• 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:
    Catalysts for the oxidation of alkenes to alkylene oxides comprise silver on supports having a surface area of 0.05 to 10 m2/g, and at least 16 mu g equivalents per square meter of potassium together with rubidium and/or cesium.
    公开号:SU1071210A3
    申请号:SU782616248
    申请日:1978-05-22
    公开日:1984-01-30
    发明作者:Хейден Перси；Вильям Клейтон Ричард；Франк Джордж Коуп Алан
    申请人:Империал Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    four
    The invention relates to catalysts for the oxidation of olefins in their oxides, in particular for the oxidation of ethylene to ethylene oxide. A known catalyst for the oxidation of ethylene to ethylene oxide, containing a water-soluble silver salt in a mixture with one or more water-soluble alkaline earth metal salts with the addition of 0.010.5 molar halide of a mouse. The disadvantage of this catalyst is low activity, the yield of ethylene oxide is 52.6-59, four%. The closest to the present invention is a catalyst for the oxidation of ethylene to ethylene oxide containing 7.8% silver, 0.00077-0.0023 g-eq / potassium catalyst, 0.00060, 003 g-eq / kg rubidium catalyst and / or 0.00035-0.0019 g-eq / kg of cesium catalyst on a carrier, ot-alumina with a specific surface, measured by the Brunauer, Emmett and Teller method, 0.03-2.2 2. The known catalyst has not enough high selectivity to 81%. The purpose of the invention is to increase the selectivity of the catalyst. This goal is achieved by the fact that the catalyst for the oxidation of ethylene to ethylene oxide containing silver, potassium, rubidium or cesium - alumina with a specific surface area, measured by the method of Brunauer, Emmett and Teller 0.3-2.2, contains these components at weight ratio: Silver8-24 Potassium0.0-0.3 Rubidium or cesium 0.001-0.15 Carrier Else The proposed catalyst has a high selectivity (88-94%). Silver is introduced into a preformed porous heat-resistant substrate in the form of a suspension. silver or silver oxide in the liquid medium, for example water, or the substrate is impregnated with a solution of a silver compound, which, if necessary, is reduced to metallic silver using a reducing agent, for example, hydrogen. If necessary, heat treatment is applied to decompose the silver compound to metallic silver. The impregnating solution contains a reducing agent in the form of an anion, for example, formate, acetate, a pionate, a lactate, a tartrate or a better oxalate compound of silver in solution. The reducing agent may be, for example, formaldehyde or acetaldehyde or alcohol, preferably with 1-4 carbon atoms, for example, methanol or ethanol. The solution is prepared in water and / or an organic solvent, for example, aliphatic alcohol, preferably with 1-4 carbon atoms, a polyhydric alcohol, for example, ethylene glycol or glycerin, ketone, acetone, ether, dioxane or tetrahydrofuran, carboxylic acid, for example, acetic acid or molten lactic, which is used in the presence of water, or an ester, ethyl acetate, or a nitrogen-containing base, pyridine, or formamide. The organic solvent acts as a reducing agent and / or complexing agent for silver. If silver is introduced by impregnating the substrate with a solution of a decomposable silver compound, it is better that ammonia or a nitrogen-containing base is present. The nitrogen-containing base acts as a ligand that retains silver in solution, for example, pyridine, acetonitrile, amine, especially a primary or secondary amine with 1-6 carbon atoms, or better ammonia. Other suitable nitrogen containing bases include acrylonitrile, hydroxylamine and alkanoyl amines, for example ethanolamine, alkylene amines with 3-4 carbon atoms or amides, such as formamide or dimethyl Lormamide. Nitrogen-containing bases can be used individually or in mixtures, with mixtures of them with ammonia being preferred. Typically, the nitrogen-containing base or bases are used together with water. The solution may be neutral or acidic, for example, a solution of silver carboxylate, especially formate, acetate, propionate, oxalate, citrate, tartrate or better lactate or a solution of silver nitrate. The impregnation is carried out in one or several stages, thus achieving a higher content of silver in the catalyst. The silver compound is reduced to metallic silver by heating to 100-350 ° C, for 15 minutes to 4 