• 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 the production of alcohols, in particular the production of Cd-C4 alcohols used in organic synthesis. The process is carried out by olefin hydration on a fixed bed of an acidic cation exchanger when heated in the presence of another cationic surfactant — dimethyl dimethylammonium chloride, trimethyl palmithylammonium, cetyltrimethyl ammonium or lauryl dimethyl benzyl ammonium, taken in the amount of 0.0005- 0.0098%, taken in the amount of 0.00098%. supplied to the reaction of water. The alcohol is then separated from the water, which is recirculated for hydration. These conditions simplify the process by eliminating the solvent and increase the output of sec-butanol to 207-208 kg / h and isopropanol to 327 kg / h. 2 ill., 3 tab. § ABOUT)
    公开号:SU1400502A3
    申请号:SU864027184
    申请日:1986-03-28
    公开日:1988-05-30
    发明作者:Генн Фридрих；Нейер Вильгельм；Штрельке Гюнтер；Веберс Вернер
    申请人:Дойче Тексако Аг (Фирма)；
    IPC主号:
    专利说明:

    O1
    about
    Hche
     CN
    1140050
    The invention relates to aliphatic alcohols, in particular, to a method for producing Cj-C-alcohols used in organic synthesis.
    The aim of the invention is to increase the yield of the target product and simplify the process by hydrating the corresponding olefin on a fixed bed of acid cation exchanger with POW- jg
    temperature and pressure in the presence of dimethyldiste-arylammonium chloride, trimethyl palmitylammonium, cetyltrimethylamine or lauryl dimethyl benzyl ammonium, taken in the amount of 0.0005-0.0098% of the mass of water supplied to the reaction.
    FIG. 1 shows the setup diagram with the flow of reagents from the bottom up
    at; reactor; FIG. 2 is the same; a mixture of olefins and alkanes is fed from above.
    way down,
    According to FIG. 1, with the help of a metering pump 1, the source gas, which can be pre-saturated; 0.3-1.8 of water, is supplied via pipe ™ to wire 2 and displaced with olefin, which is given through pipeline 3, evaporated in evaporator 4 and fed through pipeline 5 into the cube of the reactor 6. Pump 7i water, to which the cationic surface-active substance is added through the pipe 8, is fed into the reactor through pipe 9 after preheating in the heat exchanger 10. The reactor contains a highly acidic ion exchanger. based on styrene and divinylbenzene. Both reagents are fed from the bottom of the BJBepx through the catalyst bed. The reaction is usually carried out at 120-180 ° C and at a pressure of 40-200 bar with a molar ratio of water and olefin of 0.5- 10: 1. -
    From the top of the reactor, most of the water (90-97%) is withdrawn through conduit 11 and recycled to the bottom of the reactor. From the upper part of the reactor through pipe 12, the resulting alcohol is removed in the form of steam together with excess reaction gas (n-butane and n-butenes), relieved by valve 13, reduced, passed through heat exchangers 14 and 15, and then injected into the equipped high quality fabric
    step-down separator 16. Water being separated
    containing only a small amount: alcohol (1%), is withdrawn through pipeline 17 and is fed back into the process through pipeline 9. Liquid

    2
    the mixture of alcohol, butenes and butanes is removed through conduit 18, again heat exchange is exchanged in heat exchanger 14 and pressure is increased via valve 19 through conduit 20 to column 21, where it is separated into alcohol (exhausted through conduit 2-2) and the reaction gas (branch pipe 23). Pump 24 through line 25 in column 21 serves a small fpegma (reflux number about 0.1-0.5). The main amount of the reaction gas is again fed to the reaction through line 3 by means of a compressor 26. The remaining amount of the gas stream is removed through line 27.
    According to FIG. 2 through the pipeline
    5 0 s 0
    five
    0
    and through pipe 29 - water. After passing through heat exchangers 30, 31, the reactants are fed through line 32 into the tubular reactor 33 filled with acidic ion exchanger.
    The reaction temperature is 100-200 ° C. The pressure ranges from 40-120 bar. The molar ratio of olefin to water is O, 5; 1-30: 1. Preferably work with two phases when using vapor olefin and liquid water.
    In order to better control the heat of reaction, water can be supplied, as shown, along the length of the reactor. The cationic surfactant is fed through pipelines 34 and 35,
    The reaction product is fed through conduit 36 to separator 37 and there it is separated into an organic phase discharged through conduit 38 and into an aqueous phase discharged through conduit 39. Both phases are processed by known techniques. The separable olefin of the organic phase can be recycled depending on the degree of conversion desired. The separated water is recycled to the process through conduit 29.
