• 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:
    An aldehyde hydrogenation catalyst consisting essentially of a mixture of copper and zinc oxide impregnated with a minor selectivity improving amount of a selectivity enhancer comprising the combination of an alkali metal selectivity enhancer selected from the group consisting of sodium, potassium, lithium, cesium, and mixtures thereof and a transition metal selectivity enhancer selected from the group consisting of nickel, cobalt, and mixtures thereof.
    公开号:SU1731040A3
    申请号:SU874203718
    申请日:1987-11-02
    公开日:1992-04-30
    发明作者:Ерл Логсдон Джон；Аллен Лоук Ричард；Стюарт Мерриам Джей；Вилльям Войт Ричард
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of C3-Cs aliphatic alcohols, which are used mainly in organic synthesis, and to a catalyst for its implementation.
    The purpose of the invention is to reduce the content of by-products in the hydrogenation product, as well as to increase the selectivity of the kazator.
    The goal is achieved by hydrogenation of aldehydes with hydrogen in the vapor phase in the presence of a pre-reduced hydrogenation catalyst based on copper and zinc oxides with the contents of the last 33 and 67 May%, which additionally contains nickel or cobalt, or potassium, or nickel and potassium in amounts, wt.% : Ni 2.4, With 2.4 K 0.6 in
    as surface modifiers applied to the base surface by impregnation, at a temperature of 125-210 ° C and a pressure of 3.5-7.0 kg / cm2.
    The catalyst is prepared as follows.
    A solution (16 L) containing 417 g of copper supplied as copper nitrate and 858 g of zinc in the form of zinc nitrate is heated to approximately 43.33 ° C and sprayed into a 15.7% by weight sodium carbonate solution (12.75%). l), which is mechanically mixed and maintained at a temperature of about 60 ° C. The final pH value of the precipitated mixture is about 7.0 to 8.5. After precipitation, the basic copper carbonate and zinc are washed to remove sodium by decanting about 80% of the filtrate.
    m
    00
    g
    ABOUT

    with
    To reduce the sodium content in the burned filter cake, to about 0.1-0.15 wt.%, The precipitate is washed four times and decanted using water at 37.78-48.89 ° C. Calcination of basic copper carbonate and zinc gives a mixture of copper oxide and zinc oxide (the composition of the starting material of the catalyst). Then, an aqueous suspension (30% by weight of solid particles) from the starting material of the catalyst, graphite, nickel nitrate and potassium nitrate in an amount sufficient to produce the calcined catalytic composition (approximately 7.0% by weight of potassium oxide, 3.0% by weight of oxide nickel, 2.0 wt.% graphite, 32.0 wt.% copper oxide and 62.3 may,% zinc oxide), are dried by spraying. Tablets are molded from the dried powder, which are calcined at 371 ° C to decompose the nitrates. The proposed catalyst is obtained by subsequent reduction.
    EXAMPLE 1 A mixed oil aldehyde containing one part of isobutyraldehyde and nine parts of n-oil aldehyde obtained under low pressure in the reaction of propylene hydroformylation on a rhodium-containing catalyst is divided into equal parts. parts and separately fed to reactors with a two-stage reactive hydrogenation system, having an auxiliary adiabatic plant, with a bulk velocity of 0.8 (total liquid feed volumes per total catalyst volume per hour). A gas containing 60% hydrogen and 40% nitrogen is fed through the inlet of the first reactor with a polar ratio of hydrogen to aldehyde of 13: 1. The gas leaving the first reactor is mixed with another part of the mixed oil aldehyde and subsequently passed into the second reactor. An overpressure of 7.0 kg / cmg is maintained at the exit of the second reactor. A mixture of evaporated aldehyde and hydrogen is fed to the first reactor at 125 ° C, and it leaves the reactor at 201 ° C. The output stream from the first reactor after the addition of additional aldehyde is controlled to 128 ° C at the inlet to the second reactor, and its temperature at the exit from the second reactor is 196 ° C. The catalyst in both reactors is produced by reducing the calcined catalytic composition, consisting mainly of about 33 wt.% Copper oxide and 67 wt.% Zinc oxide, which is impregnated with about 3 wt.% Nickel oxide (about 2.4 wt.% Nickel) and about 1 wt.% potassium carbonate (about 6.0 wt.% potassium).
    The calcined catalytic composition is reduced in a dilute stream of hydrogen containing nitrogen as a diluent at a temperature of about
    200 ° C. The mixed product butanol, condensed from the exit end of the second reactor, contains 1.6% by weight of unreacted aldehyde and only 0.05% by weight of mixed iso- and n-butyl butyrates.