hours, better in the absence of oxygen in the presence of an inert gas, for example, nitrogen. The catalyst support has a ka at least 30 porosities with a mercury absorption method, for example, 3080, better than 30-65, better still 40-60%, and an average pore diameter of 0.1-30 microns, better 0.3-4 microns measured by mercury method of determining porosity. The pore size distribution of the substrate is bimodal, the smaller pores make up at least 70% of the total pore volume and have an average pore diameter of preferably 0.1-0.3-4 microns. and large pores have an average diameter of .25-500 microns. Most of the silver in jope catalysis is in vice discrete particles adhering to the substrate, with equivalent diameters less than 10,000, better than 20-10000, even better than 40-8000 A. Under equivalent diameter is meant the diameter of a sphere of the same silver holding cell as the particle. At least 80% of the present silver is particles with an equivalent diameter of the above range, and the amount of silver is judged by the number of particles in the specified range. Silver may be in the form of metallic silver and / or silver oxides. Silver particle sizes are determined by an electron microscope. The amount of potassium and rubidium and / or cesium extracted by water is related to the specific surface of the substrate. Atomic ratios of potassium to rubidium or cesium 1.5: 1-200: 1. The form in which potassium, rubidium and cesium are in the catalyst is determined by the conditions for the oxidation of the olefin to olefin oxide with the aid of a catalyst. The alkali metal is in the form of any compound, such as carbonate, hydroxide, bicarbonate, lower carboxylate, such as acetate or oxalate, better than nitrate, it is desirable that catalyst dyes, such as bromine, iodine and sulfur, are absent. The promoter is introduced into the substrate before, during or after impregnation with a solution of silver compound in the form of solutions of the compounds of the promoting elements, it can be a solution in water and / or an organic solvent. They consist of solvents, reducing agents and / or complexing agents mentioned above. The catalyst is used in the process of oxidizing ethylene to ethylene oxide. The ethylene partial pressure is 0.1-30, preferably 1-30 kbar. The total pressure of 1-100, better than 3.100 kbar. The molar ratio of oxygen to ethylene or propylene is 0.05100. The oxygen partial pressure is 0.01, preferably 0.1-20, even better bar. i Oxygen is supplied as air or technical oxygen. Quantity: in diluent, for example, gels, nitrogen, argon and / or carbon dioxide and / or better than methane is 1080, better than 40-70% by volume of the whole mixture; gas compositions outside the limits of explosiveness. The temperature is 200-300, better than 220-290 ° C. The contact time should be sufficient to convert 0.5-70, 2-20, better than 5-20% ethylene, unreacted ethylene is recycled. Reaction modifiers are used, for example, chlorine in the form of chlorinated alkenes with 1-6 carbon atoms, for example, methyl chloride or tert-butyl chloride, dichloromethane or chloroform, chlorinated biphenyl or polyphenyl, chlorinated benzene, for example, monoyl dichlorobenzene, especially ethylene dihydride. The concentration of the reaction modifier depends on its chemical nature, in the case of ethylene dichloride it ranges from 0.1-100, better than 0.5-25 ppm by weight, and in the case of vinyl chloride, 0.1-200, better than 580 hours. / million by weight. Example 1. Catalyst A-I for the oxidation of ethylene to ethylene oxide is prepared as follows: 5.2 g of reagent grade silver acetate is dissolved in the minimum amount of anti-chemical required to dissolve completely. Appropriate amounts of potassium acetate, rubidium carbonate and / or cesium carbonate are added to the solution and the volume of the solution is made up to b ml of water. This solution is used for the impregnation of 30 g of the substrate, which uses the composition of alpha-alumina company Norton and K ° under the trade name Alundum, pre-crushed and sifted through a sieve to obtain particles with a diameter of 0.42-1 mm. The specific surface area of the substance is 0.3, the average pore diameter is 2.8 µm, and the water porosity is 20%. The substrate impregnated with silver solution is heated in an oven with forced air circulation for 4 hours at 100-300 C. A catalyst is obtained containing 8 wt.