    Example 1. The reactor 6 shown in FIG. 1 has a diameter of 500 mm and a length of 10.0 meters. It is loaded with 1700 liters of a strongly acidic ion exchanger. The pressure drop is measured along the length of the reactor.
    Through conduit 2, 300.3 kg / h of a mixture of c - butenes and n-butanes (4.544 mol of n-butene) 5 previously saturated with 1.5% of water containing 85% and -benes are fed into the reactor, and through pipeline 9 - 204 kg / h (11.333 mol of demineralized water, and 8 g / h of a 20% dimethyl distearyl ammonium chloride solution is added to the flow of water through conduit 8. Thus, the water has a surfactant concentration of 0.00078% heat up to 155-160 0 in the heat exchanger 10, supplied through the pipeline 2 with the help of the dosing pump 1 initial hectare They are mixed with gas recirculated through pipeline 3, evaporated in an evaporator 4, brought to and through pipe 5 fed to the lower part of the reactor, pressure 60 bar is maintained in the reactor B. From the head part of the reactor through secondary pipe 17, the resulting secondary butyl alcohol in the form of steam, together with excess gas C, relieves pressure, liquefies, passes through heat exchangers 14 and 15, and is introduced into separator 16, separated water is discharged through pipeline 17 and is used again in the process. Approximately 96% of the water withdrawn from the upper part of the reactor is recycled to the bottom by pipeline 11, and the rest of the water is recycled to the bottom by pipes 17 and 9. The liquid mixture of n-butane and n-butenes is again evaporated by heat exchange in heat exchanger 14 and pressure increase - valve 19 and through pipe 20 are fed into column 21, which is divided into alcohol and reaction gas. Spir is discharged through line 22. The main amount of the mixture of n-butanes and n-butenes (2.700 kg / h) is recycled to the reactor with the aid of a compressor 26 through line 3. A small amount of residual gas is pumped through line 27. With the help of a pump 24, a small d-shegma is fed through pipe 25 into the column 21.
    The results are shown in Table 1, where: the Air Force is secondary butyl alcohol; SBE is divorbutyl alcohol,
    Example 2 Example 1 is repeated, with the difference that 80 g / h of a 20% cationic surfactant solution is used, the same results are obtained after 30 days, 4to and in Example 1.
    5 0 5 0 d
    five
    five
    0
    five
    Example 3 The reactor 33 shown in FIG. 2 has a diameter of 500 mm and a length of 10 m. It is loaded with 1,700 l of strongly acidic cation exchanger. To remove the heat of reaction, a portion of the reaction water is fed to the catalyst bed at various locations. The pressure drop is measured along the length of the reactor.
    Pipeline 28 supplies 331 kg / h of a mixture of propenes and propanes containing 92% of propenes (7250 mol of propene) to the reactor, and 29–2475 kg / h (137.5 mmol) of des1- non-purified water through the pipeline. 62 g / h of a 20% dimethyldistearylammonium chloride solution in isopropyl alcohol are fed through pipelines 34 and 35. Part of the water is preheated to 140-145 ° C in a heat exchanger 31, Another part (about 25%) of water without preheating is fed to the reactor in various places in order to remove the heat of reaction. The water has a surfactant concentration of 0.005%. The feed gas supplied through line 28 is evaporated in an evaporator 30 and fed to the reactor head along with the reaction water. A pressure of 100 bar is maintained in the reactor. Pipeline 36 water isopropyl alcohol together with excess reaction gas is fed to the separator 37. After separation of the gas phase, which is discharged through line 38, pipe 26 is diverted 2690 kg / h of aqueous isopropyl alcohol containing 327 kg of isopropyl alcohol and 15.0 kg diisoprosia ether. The water obtained during the subsequent processing of the product is recycled through conduit 29, the catalyst activity is 3.20 mol of isopropyl alcohol l / cat, x, h, and the selectivity is 95.6%. The pressure drop is measured within 1 in the reactor, 6-2.0 bar,
    Below are the results of comparative experiments using in the proposed method known surfactants.
    Example 4 (comparative) Example 1 is repeated, with the difference that -100 g / h of a 20% aqueous solution of plasticizer 257 (test A) or catapine A (test B) or catamine is added to the flow of water through pipe 8. (experience B),
     In this way, water has a concentration of cationic surfactant equal to 0.0098%.
    The results of the experiments are summarized in table.
    Similarly: the results of example 1 with the results of this example indicate an increase in the yield of the target product during a long process.
