• 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:
    1. A method of preparing a silver catalyst for the oxidation of ethylene, which includes impregnation of the carrier with an aqueous solution of silver nitrate and cesium salt, drying and reduction by heating, characterized in that, in order to obtain a catalyst with increased selectivity and service life, impregnation of the carrier is carried out in two stages, 60-74% of the total amount of silver and 25-40% of the total amount of cesium are first deposited on the carrier, dried, and then the amount of silver and cesium is left, dried and reconstituted. 2. A method of preparing a silver catalyst for the oxidation of ethylene, including the impregnation of the support. aqueous solution of silver nitrate and cesium salt, drying and reduction on heating, characterized in that, in order to obtain a catalyst with increased selectivity and service life, the carrier is impregnated in two stages: first, all silver and 20 are applied to the carrier -40% of the total amount of cesium, silver nitrate is reduced to metallic silver, then the remaining coli-1 is applied, honestly cesium and dried. e ss
    公开号:SU1218921A3
    申请号:SU833608868
    申请日:1983-06-28
    公开日:1986-03-15
    发明作者:Ребсдат Зигфрид；Майер Зигмунд；Альфранседер Йозеф
    申请人:Хехст АГ；
    IPC主号:
    专利说明:

    "one
    The invention relates to methods for preparing oxidation catalysts, in particular, to a method for preparing a silver catalyst for the oxidation of ethylene (and its variants).
    The purpose of the invention is to obtain a catalyst with increased selectivity and service life due to certain conditions of carrier impregnation with solutions of active components.
    Example 1. In a solution containing 13.03 g (37.9441 wt.%) Silver nitrate, 9.10 g (26.4997 wt.% Distilled water, 0.01 g: (0.0291 wt.%) Nitrate cesium and 12.2 g (35.5271 wt.%) of isobutylamine are immersed carrier-o (aluminum oxide in the form of a cylinder with a specific surface of 0.3 for 15 min at room temperature. After scattering an excessive amount of thief for impregnation through a sieve wet carrier cyidaT 30 min at 105 ° C in an atmosphere of air and nitrogen.
    After cooling the down-ready catalyst, it is again impregnated with a solution containing 10.03 g (28, A18 wt.%) Distilled water, 0.017 g (0%). , 0478 wt.%) Of cesium nitrate and 12.5 g (35, I 647 May.% J of isobutylamine, as described, and dried. After drying, the catalyst is subjected to a half-hour reduction in a rotary kiln, preheated to 300 ° C, through the furnace is passed through a mixture of air and nitrogen, a catalyst is obtained that contains 1.4 silver (O, 015 wt,%) cesium and the carrier — the rest.
    During the first impregnation, 74 wt.% Of the total amount of silver and 33 wt.% Of the total amount of cesium are deposited; in the second impregnation, the corresponding residual amounts are applied, 20 ml of the obtained catalyst are placed in peiiKTop Of special steel and at 210 C and 1.3 ML of danlenip gas is filled with working gas consisting of:% by volume: ethylene 30; methane 50, hydrogen cattle 8.5; Pinhlormord is 0.0003 and the rest is nitrogen. The ratio of volume to time is 3.000 nl of gas per liter of catalyst per hour.
    The gas entering the reactor hype contains 1.5 vol.% Of ethylene oxide, Selectivity, calculated as the ratio of the mole of ethylene oxide formed
    921Z
    per mole of ethylene converted is 82.1% at 6% ethylene conversion.