    0 EXAMPLE 2. In a comparative example, an experiment was carried out in the installation described in example 1 under similar reaction conditions, but a unmodified reduced copper oxide and zinc oxide catalyst was taken as a catalyst (the initial catalytic composition contains about 33 wt.% copper oxide and 67 wt.% zinc oxide). The product, condensed from the exit end of the second reactor, contains 0.3% aldehyde and 2.9% mixed butyl butyrate, which indicates a significant increase in the formation of a side ester. In another experiment, carried out with a maximum of 5% of 188 ° C, a sample of the product is recovered, which contains 1.9% unreacted aldehyde and 1.2% butyl butyrate. In both experiments, much more complex
    0 ether than in example 1, obtained with a modified catalyst.
    PRI me R 3. Propionic aldehyde is loaded into a tubular reactor with a steam jacket measuring 0.5 inches in diameter.
    5 per four feet of length, filled with a catalyst with improved selectivity as described in Example 1. During the test, the flow rate of the liquid for 1 hour is maintained at 0.4, the temperature
    0 is close to isothermal (150 ° C), pressure (3.5 kg / cm2) and pure hydrogen are supplied as a coagent at a molar ratio of hydrogen to propionic aldehyde of 20: 1. Condensed product
    5 only contains 0.02% by weight of propyl propionate and 0.04% by weight of propionaldehyde. PRI me R 4. Valeriandehyde is loaded into a small laboratory tubular reactor, working isothermally
    0 at a temperature of 150 ° C and a pressure of 4.2 kg / cm2. A catalyst with improved selectivity is used as in Example 1. At 95% aldehyde conversion, only 0.08 wt.% Of side pentyl penta5 noate is formed.
    EXAMPLE 5 The hydrogenation of aldehyde is investigated by various modifications of calcined catalytic compositions, consisting mainly of about 33% copper oxide and 67% oxide.
    zinc made before reduction. The hydrogenation tests are carried out in a group of small laboratory reactors operating under identical conditions.
    The test results are presented in table 1.
    The reaction conditions are as follows: a pressure of 4.2 kg / cm2, an outlet temperature of 192 ° C, a molar ratio of hydrogen loading to aldehyde oil of 11: 1, and a space velocity (based on gas consumption under standard conditions) 120,000 volumes of total gas / volume catalyst in 1 hour
    As shown, the use of a catalyst whose selectivity is enhanced by nickel, cobalt, or potassium results in a significant reduction in the formation of a side ester. By using a combination of potassium and nickel to improve the selectivity of the catalyst, a reduction of by-products is achieved.
    PRI me R 6. Comparative data with a high percentage of conversion, i.e. more than 99% is obtained with a catalyst based on copper oxide, zinc oxide with improved and unimproved selectivity in reactors to which mixtures of iso- and n-oil aldehydes are fed in a mass ratio of 1: 9. Maximum reaction temperatures are about 210 ° C. The inlet conditions are adjusted to obtain a partial pressure of 6 pounds per square foot. inch for oily aldehydes and 70-77 psi. inch for hydrogen. The total gas feed rate is 4,800 standard cubic feet of catalyst per hour.
    The results are presented in table. 2,
    In this example (as in Example 5), although the use of only an alkali metal to improve the selectivity of the catalyst significantly reduces the formation of the side ester by about
    80%, however, the combination of potassium and nickel gives an additional decrease by an order of magnitude. Example. Using the reactors and reaction conditions described in Example 5, tests were carried out showing the performance characteristics of various catalysts containing copper. Test catalysts were not effective in significantly reducing the formation of esters or other by-products, for example ethers.
    权利要求:
    Claims (2)
    [1]
    1. A method of producing aliphatic alcohols Cz-Cs by hydrogenating the corresponding aldehydes with hydrogen in the vapor phase in the presence of a previously reduced hydrogenation catalyst based on copper and zinc oxides with the contents of the last 33 and 67 wt.%, Respectively, at elevated temperature and pressure 3.5-7.0 kg / cm2, characterized in that, in order to reduce the content of by-products in the hydrogenation product, a catalyst is used which additionally contains nickel or cobalt, or potassium, or nickel and potassium, wt%: Ni 2.4; From 2.4; To 0.6, as surface modifiers deposited on the surface of the base by impregnation and the process is carried out at 125-210 ° C.
    [2]
    2. Catalyst for the production of C3-Cs aliphatic alcohols by hydrogenating the corresponding aldehydes with hydrogen in the vapor phase based on copper oxides and
    zinc, taken in a ratio, wt.%: copper oxide 33; zinc oxide 67, characterized in that, in order to increase the selectivity of the catalyst, it additionally contains nickel or cobalt, or potassium, or
    Nickel and potassium, wt.%: Nickel 2,4; cobalt 2,4 - potassium 0,6 as surface modifiers applied to the base surface by impregnation.
    Table 1
    Note. Butyl ether or propane was not formed in a significant amount: 1% K2CO3 corresponds to 0.6% potassium.
    table 2
    Table 3
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    申请号 | 申请日 | 专利标题
    US06/926,129|US4762817A|1986-11-03|1986-11-03|Aldehyde hydrogenation catalyst|
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