• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    1535584 Palladium acyloxylation catalyst HOECHST AG 4 March 1976 [4 March 1975] 08687/76 Heading BIE [Also in Division C2] A palladium catalyst, suitable for the oxacylation of olefines in the gaseous phase, is prepared by impregnating a catalyst carrier with a solution of a palladium compound in an unsubstituted monocarboxylic saturated aliphatic acid other than formic acid, drying the catalyst at less than 90‹C until the residual solvent content is no more than 8% by wt., and reducing it by passing a gas mixture comprising an inert gas and a reducing agent over the catalyst. The use of acetic acid to prepare Pd on silicic acid and active charcoal catalysts, including Cd, K, Mn, Au, Ba, V and Bi is exemplified.
    公开号:SU1082309A3
    申请号:SU762325903
    申请日:1976-02-23
    公开日:1984-03-23
    发明作者:Фернхольц Ханс；Рошер Гюнтер；Шмидт Ханс-Иоахим；Шмиц Хайнц；Вундер Фридрих
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    oo
    ND
    WITH
    ABOUT
    The invention relates to the preparation of catalysts for the oxidation of леlefin. A method is known for preparing a catalyst for oxacilation of olefins, for example, to obtain vinyl acetate from ethylene, acetic acid and oxygen, by impregnating a carrier, preferably silicic acid, with a solution of palladium salt, which takes palladium carboxylate, preferably palladium acetate, and after impregnation the catalyst is dried at below, preferably below, and the solvent is scrubbed to a residual content in a catalyst of less than 20% by weight, preferably less than 6% by weight, the catalyst is preferably su in a stream of inert gas, for example nitrogen, under reduced pressure of C 3. The closest to the present invention is a method for preparing a palladium catalyst for the oxidation of olefins by impregnating the carrier with a palladium carboxylate solution with an addition of carboxylic acid activators, followed by drying at a temperature below 90 ° C and by treatment, reduce it in the gas phase with hydrogen, methane, zylene, butylene, isobutylene at 40-260 C. 2. The disadvantage of the known method is that the resulting catalyst has insufficient activity. The aim of the invention is to obtain a catalyst with increased activity. This goal is achieved in that according to the method for producing a palladium catalyst for oxacilipropane olefins by impregnating the carrier with a solution of palladium carboxylate with the addition of activators in carboxylic acid, followed by drying at 0-90 ° C and treatment with a reducing agent in the gas phase - hydrogen, methanol, ethylene, butylene , isobutylene, propylene, aormaldehyde, piperylene at 40-260 ° C, using a reducing agent in a mixture with an inert gas when the content of the reducing agent in a mixture of 0.01-50%. For the preparation of the catalyst, silicic acid and activated carbon are used as the carrier. The carrier is impregnated with a solution containing palladium carboxylate in carboxylic acid, as well as solutions of such metal carboxylates, kick potassium, cadmium, bismuth, barium, vanadium and manganese. The application of selected substances is carried out in one stage. The removal of the carrier impregnated with the solutions of the active substances is preferably carried out under reduced pressure. It is recommended to carry out drying in an inert gas flow. For example in a stream of nitrogen or carbon dioxide. The residual solvent content is 8 wt. preferably: 6 wt.%. . Activation of the catalyst involves the reduction of the palladium compound, which can be carried out in vacuum at normal or elevated pressure up to 10 bar. It is recommended that the reducing agent be diluted with an inert gas — the greater the higher the pressure. The reduction temperature is 40-260 ° C, preferably 7 O-. The content of the reducing agent in the mixture is 0.0150% by volume, preferably 0.5-20% by volume. For example, nitrogen, carbon dioxide, noble gases, or paraffinic hydrocarbons such as methane, ethane, propane, isobutane and butane can be used as inert gas. Hydrogen, methanol, formaldehyde, ethylene, propylene, isobutylene, butylene and other olefins. The amount of reducing agent is calculated depending on the content of palladium salt. The reducing agent is taken in excess compared to the stoichiometric ratio. Acceptable