• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    The hydrogenation of 2-ethylhexenal to 2-ethylhexanol in the liquid phase until now led to impure products having high bromine numbers. …<??>Using the supported catalyst claimed, the hydrogenation is possible at comparatively low temperatures with a high catalyst loading. A very pure 2-ethylhexanol having low bromine numbers is obtained. …<??>Preparation of the catalyst and of 2-ethylhexanol.
    公开号:SU1739844A3
    申请号:SU894613389
    申请日:1989-02-03
    公开日:1992-06-07
    发明作者:Люкен Ганс-Герд；Тангер Уве；Дросте Вильгельм；Лудвиг Герхард；Губиш Дитмар
    申请人:Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the catalytic liquid phase hydrogenation of aldehydes, in particular, to a process for the preparation of 2-ethylhexanol.
    A known method of producing 2-ethylhexanol by liquid phase hydrogenation of 2-ethylhexenal at 80-200 ° C and a pressure of 1-500 is on a catalyst containing nickel and / or cobalt and copper and / or chromium and / or manganese and a pyro- or polyacid in free form or in the form of a salt of these metals, obtained by coating a carrier with a solution containing the salts of these metals and pyro or polyacid in a free form or in the form of a salt of these metals, and subsequent calcination and reduction.
    The disadvantage of this method is that due to the low load on the catalyst (the volumetric rate of liquid per hour is no more than 0.2) and the insufficient purity of the hydrogenation product (the bromine number is 0.1-0.13), the efficiency of the liquid hydrogenation is 2 - ethylhexenal is unsatisfactory.
    The purpose of the invention is to increase the efficiency of liquid-phase hydrogenation of 2-ethylhexenal.
    The goal is achieved by the method of obtaining 2-ethylhexanol by liquid-phase hydrogenation of 2-ethylhexenal at 120-180 ° C and a pressure of 16-80 bar on a nickel-copper-chromium catalyst prepared by applying a solution of the salts of these metals on the support and subsequent calcination and reduction The process is carried out on a catalyst containing an additional alkali metal, the alkali metal and chromium being introduced into the catalyst through an alkali metal dichromate salt.
    i y
    sl
    00 X) 00 4 l

    cm
    3
    Example 1. To obtain an impregnating solution, 37 g of copper nitrite XSIigO, 857.2 g of nickel nitrate solution containing nickel, 5.7 g of sodium dichromate 2HDO and 1.4 g of 65% nitric acid are dissolved in water. After filtration, water is added to obtain 4336 g of the solution. An aqueous solution of metal salts is sprayed onto 1899 g of silica granules at 9 ° C.
    17
    The wet carrier loaded with metal salts is dried at 110 ° C and dried
    zyniruyut at 350 ° C. The thickness of the active edge zone is 0.24 mm. The catalyst contains 0.3% copper, C, 5% nickel, 0.7% chromium, and 0.03% sodium. 90 g of catalyst are fed to an isothermal tubular reactor, where it is first reduced with hydrogen at 200 ° C. Then 1200 cm of the liquid feedstock of the composition, wt.%: 2-ethylhexenal 24.5, 2-ethylhexenal 1, 62, 2-ethylhexenol 0.01 2-ethylhexanol 73.3 and water 0.58 are fed into the reactor and the reaction is carried out at 150 ° C and a pressure of 40 bar. In this case, the liquid reaction mixture is circulated through the catalyst with a load across the cross section of the reactor equal to 36 m3 / m2. h. Hydrogen is fed in the amount of 300 l / h. Excess hydrogen is removed from the reactor. The rate of formation of 2-ethylhexanol is observed for 6 hours. The product of the composition, masd: 2-ethylhexanol 99.54, 2-ethylhexenal 0.01, 2-ethylhexanal 0.06, 2-ethylhexenol 0.04 and water 0.34, is obtained. With a conversion of 99.9% of the load, i.e. volume speed. fluid velocity / h is 2 ,. The bromine number of 2-ethylhexanol is 0.054. EXAMPLE 2. To obtain an impregnating solution, 137 g of nickel 6Hfc nitrate, 199 g of copper x nitrate, 11.2 g of sodium &quot; dichromate &quot; 2H20 and 2.8 g of 65% nitric acid are dissolved in water, in an amount that provides a solution of metal salts with a volume of 928 cm3. The solution is sprayed onto 1744 g of alumina pellets at room temperature.
    The calcining after drying is carried out at 450 ° C. The active components of the calcined catalyst are homogeneously distributed in the carrier. The catalyst contains 3% copper, 1.3% nickel l, 0.26% chromium, and 0.11% sodium.

    This catalyst was used for the liquid phase hydrogenation under the conditions of example 1 of the feedstock composition, wt.%: 2-ethylhexenal 23.5, 2-ethylhexanal 0.32, 2-ethylhexenol 0.15, 2-ethylhexanol 75.34 and water 0, 69 You get a product composition, wt.%: 2-ethylhexanol 99,29, 2-ethylhexenal 0,01, 2-ethylhexanal 0.07, 2-ethylhexenol 0.03 and water 0.61.
    At a conversion of 99.9% volume sc10
    -
    - (
    15
    fluid speed / h is 3.3 hours. The bromine number of 2-ethylhexanol is 0.04.