    With the continuation of the experience in the specified conditions for 4 months. the selectivity drop is 0.3% (i.e., the selectivity is 81.8%),
    Example 2 (comparative). The carrier, as in Example 1, is fed once with a solution containing 31.5 g (49.4910 wt.%) Silver nitrate, 15.6 g (24.5098 wt.%) Distilled water, 0.048 g ( 0.0754 wt.% Cesium nitrate and
    5 6.5 g (25.9238 wt.%) Of ethylenediamine, dried and reconstituted by analogy -Fro of Example 1. The resulting catalyst contains 11.3 wt.% Silver and 0.016 wt.% Cesium,
    0 When testing this catalyst for 4 months. under the conditions of Example 1, the following was established: a temperature is required for, 5% by volume of ethylene oxide 218 ° C, selectivity at
    5 b% conversion of ltilene to 79.3%, selectivity after 1 month. 79.1%
    Example 3. A solution is prepared from 12.0 g (37.4859 wt.%) Of serrabra nitrate, 9.0 g (28.1145 wt.%)
    „Distilled water, 0,012 g
    (0.0375 masl) of cesium acetate and I 1, 0 g (34.3621 wt.%) Of secondary butylamine. In this solution, carrier-it-alumina is placed in the form of balls with a diameter of 8 mm and a particle size of 0. , 2 for 10 min and dried, analogously to example 1,
    After cooling, the semi-finished catalyst is again impregnated with a solution containing 12 g (37.4789 May,% |
    ° silver nitrate, 9.0 g (; 28, 1092 wt.%) Distilled water, 0.018 g (0.0562 wt.%) Cesium acetate and 11.0 g (34.35579 wt.%) Secondary butyl amine, and dried. For 20 minutes, the catalyst was restored in a quenched tube, preheated to 280 ° C, which is used as an oven, 40 l of air and 20 l of nitrogen are passed through the furnace
    O
    in hours. The catalyst contains, wt%: silver 11.5, cesium 0.019.
    As a result of the first impregnation, 68% by weight of silver and 55% by weight of 37% by weight of total cesium were applied, at. second impregnation - the rest. 20 ml of the obtained catalyst was tested for 4 months in a dnnapata under pressure as in Example I. The following results were obtained: the temperature required for 1.5% by volume of ethylene oxide was 222 ° C, the selectivity at 6% ethylene conversion was 81.8%, selectivity after 4 months 81.5%.
    Example 4 A catalyst is prepared analogously to example 3.
    The solution for the first impregnation has the following composition: 12.0 g (37.4906 wt.%) Of silver nitrate, 9.0 g, (28.1180 wt.%) Distilled water, 0.005 g (0.0156 wt.%) Of cesium carbonate, 0.003 g (0.0094% by weight) of rubidium nitrate, 11.0 g (34.3664% by weight) of secondary butylamine.
    The solution for the second impregnation contains 12.0 g (36.8992 wt.%) Nit-, silver silver, 9.5 g (29.2119 wt.%). water, 0.012 g (0.0369 wt.%) cesium carbonate, 0.009 g (0.0277 wt.) rubidium nitrate, 11.0 g (33.8243 May of secondary butylamine.
    The finished catalyst contains, wt%: silver 11.2, cesium 0.013, rubidium 0.008. In this case, at the first impregnation, 7% by weight of the total silver, 25% by weight of the whole promoter are deposited, and the rest is applied at the second impregnation.
    The catalyst was tested as in Example 1 for 2 months and the following results were obtained: the required temperature for 1.5% ethylene oxide was 226 ° C, the selectivity at 6% ethylene conversion was 81.7%, after 2 months. 81.5% selectivity.
    40
    Example 6. A carrier of X. aluminum oxide in the form of balls with a diameter of 8 mm and a specific surface of 0.2 m / g is impregnated with a solution consisting of 30.0 g (39.4659 wt.%) Silver nitrate, 20.0 g ( May 26,3106.
