• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A supported silver catalyst for the oxidation of ethylene to ethylene oxide with molecular oxygen is made by impregnating a support with a hydrocarbon solution of a silver salt of a neo-acid having 7 or more carbon atoms, the solution being substantially free of water and said neo-acid. Preferably, the hydrocarbon solvent is toluene, xylene, ethyl benzene, cyclohexane, or cumene. The impregnated support is dried and the silver is activated under conditions chosen to provide the optimum selectivity to ethylene oxide. Thereafter, the activated silver catalyst may be impregnated with an alkali metal solution sufficient to increase selectivity of the silver catalyst above its alkali-free state. The amount of alkali metal on the finished catalyst is the optimum for the particular support selected and preferably will be about 1-6 x 10-3 gew/kg of catalyst. The catalyst may also include additional promoters, such as the alkaline earth metals, preferably barium.
    公开号:SU1598856A3
    申请号:SU853898659
    申请日:1985-05-13
    公开日:1990-10-07
    发明作者:Д.Армстронг Уильям
    申请人:Сайентифик Дизайн Компани,Инк (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the manufacture of catalysts, in particular, to a method for preparing a silver-containing catalyst for the oxidation of ethylene.
    The aim of the invention is to obtain a catalyst with increased selectivity by using as an silver salt solution an anhydrous neo-acid silver salt solution in an aromatic hydrocarbon solvent.
    Example. An impregnating silver solution is obtained by dissolving 173 g of silver oxide in a solution of 173 g of absolute ethanol and 520 g of neodecanoic acid (Exxon Chemical Company), which contains 67% 2-ethyl-2-methylheptanoic acid, 31% 2,2-dimethyl octanoic acid and 2% 2,2-diethylhexanoic acid. Uncaecanoic acid and ethanol are mixed and heated to 80 ° C. With vigorous stirring, silver oxide is added in increasing portions. To clean the solution of prematurely reduced silver, ten drops of 30% hydrogen peroxide are added. To the precipitate of neodecanoate silver is added 3000 g of absolute ethanol, which is filtered, and then twice re-suspended in 3000 g of ethanol, filtered and dried in air. About 85% of silver oxide is regenerated as silver neodecanoate. 217 g of silver neodecanoate powder is dissolved in 117 g of toluene, after which the mixture is heated to 80 ° C for carrier feeding.
    150 g of carrier material (Norton 5552 in the form of 1/4 x 1/4 inch rings), having the parameters:
    Alumina, wt.% 93.1
    Silica wt.% 5.6
    Porosity is open,% 55-57
    l you sh
    00
    ate
    ON

    CJ
    The percentage of pores with a range of diameters, microns:
    15
    1-1087
    10-1008
    100
    Surface area, m / g 0.3-0.37 Pore volume, cm / g 0.31
    The selective absorption,% 88, is preheated to 85 ° C and immersed in a solution of silver neodecanoate and toluene for 20 minutes. The saturated carrier is allowed to drain and is subjected to a programmed heat treatment in air to decompose the organic residue and precipitate metallic silver in the form in which it is suitable for use in the finished catalyst. The impregnated carrier is heated at 100 ° C for 1.5 hours to evaporate toluene, then heated at 250 ° C. When the temperature reaches 200-225 ° C, the decomposition of organic matter begins, which causes the temperature to rise to 335-350 ° C. After 30 minutes, the catalyst is removed from the heat source and allowed to cool to room temperature.
    In order to improve the performance of the activated silver catalyst, it is impregnated with a solution of cesium acetate in a mixture of water and ethanol. This solution is obtained by dissolving 4.19 g of cesium acetate in 15.7 g of distilled water. The resulting solution is mixed with 380 -H anhydrous ethanol. The resulting solution contains about 7,000 ppm by weight of cesium. The impregnating solution described is circulated through a layer of activated silver catalyst for 2 hours. The excess solution is drained, after which the catalyst is washed three times with pure anhydrous ethanol. The catalyst is dried and then crushed to form 12-18 mesh particles to be tested. In accordance with the analysis, the catalyst contains 9% silver and 183 ppm cesium (1.39 X 10 g-eq./kg). As a result of saturating the dry catalyst with a solution obtained from 0.005 g of cesium acetate in 0.5 g of water and 9.8 g of ethanol, more
    parts by weight per million cesium
    36 g of this catalyst are placed in a reactor consisting of a stainless steel U-shaped tube with an internal diameter of 5.33 mm heated in a bath of molten salt. A mixture containing,% ethanol 0,2; ethylene 14; oxygen 6.7; carbon dioxide 5.5 and 0.5 ppm of ethylene chloride and equilibrating nitrogen are fed to the catalyst with a bulk velocity of 6000 hours. The pressure is maintained at 20.4 bar and the temperature is 230-280 ° C.