    Example 5 (comparative). Example 3 is repeated, with the difference that -4TO as a cationic surfactant use 100 g / h of a 20% isopropyl solution of plasticizer 257 (test A) or catapine A (test B) or catamine (test at). Thus, water has a concentration of cationic surfactant equal to O, 0098%. The process is carried out for 30 days. At day after day, the yield of isopropyl alcohol is 325, 327, and 327 kg, respectively, at 16, 15, and 15 kg, respectively, of disinpropyl ether and pressure drop, of 1.8, 1.6, and 1.6 bar, respectively; and in 30 days, the yield of isopropyl alcohol is 308, 316, and 318 kg, respectively, at 21.5, 18, and 17 kg. Accordingly, diisopropyl ether and a pressure drop of 2.8, j1, and 2.0 bar. respectively.
    Comparison of the results of example 3, and where dimethyl distearylamine monomer chloride is used in an amount of 0; 00050% by weight of water and the nut process is carried out for 30 days, with the results of this example indicates an increase in the yield of the desired product the difference is that 8 g / h of butyl solution of trimethyl-palmitylammonium chloride is used as a cationic surfactant, which corresponds to a concentration in water equal to 0.00078% (experiment A) or 100 g / h of a 20% butyl solution of cetyltrime chloride - tilammoni, h o corresponds to a concentration in water equal to 0.0098% 1 (experiment B), or 100 g / h of a 20% butyl solution of lasfildydimethylbenzylammonium chloride, which corresponds to a concentration in water equal to 0.0098% (experiment C) .
    The results are shown in Table. 3

    The proposed method allows to simplify the process due to the exclusion of a polar organic solvent from the process, such as acetone or dioxane, and to increase the yield of secondary butyl alcohol to 207-208 kg / h ((against 180-192 kg / h) and isopropyl alcohol to 327 kg / h (against 308-316 kg / h).
    Formula of Invention
    The method of producing alcohols with 3- or 4-carbon atoms by hydrating the corresponding olefin on a fixed bed of acidic cation exchanger at elevated temperature and under pressure in the presence of a cationic surfactant, followed by processing the resulting product with the separation of the resulting alcohol and recycling water, characterized in that, in order to increase the yield of the target product and simplify the process, dimethyldistearylammonium chloride is used as a cationic surfactant, methyl palmitylammonium, cetiptrimethylammonium or lauryldimethylbenzylammonium in the amount of 0.0005-0.0098% of the mass of the water supplied to the reaction.
    on
    Table 1
    table 2
    Fi.2
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing alcohols with 3- or
    4 carbon atoms by hydration of the corresponding olefin on a fixed layer of acidic cation exchange resin at elevated temperature and pressure in the presence of a cationic surfactant, followed by processing of the resulting product with separation of the resulting alcohol and recycling of water, characterized in that, in order to increase the yield target product and simplification of the process. As the cationic surfactant, dimethyldistearylammonium chloride, trimethyl palmitylammonium chloride, cetyltrimeth are used lammoniya or lauryldimethylbenzylammonium in an amount 0,0005-0,0098% by weight of the water fed to the reaction.
    Table 1 —-------- f ------------
    Duration- (Difference (Quantity - | QuantityI of pressureJbo Air Force,> in SBE, experience, days j bar kg / h kg / h
    1 0.6 208 1.9 3 0.8 207 1.8 5 0.7 207 1.7 7 0.7 208 1.8 9 0.8 207 1.8 eleven 0.8 208 1.9 fifteen 0.7 208 1.8 20 0.8 208 1.8 30 0.8 207 1.8
    7 1400502
    table 2 The duration of the process, days Drop pressureexperience bar Number of Air Force experience kg / h The number of SBE,experience kg / h A B IN A B IN A B IN 1 0.90.7 0.7 205 208 208 2.01.9 1.9 5 1,00.7 0.8 203 207 207 2.11.8 1.8 eleven 1,20.8 0.8 195 201 202 2,51.8 1.9 20 1,50.8 0.8 182 195 197 3.21.8 1.8 thirty 1.70.8 0.9 180 192. 192 3,51.8 1.8
    Table 3
    Process duration ----- ----------------Pressure drop, bar, experience The number of VBS, kg / h, experience The number of SBE, kg / h experience A B IN A B IN A B IN 1 0.6 0.7 0.6 207 207 208 1.9 .1.9 1.9 eleven 0.8 0.8 0.7 207 207 208 1.9 1.9 1.9 thirty 0.8 0.9 0.8 206 207 208 1.9 1.9 1.9
    FIG. 1
    Figure 2
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