    distilled water, .22,0 g
    /
    Example 5. A carrier / alumina in the form of balls with a diameter of 8 mm and a specific surface of 0.3 is passed through a solution containing 30.0 g (38.4556 masl) / „„ „, -, о,
     1, l D / wasps: -Ст1 7 .. g (28.9417 May L) of secondary butylamine-silver nitrate, 20.0 g (25.637 1 May.% J 45
    distilled water, 28.0 g (35.8919 wt.%) of isobutalamine and 0.012 g (0.0154 wt.%) of cesium nitrate. After 15 min, the excess amount of the solution is drained. Then you- 50
    and 4.0 g (5.2621 wt.%) of ethylene diamine and 0.015 g (0.0197 wt.%) of cesium nitrate for 15 minutes. After removing the excess solution
    The lyser is dried in a drying cabinet under nitrogen at 100 ° C. To reduce the silver nitrate to metallic silver, the catalyst is placed in a drying cabinet, rinsed with 80 liters of air and 60 ml of nitrogen per hour, and heated for 1 hour to.
    narrowed for 45 minutes in a drying cabinet, washed with nitrogen at 10 The dried catalyst is placed in a glass tube through which a mixture of air and nitrogen (40 liters of air and 20 liters of nitrogen per hour) is passed and heated to 30 ° C for 30 minutes The received message is restored
    892 14
    The lazy catalyst contains 8.6 wt.% silver and 0.0038 wt.% cesium.
    The catalyst cooled to room temperature is passed through a solution containing, in wt%: methanol 95, cesium nitrate 0.045, distilled water 4.955. For this, the catalyst is placed entirely in a vessel with a solution and left to stand at room temperature for 10 minutes.
    After removing the excess solution and drying at 110 ° C in an oven flushed with nitrogen, the catalyst contains 0.0125 May L. cesium and t5 8.6 wt.% Silver, and during the first impregnation the whole amount of silver and 30 wt.% Are applied. the amount of cesium, with the second impregnation, the remaining amount of cesium is applied. 25 ml
    ten
    20
    )
    25
    thirty
    35
    40
    The resulting catalyst is placed in a reactor and at 200 ° C and normal pressure, the gas mixture consisting of:% ethylene 30, methane 50, oxygen 8.5, vinyl chloride 0.0003, and the rest is reacted. The ratio of volume - time - speed of 400 nl gas per liter of catalyst per hour. The gas leaving the reactor contains 1.3 vol.% Of ethylene oxide.
    The selectivity, calculated as the ratio of the mole of ethylene oxide produced per mole of ethylene subjected to interaction, is 81.5% at 5% ethylene conversion.
    After 3 months test selectivity of 81.2%, a drop in activity of 0.3%.
    Example 6. A carrier of X. aluminum oxide in the form of balls with a diameter of 8 mm and a specific surface of 0.2 m / g is impregnated with a solution consisting of 30.0 g (39.4659 wt.%) Silver nitrate, 20.0 g ( May 26,3106.
    distilled water, .22,0 g
    /
    /"" ",,-, about,
    (28,9417 May L) secondary butylami-
    and 4.0 g (5.2621 wt.%) of ethylene diamine and 0.015 g (0.0197 wt.%) of cesium nitrate for 15 minutes. After removing the excess solution
    The lyser is dried in a drying cabinet under nitrogen at 100 ° C. To reduce the silver nitrate to metallic silver, the catalyst is placed in a drying cabinet, rinsed with 80 liters of air and 60 ml of nitrogen per hour, and heated for 1 hour to.
    The catalyst has a composition, wt.%; silver 8.6 and cesium 0.0045.
    Next, the catalyst is impregnated with 15 cesium salt solution, the following composition, mS,%: methanol 95 distilled water 4.95, cesium acetate 0.05.
    After removing the excess solution and drying for 30 mic at 100 ° C, a catalyst containing, in wt.%: Silver 8.6, cesium, 0.0107, and 40 wt.% Of the total cesium in the course of the first impregnation, is obtained.
    The catalyst was tested as in example 1 for 3 months. The following results are obtained: the required temperature for o5.% Ethylene oxide is 196 ° C, the selectivity at 5% conversion is 81.6%, after 3 months. 81.3%.