    The test results are shown in table 1
    Example 2 (for comparison). An impregnating silver solution is obtained by reacting 80 g of silver oxide with a solution of 240 g of neodecanoic acid (Ex-Chemical Company) and 80 g of absolute denatured ethanol (Ashland Chemical Company LOCEX is added over 25 minutes. To purify the solution, add 30 drops of 30% hydrogen hydrogen peroxide. This solution is evaporated to achieve a silver concentration of 23.2% by weight. For every 1 mole of silver neodecanoate formed, 3 moles of free neodecanoic acid remain. 0 Instead of precipitating neodecanoate with ribs, as in Example 1, this solution is used directly for the preparation of a silver catalyst.
    300 g of the catalyst carrier Norton 5 5552 immersed in the newly obtained weak solution. After removing the impregnated carrier, the excess solution is allowed to drain. Then the carrier is heated in an oven in an atmosphere of air at 130 ° C for 0 2 hours) At 200 ° C for 2 hours, at 260 ° C for 2 hours and at 300 ° C for 2 hours
    After cooling, the activated silver catalyst is again impregnated with an alcoholic solution of cesium and 5 are tested as in Example 1.
    The test results are shown in Table. 2
    The results shown by the catalyst prepared in accordance with Example 2, 0 are worse than those obtained in Example 1, where the free neodecanoic acid is removed.
    EXAMPLE 3. As in Example 1, silver neodecanoate is obtained in the form of a solid, after which 316 g of this substance is dissolved in 166 g of toluene. The resulting solution is used to impregnate 464 g of Norton 5552 carrier. After draining the excess solution, the impregnated carrier is activated by drying and heating to 250 ° C in a forced-air oven in the same way as in Example 1. The activated catalyst is then impregnated with water-ethanol 55 solution of cesium acetate as in example 1.
    B) For comparison, a catalyst is prepared using xylene as a solvent. 165 g of neodecanoate silver is dissolved in 110 g of xylene and impregnated with this
    With a solution of 194 g of a carrier made of Norton 5552 material, the Impregnated carrier is activated by placing it in a single layer on a movable metal band with holes to which air heated to 500 ° C is fed for about 2 minutes. After cooling, the activated catalyst is again impregnated with water. ethanol cesium acetate solution.
    c) A third sample is prepared by dissolving 142 g of silver neodecanoate in 95 g of cumene and impregnating 220 g of a carrier from Norton 5552 with this solution. Impregnated activator carrier by air at 500 ° C supplied for 2 minutes while the carrier is on a moving belt . The activated catalyst is again impregnated with a water-ethanol solution of cesium acetate.
    All finished catalysts are tested as in example 1.
    The test results are given in table. 3. Example 4. The cesium salt of neodecanoic acid is obtained by adding 11.27 g of an aqueous solution containing 50% cesium hydroxide to 6.50 g of neodecanoic acid. As a result, a homogeneous solution is formed, which is evaporated in order to regenerate cesium neodecanoate crystals. These crystals are introduced into an organic solution containing silver neodecanoate and used to impregnate the support. As in Example 1, 1.65 g of silver neodecanoate is dissolved in 86.3 g of toluene. This solution is filtered to remove insoluble solids, after which 0.365 g of cesium neodecanoate is added. The result is a clear, uniform solution that is stable. The carrier is impregnated and then activated in accordance with Example 1 in order to form a promoted silver catalyst, in which the analysis makes it possible to detect the content of 250 mash per million cesium.
    Example 5 Sodium neodecanoate is prepared by reacting 31.1 g of neodecanoic acid with 7.2 g of sodium hydroxide. This solution is diluted with water to 500 ml. An aqueous solution of silver nitrate is prepared by dissolving 30.6 g of silver nitrate in distilled water and diluting with water to a total volume of 500 ml. Both aqueous solutions are mixed, resulting in the formation of silver neodecanoate, which precipitates out of solution. The solids are filtered, washed with distilled water and dried. Later they are used to obtain silver
    catalysts in accordance with the techniques described in examples 1-4.