use of excess reducing agent. For example, at least 1 mole of hydrogen should be applied per mole of palladium. Recovery can be carried out at the end of drying in the same apparatus. It is most convenient to carry out the reduction in the same reactor where the olefin is oxidized, i.e. immediately before oxacylation. In this case, it is expedient to use as a reducing agent an olefin that is to be oxidized. Oxacylation is carried out by passing carboxylic acid, olefin and oxygen or oxygen-containing gases at 100-250 ° C, preferably 120 ° -220 ° C, and at a pressure of 1-25 bar, preferably 1-20 bar, over the finished catalyst, and unreacted components are introduced again. in the cycle. In this case, the concentration ratios should be chosen so that the reaction mixture is outside the known limits of exposure. The oxygen content when using ethylene should be below 8 vol.% (Relative to the gas mixture not containing acetic acid). The reaction mixture is suitably diluted with inert gases, such as nitrogen or carbon dioxide. Particularly suitable for diluting CO in a cyclic process, as it is formed in small quantities during the reaction. Catalyst productivity reaches 1180-1210 grams of vinyl acetate per liter of catalyst per hour. Example 1. A 500 g carrier of silicic acid (1 liter; with a surface of 120 and a pore volume of 0.8 ml / is applied is a solution containing, g: palladium acetate 28.8; potassium acetate 26.8 cadmium acetate 23.4; manganese acetate, 1.8 to 340 ml of acetic acid, and dried under a pressure of 200 mm Hg under nitrogen atmosphere. As soon as the weight of the catalyst ceases to increase, 10% of hydrogen is added to the nitrogen, and in general, 4 liters of hydrogen are passed over the catalyst (1.4 mol H2 / 1 mol palladium), and then washed with nitrogen. The finished catalyst contains 2.3 wt.% Manganese. The catalyst is introduced into the reaction tube with a nominal passage of 30 mm. Above the catalyst at a pressure of 9 bar at the reactor inlet and at a catalyst temperature of 175-178 ° G, a gas flow (4.5 N / h) is passed, which consists of% by volume: ethylene 60 , 8; inert gases (K2 and C02) 15.5; acetic acid 17.4; oxygen 6.3. Capacity is 1180-1210 grams of vinyl acetate per liter of catalyst per hour. The catalyst does not change for 600 hours. Example 2. 500 g specified in example 1, the carrier is impregnated with a solution containing, g: palladium acetate 24,4; cadmium acetate 23.4; potassium acetate 26.6 manganese acetate 1.8, in 340 ml of acetic acid, and dried as in example 1. After drying, the catalyst is heated in a tubular furnace in an atmosphere of ethane as an inert gas at normal pressure under, then ethane before starting the furnace passes through the flask with methanol at 20 ° C until 3 g of methanol passes over the catalyst (1 mol of methanol / 1 mol of palladium). The reduced catalyst is cooled in a stream of ethane. It contains, wt%: palladium 2; cadmium 1.7; potassium 1.9; manganese 0.07. Under the conditions of Example 1, this catalyst has a productivity of 1050-1070 grams of vinyl acetate per liter of catalyst per hour. Example 3. 500 g of the support indicated in Example 1 are impregnated with a solution containing, g: palladium acetate 19, cadmium acetate 23.4; potassium acetate 26.6; manganese acetate 1.8 in 340 ml of acetic acid (70%, 30%. The catalyst is dried as in example 1. After drying, the catalyst is reduced in the oxidation reactor described in example 1 with a mixture of 1% ethylene and 99% nitrogen. Ready the catalyst contains, wt%: palladium 1.5; cadmium 1.7; potassium 1.9; manganese 0.07. After reduction under the conditions of Example I, ethylene, inert gas, acetic acid, and oxygen are passed over the catalyst. is 735-750 grams of vinyl acetate per liter of catalyst per hour. Example 4. 500 g of this in example I, the carrier is impregnated with a solution containing, g: palladium acetate 9, cadmium acetate 23.4, LIA acetate 26.6, manganese acetate 1.8 in 345 ml of acetic acid, and dried as in example 1. After drying, the catalyst they are heated in a current of sol at normal pressure at lOOc. Then 1Z of butylenogene is added to CO, up to passing over a catalyst of 10 l of butylene (10 mol of butylene / mol of palladium). The finished catalyst is cooled in a current of SS. It contains, aec.Z: palpadium 0.7; cadmium 1.7; potassium 1.9; manganese 0.07. When tested under the conditions of Example 1, the catalyst provides a productivity of 470-505 grams of vinyl acetate per liter of catalyst per hour. Example 5. 