    Example 7 f / vHH comparison. The catalyst is prepared similarly to measure 1, however, the entire amount of silver and the entire amount of cesium are applied simultaneously by a single impregnation of the carrier with a solution of the following; lo the filter: 30.0 g (38.4369 wt.%) Silver nitrate; 20.0 g (25.6246 wt.%) Distilled water ;; 28.0 g (35.8744 wt.% Secondary butylamine and 0.05 g (0.0641 wt.%) Cesium nitrate.
    The catalyst has the following composition, wt.%: Silver 8.5, cesium 0,0130.
    Testing the catalyst for 2 Mecj carried out under the conditions described in the example gives the following results: the temperature is required for 1.3% by volume of oxide (ethane 193 ° C, selectivity at 5% ethylene conversion 80.2%, selectivity after 2 months of 80.1%.
    Example 8 (/ hl comparison, the catalyst is prepared as in example 1, but the entire amount of cesium is applied during the second impregnation, and the first impregnation yields the entire amount of silver. On the first impregnation, the solution has the following composition: 30.0 g (38.46 wt.% % silver nitrate; 20.0 g (25.64 wt.%) of distilled water; 28.0 g (35.9 wt.%) of secondary orylamine. Catalizato) after reduction of amphibious, 6 wt. % silver.
    The entire amount {ganos t from a solution containing; -o, us. methanol 95.0, distilled water 4.93, cesium nitrate 0.07. Goto10
    15
    0
    S
    0
    five
    0
    five
    0
    This catalyst contains 8.6 wt.% silver and O,.% cesium.
    Test catalyst for 1 month. under conditions similar to hfimer 1, the following results were shown: the temperature for 1.3 vol.% of ethylene oxide is 194 ° C, the selectivity at 5% of ethylene conversion is 79.8%, after 1 month. 79.6% ..
    Example 9. An impregnation solution is prepared consisting of 9.449 g (26.250 wt.%) Silver nitrate, 18,000 g (50,000 wt.%) Distilled water, 0.009 g (0.025 wt.%) Cesium nitrate, 8.548 g (23.725 wt. %) secondary butylamine.
    90 J of the carrier material, according to the conditions of example 1, is treated in a rotating drum with the addition of 36 g of impregnation DD1I solution, and the mixture is stirred for 2 minutes. After holding still in flow 1.; E for 5 minutes, remove the carrier for 1 hour in a drying oven at 110 C.
    After cooling to room temperature; 1) of the catalyst, the semi-finished catalyst, by analogy with the one described above, is again impregnated with a solution consisting of - 6,300 g (3,500% by weight) of silver nitrate; 7.980 g (39.900 wt.%) Distilled water; 0.020 g (0.100 wt.%) Of cesium nitrate; 5,700 g (28,500 wt.%) Of secondary butylamine, and.
    Immediately thereafter, according to analysis described in Example 1, j g po; The recovery is recovery. A catalyst, containing 10 wt.% Silver and O, (.iac.% Cesium.
    i as a result of the first impregnation, 60 wt.% of the total amount of cesium and 30 wt.% of the total amount of cesium are deposited, and in the second impregnation process, the remaining amounts of these components are applied, 20 ml of the prepared silver catalyst, analogously to example 1, test B working under pressure reactor at a gas pressure of 1.3 MPa. The gas at the exit of the reactor contains 1.5% by volume of ethylene oxide, which corresponds to a selectivity of 31.5% with a degree of ethylene conversion of 6%, after 2 months the selectivity of 81.3%.
    Example 10 A solution impregnator is prepared consisting of: 10.236 g (28.433 wt.%) Silver nitrate; 16.502 g (45.839 wt.%) Distilled water; 0.012 g (0.033% by weight) of cesium nitrate and 9.250: (25.694% by weight) of secondary butylamine.