    EXAMPLE 6 Neo-heptanoic acid silver salt is obtained by reacting 3.87 g of silver oxide with 50 g of neoheptanoic acid (Exxon Kemikal Company) in 15 g of absolute ethanol in a hot bath. water, the temperature of which is maintained at 80-85 ° C. After 10 hours, some silver salt precipitates, but to obtain the dissolved salt, 1000 ml of additional ethanol is used to dilute the reaction mixture. Since the dissolved salt does not dissolve in ethanol, it is precipitated, removed by filtration, and washed with ethanol before use.
    Silver neoheptanoate is less than 20 soluble in hydrocarbon solvents than silver neodecanoate. The saturated solution is obtained by dissolving. 11 g of silver heptanoate in 87 g of toluene at 85 ° C. This solution is filtered to separate 5 any insoluble solids, and then used to make a silver catalyst. The maximum silver concentration is only 1.5 May. %, which makes it difficult to obtain a catalyst with a silver content of 8-15% by weight.
    EXAMPLE 7 Neopentanoic acid silver salt is prepared as in Example 6. The salt is precipitated in the reaction mixture 5. Silver neopentanoate has been found to be almost insoluble in aromatic solvents ethanol, acetone and water.
    The whole procedure is repeated using 2-ethylhexanoic acid and decanoic acid, and results similar to those obtained using neopentanoate silver are obtained.
    The results obtained with the use of various acids are given in Table. four.
    Neodecanoic acid is suitable, since its silver salt is characterized by significant solubility in toluene 0 or in similar aromatic solvents, which makes it possible to obtain silver catalysts containing 8-15% silver. Other acids lead to the formation of silver salts, which are unsuitable for use for practical purposes. Therefore, it is believed that silver salts of neo-acids are useful only when using neo-acids containing 7 carbon atoms. Silver neodecanoate is particularly preferred, since this acid is easily obtained under industrial conditions.
    Froze Silver neodecanoate is highly soluble in aromatic hydrocarbons. However, it is possible to obtain silver salts of geoacids with a higher molecular weight, which also dissolve in aromatic hydrocarbons, so silver catalysts can be made from them.
    Silver salt of neotridecanoic acid is obtained by reacting 114.19 g of silver oxide with 393 g of neotridecanoic acid (Exxon Chemical Company) in 30 g of absolute ethanol. As in the case of neodecanoic acid, non-tridecanoic acid is not a pure compound and contains various acids having a non-configuration defined above, and on average about 13 carbon atoms. After refluxing for 1 h, five drops of 30% hydrogen peroxide are added, resulting in a bright solution. A mixture of neotridecanoate silver and unreacted neo-acid is mixed with an excess of ethanol (about 3000 cm and with silver precipitates, which makes it easy to separate the silver salt from the unreacted acid, Unlike silver neodecanoate, which has a clearly pronounced crystalline structure and forms a suspension in ethanol, neoteridecanoate silver forms a compacted, sticky mass. The solid is washed with ethanol to remove most unreacted neo-acid.
    The catalyst is obtained by dissolving 194.3 g of silver neoteridecanoate in
    77.7 g of cumene. This solution contains 20% more silver than is possible with silver neodecanoate. 278 g of the carrier material from Norton 5552 is impregnated with a solution of silver in the usual way. The impregnated carrier is activated on the described belt dryer,
    PRI me R 9. Using the procedure of example 8, a catalyst was prepared using silver neotridecanoate in cumene as a solvent, which was tested by the method of example 1 and the results are shown in Table 5,
    Thus, the proposed method
    allows to obtain a catalyst showing an increase in the selectivity of the catalyst obtained from silver neodecanoate in cumene, 76.7% compared with the 74.3% known from silver lactate,
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of preparing a silver-containing catalyst for the oxidation of ethylene to ethylene oxide by impregnating the carrier, which is a mixture of alumina and silica, with a solution of silver salt, separating the carrier from the impregnating solution, heating in the presence of
    molecular oxygen for the time required to reduce the silver salt to metallic silver, to impregnate the alkaline promoter solution and to dry, characterized in that
    to obtain a catalyst with increased selectivity; anhydrous solution of Cy-Cia neo-acid silver salt in an aromatic hydrocarbon solvent is used as a silver salt solution.
    a b and c a 1
    table 2
    Ta lb and c and 3
    Table 4
    Table 5
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/610,229|US4555501A|1984-05-14|1984-05-14|Process for preparing silver catalysts|
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