled to the reaction of the ether phase are withdrawn from the extraction stage. consisting of 80.3% (134.1 mol) of disopropyl ether. 13.1% isopropyl alcohol, 4% (37.9 mol) of water and 2.6% propylene.
    In addition, 3440 g / h of the aqueous liquid phase, consisting of 93.6% water, 5.9% isopropyl alcohol and 0.5% ether, are withdrawn from the reactor.
    Only 194 g (3.2 mol) of isopropyl ether are obtained per liter of catalyst per hour.
    Thus, the yield of isopropyl alcohol is 91.2% based on the starting ether.
    Example 4. Example 1 is repeated, with the difference that 600 g / h (6.8 mol) of methyl tert-butyl ether is reacted with 3100 g / h (172 mol) of demineralized water at 110 ° C and a pressure of 50 atm. In addition, another 23 l / h (18,200 g / h) of the organic phase obtained in the upper part of the reactor, consisting of 46% tert-butyl alcohol, 24% (49.6 mol) of unreacted ether, 18% (181.8 mol) of water, 5% methyl alcohol and 7% isobutene. Thus, the molar ratio of ether and water is 1: 6.27. 3700 g / h of liquid aqueous phase consisting of 80.8% water, 12.5% tert-butyl alcohol, 5 , 4% methanol and 1.3% methyl tert-bully ether.
    185.2 g (2.5 mol) of tert-butyl alcohol are obtained per liter of catalyst per hour. No gas phase formation is observed.
    Thus, the yield of tert-butyl alcohol is 92% based on the starting ether.
    Example 5. Example 1 is repeated with the difference that the reaction is carried out at a pressure of 100 atm, and 3 l / h (2265 g / h of the organic phase consisting of 78.5 (17.4 mol) diisopropyl ether are recycled to the reaction , 15% isopropyl alcohol, 4.5% (5.66 mol) of water and 2.0% propane. The molar ratio of ether to water is 1: 6.49.
    2445 g / h of a liquid aqueous phase consisting of 88.5% water, 7.5% isopropyl alcohol and 4.0% diisopropyl ether are withdrawn from the reactor. 1.2 mol of isopropyl alcohol is produced per liter of catalyst per hour.
    Thus, the yield of isopropyl alcohol is 61.6% based on the starting ester.
    Example 6. Example 1 was repeated, with the difference that the reaction was carried out at 180 ° C, supply of isopropyl ether in the amount of 450 g / h (4.4 mol) and recirculation of the organic phase consisting of 62% (105.4 mol ) diisopropyl ether, 28.5% isopropyl alcohol, 6% (57.8 mol) of water and 3.5% propylene. Here, the molar ratio of ether and water is 1: 1.65. 2650 g / h of liquid phase consisting of 80.3% water, 15.0 isopropyl alcohol and 4.2% diisopropyl ether are withdrawn from the reactor.
    Thus, the yield of isopropyl alcohol is 75.1%, based on the starting diisopropyl ether (ip. 2.65 mol of isopropyl alcohol per liter of catalyst per hour).
    Example 7. Example 1 is repeated with the difference that fresh water is fed to the reaction in the amount of 4500 g / h (249.7 mol), and the organic phase recycled to the reaction consists of 83% (141.1 mol) of diisopropyl ether , 12% isopropyl alcohol, 3.0% (28.9 mol) of water and 2.0% propylene. Here, the molar ratio of ether to water is 1: 1.94. 4754 g / h of liquid phase consisting of 93.7% water, 6.2% isopropyl alcohol and 0.1% diisopropyl are withdrawn from the reactor.
    Thus, the yield of isopropyl ether is 98.6% based on the starting ester.
    Per liter of catalyst per hour, 1.97 mol of alcohol is formed.
    The proposed method allows to increase the yield of lower alcohols to 61-98% versus 25% in the known.
    权利要求:
    Claims (2)
    [1]
    1. A method of producing lower aliphatic alcohols, including the treatment of a simple Lbromula
    R - O - F ,,
    where R and RJ are lower alkyl, in the presence of an acidic catalyst at elevated temperature and pressure, followed by separation of the target product, characterized in that, in order to increase the yield of the target product, the ether is treated with water in the liquid phase their molar ratio of 1:: (1.37-6.49) at a temperature of 110-180 ° C and a pressure of 15-100 atm in the presence of an ion-exchange resin of the sulfo-acid type as an acidic catalyst to produce an organic phase containing alcohol and unreacted simple ether which I subject recirculation, and the aqueous phase containing the alcohol from which the desired product is isolated.
    [2]
    2. A method according to claim 1, characterized in that the recycled organic phase is subjected to extraction with water.
    Vus.j
    Tf
    Phi, i
    Editor M. Nedoluzhenko
    Compiled by I. Kipitanova
    Tehred V. Kadar Proofreader A. Zimokosov
    Order 1163/58 Circulation 372
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab, d. A / 5
    Production and printing company, Uzhgorod, st. Project, 4
    Subscription
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2519061A|1947-04-12|1950-08-15|Standard Oil Dev Co|Hydration of ethers|
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    US4374286A|1982-02-26|1983-02-15|Uop Inc.|Hydration of olefins|DE3419392C1|1984-05-24|1985-12-05|Deutsche Texaco Ag, 2000 Hamburg|Process for the continuous production of isopropyl alcohol or sec. Butyl alcohol|
    DE3628007C1|1986-08-19|1987-11-05|Deutsche Texaco Ag, 2000 Hamburg, De|
    US5043486A|1990-08-23|1991-08-27|Exxon Research And Engineering Company|Aquathermolytic cleavage of ethers|
    US5453561A|1994-01-27|1995-09-26|Exxon Research & Engineering Co.|Reactive separation process|
    TW321634B|1994-07-05|1997-12-01|Mitsui Toatsu Chemicals|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19833336644|DE3336644A1|1983-10-08|1983-10-08|METHOD FOR THE CONTINUOUS PRODUCTION OF ALCOHOLS|
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