    90 g of carrier material (corresponding to example 1), 9.36 g of impregnation solution are treated, after which the product is dried. After cooling to room temperature, the semi-finished catalyst is again impregnated with a solution consisting of: 5.511 g (27.555 wt.%) Silver nitrate; 6.634 g (33.170 wt.%) Distilled water; 0, g (0.075% by weight) of pezi carbonate and 7.840 g (39,200% by weight) of secondary butylamine, and dried in a similar manner as Mepiy 9. After this, reduction is performed .. As a result, a silver catalyst containing 10% by weight silver and 0.02 wt.% cesium.
    As a result of the first impregnation, 65 wt.% Of the total amount of silver and 40 wt.% Of the total amount of cesium are deposited, and in the second impregnation process, the remaining amounts of said components are deposited. 20 ml of the catalyst obtained in this way are tested in the same way as in Example 1, in a reactor operating under pressure at 213 ° C. and a gas pressure of 1.3 ml. The gas at the exit of the reactor contains 1.5% ethylene oxide, which corresponds to a selectivity of 81.6% with a degree of ethylene conversion of 6%, after 2 months of work, a selectivity of 81.3%.
    Example II A carrier material according to example 5 is used. 90 g of this material is poured in a rotating drum with a solution of silver salt and cesium salt, consisting of: 15,750 g (40.070 wt.%) Silver nitrate; 10.000 g (25.440 wt.%) Distilled water, 0.006 g 0.015 wt.% Of cesium nitrate and 13.550 g of p4.475 wt.%) Of secondary butylamine, after which the mass is stirred for 2 minutes. After additional addition for 5 minutes, the wet media is dried as in Example 5 and heated to reduce the silver salt. After reduction, a catalyst is obtained,
    ten
    15
    0
    five
    0
    five
    0
    five
    O
    holding, 10 wt.% silver and 0.004 maa.% cesium. -i
    The crude catalyst, cooled to room temperature, is poured over with the following cesium salt solution and treated in the indicated rotating drum by analogy with the described Bbmie: 23,000 g (95.74 wt.%) Methyl alcohol; 1,000 g (4.16 wt.%) Of distilled water and 0.024 g (0.10 wt.%) Of cesium nitrate,
    Drying is carried out as in Example 5. As a result, a catalyst containing Yu wt.% Silver and 0.02 wt.% Cesium is obtained (i.e., the entire amount of silver and 20% by weight of the total the amount of cesium, and in the second impregnation process, the remaining amount of cesium is applied).
    20 MP of the catalyst prepared by this method are tested at 191 (; at atmospheric pressure, as in Example 5. The gas leaving the reactor contains 1.3% by volume of ethylene oxide, which corresponds to a selectivity of 81.2% with an ethylene conversion of 5% after 2 months, the selectivity is 81.0%.
    Example 12-. A carrier material according to example 5 is used. 90 g of this material is treated with a solution of silver salt and cesium salt, consisting of: 15.750 g (40.065 wt.%) Silver nitrate; 10,000 g (25.438 wt.%) Distilled water; 0.01 g (0.028% by weight) of cesium nitrate and 13.550 g (34.469% by weight) of isobutylamine, after which the product is heated to reduce the silver salt. After reduction, a catalyst is obtained containing 10% by weight of silver and 0.007% by weight of cesium.
    Cooled to room temperature with catalyst, process - with the following solution of cesium salt 23,000 g (95.75% by weight) of methyl alcohol; 1,000 g (4.16 wt.%) Of distilled water and O, 019 g (o, 09 wt. 1 of cesium nitrate, after which they are dried as in Example 11.
    The result is a catalyst with 10 wt.% Silver and 0.02 wt.% Cesium. During the first impregnation, the entire amount of silver and 35% by weight of the total amount of cesium is applied, and
    9I; 1892110
    In the process of the second impregnation, the substrate is deposited at an ambient of 192 ° C and at atmospheric pressure, the tal amount of cesium. The gae leaving the reactor
    1.3 vol.% Ethylene oxide, which is
    The 20 4L of the resulting product compares with a selectivity of 8.6%. The catalyst is tested according to the degree of conversion of ethylene to 5%, the analogy with that described in Example 5, 2 months, the selectivity is 81.2%.