530 g of a carrier of silicic acid with a surface of 180 and a pore volume of 0.7 ml / g impregnated with a mixture of a solution containing, g: palladium acetate 24.4; potassium acetate 26.6 in 200 ml of acetic acid, and a solution of 34.6 g of freshly precipitated barium aurata (4.6 g of barium aurata and 30 g of water) in 140 ml of acetic acid and dried as in example 1. The dried catalyst is heated in current nitrogen at a pressure of 4 bar with and then reduced with a mixture of nitrogen and hydrogen (99: 1), then cooled in a stream of nitrogen. The finished catalyst contains, wt%: palladium 2, gold, 0.5; potassium 1.9. Under the conditions of Example 1, a productivity of 950 grams of vinyl acetate per liter of catalyst per hour is obtained with this catalyst. EXAMPLE 6 500 g of the carrier used in Example I are impregnated with a solution of 30.5 g of wahiad acetylacetonate in 360 ml of 50% acetic acid and dried. Then, 24.4 g of palladium acetate and 26.6 g of potassium acetate are dissolved in 340 ml of acetic acid and applied to a carrier. After drying, the catalyst is heated in a stream of nitrogen (20 l / h) at 200 s, and then the nitrogen is passed through a previously connected, maintained at 20 ° C, washing tank with methanol until 6 g of methanol is evaporated. The catalyst is cooled in a stream of nitrogen (without methanol) at room temperature. The finished catalyst contains, wt%: palladium 2; potassium 1.9; vanadium 0.9. Over 1 liter of catalyst at a pressure of 7.5 bar (at the reactor inlet) and a catalyst temperature of 180 ° C per hour, 2.6 standards are passed, a gas mixture consisting by volume,% by volume: propylene 41.6; inert gases (N2 and CO) 32.2; acetic acid 19.0; oxygen 7.2. A productivity of 940-950 g of allyl acetate per liter of catalyst per hour is obtained. Example 7. 500 g of activated carbon obtained from coal with a surface of 700 and a pore volume of 1.1 ml / g are impregnated with a mixture of a solution containing, g: palladium acetate 24.4; bismuth acetate 20; potassium acetate 26.6 in 350 ml of acetic acid and a solution of 34.6 g of freshly precipitated barium aurata (4.6 g barium aurata and 30 g of water) in 100 ml of acetic acid and then dried. Nitrogen (100 l / h) with a content of 1% isobutylene is passed over the dried catalyst for 20 hours at 40 ° C. The finished catalyst contains, wt%: palladium 2; gold 0.5; bismuth 1.6; potassium, 9. This catalyst is introduced into the reactor described in Example 1. At a pressure of 7 bar (at the entrance to the reactor) and a catalyst temperature of 180 ° C, 2400 normal l of isobutylene, 1600 g of acetic acid and 200 normal l of oxygen are hourly passed over the catalyst. Get 620-640 g of methyl-ethyl acetate. Example 8. 500 g of the carrier of silicic acid (1 l) with a surface of 120 and a pore volume of 0.8 ml / g is impregnated with a solution containing, g: lead acetate 28.6; potassium acetate 26.8; cadmium acetate 23.4; manganese acetate 1.8 in 340 ml of acetic acid, and then at 60 ° C and a pressure of 200 mm Hg. dried in a stream of nitrogen. When the catalyst reaches a constant weight, it is heated to 260 ° C and then 0.5% hydrogen is added to the nitrogen. After nponymejHo over a catalyst of 5 liters of hydrogen, it is washed with nitrogen. The finished catalyst contains, wt%: palladium 2.3; cadmium 1.7; potassium 1.9; manganese 0.07. The catalyst provides, under the conditions of Example 1, a capacity of 1050-1120 g / l h of vinyl acetate, which remains stable for 580 h, Example 9. 500 g of activated carbon obtained from coal with a surface of 700 and a pore volume of 1.1 ml / g are impregnated with a solution mixture g: palladium acetate 24.4; bismuth acetate 20; potassium acetate 26.6 in 350 ml of acetic acid, and a solution of 34.6 g of freshly precipitated barium aurata (4.6 g of barium aurata and 30 g of water) in 100 ml of acetic acid at 100 mm Hg. in a stream of nitrogen, dried to obtain a weight of 625 g (residual solvent content is 7.99%); A mixture of 100 l / h of nitrogen with 1% isobutylene is passed over this catalyst at 90 ° C for 20 hours. The prepared catalyst contains, in wt.