% Silver. Table 1 lists the amount of promoter, rubidium and cesium) and properties of the catalysts. Example 2. A TH6 irradiated catalyst as described in Example 1 (20 g) was loaded into a stainless steel reactor (internal diameter 8 mm) in a thermostatically controlled liquid bath, treated for 24 hours under increasing harsh reaction conditions. Upon reaching the established operating mode, the selectivity to ethylene oxide and oxygen conversion is determined using a process gas containing 30% ethylene, 8% oxygen and 30 ppm of vinyl chloride at a pressure of 1.05 atm, temperature of the reactor, gas hourly rate of 400 h Then, the pressure of the process gas is raised to 16.8 atm and the selectivity and conversion of oxygen is determined at a gas hourly rate of 4000 hours after the catalyst is set again. The test results of the catalyst are given in table.1. Example 3. To obtain I-N catalysts for the oxidation of ethylene with ethylene oxide, 8.9 g of silver oxalate are dissolved in 7 ml of a 50% solution of 1,2-diaminoethane in water. The solution is made up to 8 ml by adding ethanolamine, the appropriate amounts of potassium acetate, rubidium carbonate and / or cesium carbonate are added and 20 g of substrate are used for impregnation, which uses porous alpha alumina in the form of cylindrical granules with a diameter of 3 and a length of 3 mm The specific surface area is 2.2, the average pore diameter is 1 µm, the pore volume is 0.5 ml / g. The impregnated substrate is heated for 3 hours in a forced-circulation air oven. A catalyst is obtained containing about 24 wt.% Silver. The amount of potassium, rubidium and cesium is given in table 1. Example 4. A stainless steel reactor (inner diameter 8 mm) was loaded with 10 g of catalyst and subjected to an increase in harsh reaction conditions, and after the regime was established, the selectivity and oxygen conversion was determined using a process gas containing 30% ethylene, 8% oxygen and 30 h / m of vinyl chloride. The temperature of the reactor is 240 ° C, the hourly volumetric velocity of ha for 2000 hours. The pressure of the process gas is raised to 16.8 atm and the selectivity and conversion of oxygen at 240 ° C and a space velocity of 15000 hours are determined after the catalyst is stabilized again. The test results are shown in Table 1. Example 5. To prepare catalysts 1A-1L, 5.2 g of silver acetate is dissolved in the minimum amount of ammonia required to dissolve, an appropriate amount of potassium nitrate and rubidium nitrate is added to the solution and the volume of the solution is made up to bml with water, using to impregnate 30 g of the substrate. Use the substrate of the composition of alpha-alumina company Norton and K under the trade name Alundum, which is pre-crushed and sieved to particles with a diameter of 0.42-2.0 mm. The specific surface area of the substance is 0.3, the average pore diameter is 2.8 µm, and the water porosity is 20%. The substrate impregnated with a solution of silver is heated in an air oven with forced circulation for 3 hours at. Get the catalyst containing 8 wt.% Silver. The content of potassium and rubidium is given in table 2. Example 6. A 20 g of catalyst is loaded into a stainless steel reactor (inner diameter 8 mm) and subjected to its increasing harsh reaction conditions; after establishing the operating mode, the selectivity and oxygen conversion is determined with a process gas containing 30% ethylene, 8% oxygen and 20 ppm of vinyl chloride and 63% nitrogen at a pressure of 16.8 atm. The temperature of the reactor is 240 ° C, the gas velocity is 3000. The results of testing the catalysts are given in table 2. Table 1
    0.1
    0.001 0.1
    0.003 0.1
    0.01 0.1
    0.03 0.1
    0.3 0.1
    0.1 0.1
    0,003 0,1 0,010 0,3
    0.015
    9
    91 89 90 90 90 9G
    9 b b
    11 9 8 8 5 8 5 20
    8 9 б 7 б 4 88 90 90
    Continued table. one
    table 2
    权利要求:
    Claims (1)
    [1]
    Catalyst for the oxidation of ethylene to ethylene oxide containing silver, potassium, rubidium or cesium, and the carrier is aluminum oxide with a specific surface area, measured by the method of Brunauer, Emmett and Teller, 0.3 - 2.2 m 2 / g, about l and. hours and th weight.%:
    8-24 0.1-0.3 s in that, in order to increase the selectivity of the catalyst, it contains these components in the following ratio.