    EXAMPLE 3 Analogously to Example 2, a catalyst was prepared containing 6.5% copper, 3.1% nickel, 0.6% chromium and 0.24% sodium, which is used for liquid phase hydrogenation under the conditions of example 1 feedstock composition, wt.%: 2-ethylhexenal 27,59, 2-ethylhexanal 0.21, 2-ethylhexenol 0.06, 2-ethylhexanol 71.29 and water
    , 0.85. You get a product composition, wt0%: 2-ethylhexanol 99,39, 2-ethylhexenal 0,01, 2-ethylhexanal 0,01, 2-ethylhexenol 0.04 and water 0.57.
    At a conversion of 99.9%, the liquid / h volume rate is 6.8 hours and the bromine number of 2-ethylhexanol is 0.018.
    Example 4 Analogously to Example 1, a catalyst is prepared containing 5.3% copper, 5.5% nickel, 2.5% chromium and 1.1% sodium, which is used for liquid phase hydrogenation under the conditions of example 1 feedstock composition, wt.%: 2-ethylhexenal 25,53, 2-ethylhexanal 0.71, 2-ethylhexenol
    40 0.03, 2-ethylhexanol 73.17 and water 0.56. A product of the composition is obtained, wt%: 2-ethylhexanol 99.63, 2-ethylhexenal 0.01, 2-ethylhexanal "Ј0.01, 2-ethylhexenol 0.03 and
    45 water 0.34.
    At a conversion of 99.9%, the liquid flow rate / h is 2, and the bromine number of 2-ethylhexanol is 0.055. Example 5: Example 1 is repeated.
    50 with the difference that the process is carried out at 120 ° C and a pressure of 80 bar using the raw material composition, wt.%: 2-ethylhexenal 21.53, 2-ethylhexanal 0.1, 2-ethylhexenol 0.01,
    55 2-ethylhexanol 77.58 and water 0.79. A product of the composition, wt.% G 2-ethylhexanol 99.26, 2-ethylhexenal 0.01, 2-ethylhexanal 0.01, 2-ethylhexenol 0.01 and water 0.71 are obtained.
    the product of the composition, masd: 2-ethylhexanol 99.18, 2-ethylhexanal 0.01, 2-ethylhexanal 0.03,, 2-ethylhexenol С 0.01 and water 0.77 are obtained.
    With a conversion rate of 99.9%, the volume rate of fluid / h is 2.1 h. The bromine number of 2-ethylhexanol is 0.02.
    At a conversion of 99.9, the volume velocity of the liquid / h is 2, the Bromine number of 2-ethylhexanol is 0.05,
    EXAMPLE 6 Example 1 is repeated with the difference that the process is carried out at 120 ° C and a pressure of 16 bar using the feedstock composition, mAb: 2-ethylhexenal 22.13, 2-ethyl-1 hexanal 0 , 09, 2-ethylhexenol 0.01 JQ formula of the invention 2-ethylhexanol 76.90 and water O, G
    The method of producing 2-ethylhexanol by liquid-phase hydrogenation of 2-ethylhexenal at a temperature of 12015 and a pressure of 16-80 bar on a nickel, copper and chromium based catalyst prepared by coating a carrier with a solution of salts of these metals and then calcining h At the same time receive the product composition, wt.%: 2-ethylhexanol 99.55, 2-ethylhexenal 0.01, 2-ethylhexanal, 01, 2-ethylhexenol 0.01 and water. 0.62.
    At a conversion of 99.9%, the liquid volumetric rate / h is 2.1-h. The bromine number of 2-ethylhexanol is 0.1.
    EXAMPLE 7 Example 1 is repeated with the difference that the process is carried out at 180 ° C and a pressure of kO bar using the feedstock composition, in wt.%:
    u and u with the fact that, in order to increase the efficiency of the process, the latter is carried out on a catalyst containing additionally alkaline
    2-ethylhexenal 23,19, 2-ethylhexanal 25 is a metal, with the alkali metal and chromium 0.12, 2-ethylhexenol 0.01, 2-ethyl- introduced into the catalyst through dichrohexanol 75.86 and water 0.82. At the same time the matt salt of an alkali metal.
    five,
    a product of composition, mash: 2-ethylhexanol 99.18, 2-ethylhexanal 0.01, 2-ethylhexanal 0.03, 2-ethylhexenol C 0.01 and water 0.77 are obtained.
    With a conversion rate of 99.9%, the volume rate of fluid / h is 2.1 h. The bromine number of 2-ethylhexanol is 0.02.
    invention formula
    u and u with the fact that, in order to increase the efficiency of the process, the latter is carried out on a catalyst containing additionally alkaline
    权利要求:
    Claims (1)
    [1]
    IQ claims
    The method of producing 2-ethylhexanol by liquid-phase hydrogenation of 2 ethylhexenal at a temperature of 12015 180 ° C and a pressure of 16-80 bar on a catalyst based on nickel, copper and chromium obtained by depositing a solution of the salts of these metals on a carrier and subsequent calcining and reduction, characterized in that that, in order to increase the efficiency of the process, the latter is carried out on a catalyst additionally alkaline
    25 metal, with an alkali metal and chromium introduced into the catalyst through a dichroic acid salt of an alkali metal.
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    同族专利:
    公开号 | 公开日
    CS72789A3|1992-11-18|
    EP0326674A3|1991-07-03|
    DE3803464A1|1989-08-17|
    JPH021416A|1990-01-05|
    US4968849A|1990-11-06|
    EP0326674A2|1989-08-09|
    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19883803464|DE3803464A1|1988-02-05|1988-02-05|METHOD FOR PRODUCING 2-ETHYLHEXANOL BY HYDROGENATING 2-ETHYLHEXENAL IN THE LIQUID PHASE, AND CATALYST FOR ITS PRODUCTION|
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