%: Palladium 2; gold 0.5; bismuth 1.6; potassium 1.9. Under conditions of example 7, the throughput of the catalyst is 580610 g / l h of metal acetate. JO example. 500 g of silica carrier with a surface of 120 with a pore volume of 0.8 ml / g are impregnated with solution containing, g: acetate pal. 71 lad 28.8 (47.3%); potassium acetate 26, cadmium acetate dihydrate 23.4; manganese acetate tetrahydrate 1.8 in 340 ml of 10% acetic acid, and dried at 60 ° C and at a pressure of 200 mm Hg in nitrogen atmosphere until the weight reaches .577.1 g (i.e., the weight is make up 0.64% of the weight of the carrier and the salts introduced, since the crystalline water of the salts is removed). The catalyst thus dried in the analysis contains a 7.0% acetate residue, i.e. the acetate content within the accuracy of the analysis corresponds to the theoretical value. A reduction is then carried out as in example 8. The finished catalyst has the same composition as in example 8, and the same productivity per unit of time and volume. , . Example 11. As in example 10, 500 g of silicic acid carrier is impregnated with a solution of the active components containing, g: palladium acetate 28.8; potassium acetate 26.8; cadmium acetate 23.4 manganese acetate I, 8 in 340 ml of 10% acetic acid, and dried at a pressure of 100 Torr to a residual weight of 604.4 g. In this case, the catalyst has a solvent residue content of 3.9% and is reduced and tested as in example B. It provides a performance of 640 g / lh for vinyl acetate. Example 12. 500 g of silica carrier (1 l) with a surface of 120 m / g and a pore volume of 0.8 ml / g are impregnated in 340 ml of propionic acid with a solution containing, g: palladium acetate 28.8; acetate ca-, LIA 26.8; cadmium acetate 23.4; manganese acetate 1.8 and dried at 60 ° C and 200 mm Hg, under nitrogen to obtain a propionic acid residue of 8 wt.%. The nitrogen is then heated in a stream of 300 l / h at normal pressure up to 180 ° C. As soon as this temperature is reached, 0.01% by volume of ethylene is added to the nitrogen. After that, a total of 5 l of ethylene is passed through a catalyst, which contains, wt%: palladium 2.3; cadmium 1.7; potassium 1.9; manganese oh 07. Under the conditions of Example 1, the catalyst achieves a production of 9501050 g / l h of vinyl acetate, which does not change after 620 h. 09 13. All operations are as described in Example 12, with the following two changes: instead of 340 ml of propionic acids as the solvent for the active ingredients use the same amount of butyric acid; the reduction is carried out with a mixture of 50% by volume of ethylene and 50% by volume of carbon dioxide, namely, 10 liters of this mixture, which is passed through for one hour. through the catalyst. The productivity of the finished catalyst is 900-1000 g / lh, which does not change after 590 h. Example 14 (palladium propionate). Act as in example 12, except that instead of ace-. tata palladium used 32.6 g of palladium propionate. Performance by volume and time - as in example 12. Example 15 (palladium butyrate). The operation is the same as in Example 13, except that 35.2 g of palladium butyrate is added instead of palladium acetate. Performance by volume and time - as in example 13. Example 16 (palladium acetylacetonate). The operation is carried out as in Example 1, except that instead of palladium acetate, 39.1 g of palladium acetylacetonate are added. Productivity by volume and time 1070 1120 g / l h of vinyl acetate. Example 17. The carrier is impregnated and dried as in Example 1. Then heated in a stream of argon supplied at a rate of 30 l / h to 80 ° C and 2 vol.% Formaldehyde is added to the noble gas for 3 h. Then 30 l / h are passed again noble gas for 5 hours. The finished catalyst has the same composition as in example 1, and when used in a catalytic reaction under the same conditions as in example 1, vinyl acetate yield is 1190 g / l of catalyst per hour. Example 18. The carrier — silica gel — is impregnated with a solution of the active components and dried as in Example 17. After drying, it is heated to 120 ° C in a stream of methane, which is passed at a rate of 60 l / h and which contains 1% by volume of nitrogen, then added to methane 6% by volume of propylene are boiled over 5 hours. After reduction, it is again flushed with methane.