    权利要求:
    Claims (2)
    [1]
    1. A method of preparing a silver catalyst for the oxidation of ethylene, comprising impregnating the support with an aqueous solution of silver nitrate and cesium salt, drying and recovering when heated, characterized in that, in order to obtain a catalyst with increased selectivity and service life, the support is impregnated in two stage) is first applied to the carrier, 60-74% of the total amount of silver and 25-40% of the total amount of cesium, dried, and then the remaining amounts of silver and cesium are applied, dried and restored.
    [2]
    2. A method of preparing a silver catalyst for the oxidation of ethylene, comprising impregnating the carrier. an aqueous solution of silver nitrate and cesium salt, drying and recovery when heated, characterized by the fact that, in order to obtain a catalyst with increased selectivity and service life, the carrier is impregnated in two stages: first, the entire amount of silver and 20— 40% of the total amount of cesium, restore silver nitrate to metallic silver, then apply the remaining amount of cesium and dry.
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    同族专利:
    公开号 | 公开日
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    PL242748A1|1984-07-02|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4010115A|1972-01-07|1977-03-01|Shell Oil Company|Catalyst for the oxidation of ethylene to ethylene oxide|
    GB1489335A|1973-10-26|1977-10-19|Shell Int Research|Catalyst for the production of ethylene oxide|
    US4066575A|1976-07-26|1978-01-03|Halcon International, Inc.|Process for the preparation of a supported silver catalyst|
    GB1594362A|1977-05-23|1981-07-30|Ici Ltd|Production of alkylene oxides and catalysts therefor|
    JPS5929293B2|1977-07-01|1984-07-19|Nippon Shokubai Kagaku Kogyo Kk|
    DE2914640C2|1979-04-11|1986-01-30|Hüls AG, 4370 Marl|Process for the production of silver catalysts for the production of ethylene oxide|
    DE2938245A1|1979-09-21|1981-04-09|Hoechst Ag, 6000 Frankfurt|METHOD FOR IMPROVING THE EFFECTIVENESS OF SILVER CARRIER CATALYSTS|
    JPS6155416B2|1980-12-26|1986-11-27|Nippon Shokubai Kagaku Kogyo Kk|JPH0468974B2|1984-04-13|1992-11-04|Nippon Catalytic Chem Ind|
    US4690913A|1984-08-21|1987-09-01|Mitsubishi Petrochemical Co., Ltd.|Silver catalyst for production of ethylene oxide from ethylene and process for producing the catalyst|
    DE3528313A1|1985-08-07|1987-02-12|Basf Ag|SILVER CATALYST, ITS PRODUCTION AND USE|
    FR2597098B1|1986-04-11|1989-01-13|Atochem|SILVER-BASED CATALYSTS FOR THE MANUFACTURE OF ETHYLENE OXIDE|
    GB8613818D0|1986-06-06|1986-07-09|Ici Plc|Catalysts|
    US4908343A|1987-02-20|1990-03-13|Union Carbide Chemicals And Plastics Company Inc.|Catalyst composition for oxidation of ethylene to ethylene oxide|
    TW426545B|1997-12-25|2001-03-21|Nippon Catalytic Chem Ind|Silver catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide|
    US6987080B2|2002-03-01|2006-01-17|Scientific Design Company, Inc.|Ethylene oxide catalyst carrier preparation|
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    KR20070057974A|2004-09-24|2007-06-07|셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이|A process for selecting shaped particles, a process for installing a system, a process for reacting a gaseous feedstock in such a system, a computer program product, and a computer system|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19823224323|DE3224323A1|1982-06-30|1982-06-30|Silver catalysts, process for their preparation, and their use for the preparation of ethylene oxide|
    DE19823224322|DE3224322A1|1982-06-30|1982-06-30|Silver catalysts, process for their preparation, and their use for the preparation of ethylene oxide|
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