    Silver
    Potassium
    Rubidium or Cesium. Carrier
    0.001-0.15. The rest /
    类似技术:
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    US5374748A|1994-12-20|Process for preparing silver catalyst for ethylene epoxidation
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    同族专利:
    公开号 | 公开日
    FR2391771A1|1978-12-22|
    AU3550478A|1979-11-01|
    AU520958B2|1982-03-11|
    FR2391771B1|1985-05-17|
    NL7805163A|1978-11-27|
    US4226782A|1980-10-07|
    MX148855A|1983-06-27|
    IT7823625D0|1978-05-19|
    BE867185A|1978-11-17|
    JPS53144898A|1978-12-16|
    IT1094776B|1985-08-02|
    DE2820170A1|1978-12-07|
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    CA1117515A|1982-02-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3962136B1|1972-01-07|1983-11-15|
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    US4010115A|1972-01-07|1977-03-01|Shell Oil Company|Catalyst for the oxidation of ethylene to ethylene oxide|
    GB1491447A|1973-12-05|1977-11-09|Ici Ltd|Alkylene oxide production and catalysts therefor|
    CA1026763A|1974-05-20|1978-02-21|Robert P. Nielsen|Silver catalysts used in ethylene oxide production|
    GB1574426A|1976-03-25|1980-09-10|Shell Int Research|Process for preparing modified silver catalysts|
    US4066575A|1976-07-26|1978-01-03|Halcon International, Inc.|Process for the preparation of a supported silver catalyst|EP0002045B1|1977-11-19|1981-09-02|BASF Aktiengesellschaft|Process for preparing an ethylene oxide catalyst|
    US5387751A|1978-02-10|1995-02-07|Imperial Chemical Industries Plc|Production of olefine oxides|
    JPS5558972U|1978-10-16|1980-04-22|
    US4916243A|1979-03-20|1990-04-10|Union Carbide Chemicals And Plastics Company Inc.|New catalyst composition and process for oxidation of ethylene to ethylene oxide|
    DE2925625C2|1979-06-26|1981-10-01|Chemische Werke Hüls AG, 4370 Marl|Process for increasing the activity and for extending the service life with high selectivity of silver-supported catalysts for use in the synthesis of ethylene oxide|
    US4361504A|1981-09-04|1982-11-30|The Dow Chemical Company|Process for making a silver catalyst useful in ethylene oxide production|
    US4455392A|1981-10-05|1984-06-19|Union Carbide Corporation|Process for preparing a supported silver catalyst|
    US4760042A|1982-03-24|1988-07-26|Scientific Design Company, Inc.|Process for preparing an alkali metal-promoted silver catalyst|
    US4774222A|1982-06-16|1988-09-27|Scientific Design Company, Inc.|Catalyst for oxidation of ethylene to ethylene oxide and process for preparing the catalyst|
    BG37835A3|1982-06-30|1985-08-15|Hoechst Ag,De|Method for preparing silver catalyst|
    JPH0119605Y2|1982-11-09|1989-06-06|
    US4575494A|1984-02-08|1986-03-11|The Dow Chemical Company|Alumina compositions useful as catalyst supports for ethylene oxidation|
    NL8600959A|1986-04-16|1987-11-16|Veg Gasinstituut Nv|CATALYST FOR THE SELECTIVE OXYDATION OF SULFUR-CONTAINING COMPOUNDS, IN PARTICULAR SULFUR HYDROGENIC TO ELEMENTAL SULFUR; METHOD FOR PREPARING THE CATALYST AND METHOD FOR SELECTIVE OXIDIZATION OF SULFUR CONTAINERS, IN THE PARTICULAR SULFUR HYDROGENIC SODIUM SULFUR.|
    US4897498A|1988-01-28|1990-01-30|Eastman Kodak Company|Selective monoepoxidation of olefins|
    US4874879A|1988-07-25|1989-10-17|Shell Oil Company|Process for starting-up an ethylene oxide reactor|
    US5008413A|1989-10-23|1991-04-16|Scientific Design Company, Inc.|Catalyst for oxidation of ethylene to ethylene oxide|
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    WO2006120135A1|2005-05-10|2006-11-16|Ciba Specialty Chemicals Holding Inc.|Antimicrobial porous silicon oxide particles|
    TWI446964B|2007-05-09|2014-08-01|Shell Int Research|An epoxidation catalyst, a process for preparing the catalyst, and a process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine|
    US7714152B2|2007-08-30|2010-05-11|Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg|Carrier for olefin oxide catalyst|
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    CN101265242B|2008-04-16|2011-07-20|浙江师范大学|Method for directly preparing epoxy ethane by ethane one-step oxidation|
    BRPI0912391B1|2008-05-07|2018-04-17|Shell Internationale Research Maatschappij B.V.|OLEFINE EPOXIDATION PROCESS|
    US8349765B2|2008-07-18|2013-01-08|Scientific Design Company, Inc.|Mullite-containing carrier for ethylene oxide catalysts|
    US8586769B2|2010-06-04|2013-11-19|Scientific Design Company, Inc.|Carrier for ethylene oxide catalysts|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB21611/77A|GB1594362A|1977-05-23|1977-05-23|Production of alkylene oxides and catalysts therefor|
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