    91082309 10
    and then nitrogen. Under the same conditions, a mixture of 180 g of petroleum ether will be stored
    catalytic process, as in the case of (ie. mixtures of propane, butane and isobumer 1), is obtained the yield of vinyl acetate-catalyst t. bale, 40-80 C) and 20 g of piperi 1080 g / l of catalyst per h. of C1-methyl-butadiene ) within 2 hours
    Example 19. Similarly, s-Then hydrocarbons are displaced by nitrogen,
    ru 17 carrier - silica gel - impregnated in a catalytic reaction under conditions
    the solution of the active components is similar to example 1, get the output
    and dried. Then dovinate acetate is heated to 1060 g / l of catalyst
     and process the catalyst on-hour.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A PALLADIUM CATALYST FOR OCAFILING OLEFINS BY IMPREGNATING THE CARRIER WITH A PALLADIUM CARBOXYLATE solution with the addition of activators in carboxylic acid, followed by drying in the gas phase with hydrogen, methanol, ethylene, butylene, isobutylene-pomeneomene phenomeneomene formaldemene formaldehyde pomeneomeneomene at 40-260 ° C, characterized in that, in order to obtain a catalyst with increased activity, a reducing agent is used in a mixture with an inert gas with a reducing agent in the mixture of 0.01-50 vol. X. g
    SL with a
    1082309
    1 1082309 2
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    同族专利:
    公开号 | 公开日
    GB1535584A|1978-12-13|
    FR2302781A1|1976-10-01|
    DK153370C|1988-11-21|
    IE42499B1|1980-08-27|
    US4093559A|1978-06-06|
    LU74458A1|1977-01-07|
    JPS5911342B2|1984-03-14|
    CA1070659A|1980-01-29|
    AR209347A1|1977-04-15|
    JPS51111495A|1976-10-01|
    RO70540A|1980-05-15|
    DE2509251C3|1978-07-13|
    BR7601290A|1976-09-14|
    CS195723B2|1980-02-29|
    FR2302781B1|1979-08-24|
    AU1162076A|1977-09-08|
    DD123573A5|1977-01-05|
    BG25200A3|1978-08-10|
    YU54676A|1982-05-31|
    IE42499L|1976-09-04|
    HU179197B|1982-09-28|
    YU39203B|1984-08-31|
    NL7602049A|1976-09-07|
    ZA761267B|1977-03-30|
    NO146845B|1982-09-13|
    NO760718L|1976-09-07|
    SE7602343L|1976-09-06|
    PL99997B1|1978-08-31|
    DK153370B|1988-07-11|
    DE2509251B2|1977-11-10|
    SE415450B|1980-10-06|
    DE2509251A1|1976-09-16|
    BE839191A|1976-09-06|
    AU502067B2|1979-07-12|
    IT1056816B|1982-02-20|
    DK90876A|1976-09-05|
    NO146845C|1982-12-22|
    ES445603A1|1977-06-01|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2509251A|DE2509251C3|1975-03-04|1975-03-04|Process for the preparation of a palladium catalyst|
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