• 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:
    A process for the preparation of a silver-containing catalyst suitable for the oxidation of ethylene to ethylene oxide, characterized in that a silver compound is applied to a carrier, after which the silver compound is reduced to metallic silver, and in which process the carrier has been prepared by mixing an aluminium compound with a tin compound and by calcining the obtained mixture.
    公开号:SU1595331A3
    申请号:SU864027725
    申请日:1986-06-26
    公开日:1990-09-23
    发明作者:Боксхоорн Госсе；Менте Вельтхейс Отто；Хендрик Кладинга Аан
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for preparing silver-containing catalysts for the oxidation of ethylene to ethylene oxide.
    The purpose of the invention is to obtain a catalyst with increased activity due to the use as a carrier of a mixture obtained by mixing alumina with sulphate with a tin amount of 1-23 wt.% In water, extruding and roasting at 1400-1600 0.
    Example 1. 6.1 g of tin sulphate in 160 ml of water are mixed with 133.3 g of alumina (AlOj-HjO), and tin sulphate with water is added to alumina. The mixture is stirred in a plasticizer for 8 minutes. The paste is extruded. The resulting products of a certain form are dried at and then burned at a gradually higher temperature. The rate of increasing the temperature up to 500 ° C is 200 ° C / h, after which the calcination is continued for 1 hour at, and then for 2 hours, the temperature is raised to 140. i sec, and the calcination is carried out at 1400 ° C for 1 hour. The pore volume of the molded products is 0.45 ml / g, and the average dia-. pore meter 1.0 micron. The ratio of tin / aluminum to minium on the surface is greater than the mass ratio of tin / aluminum; The finished molded product is impregnated with an aqueous solution of silver oxalate, in the cop.
    with
    ABOUT
    00 00

    cm
    The second is cesium hydroxide. The impregnation is carried out for 10 minutes under vacuum, after which the product is separated from the solution. And at 10 minutes, they are placed in a hot air stream with a temperature of 25P-.71) C to convert the silver salt to silver. As an aqueous solution of silver oxalate use
    17 C below,
    A 28% aqueous solution of silver, in which the silver of the catalyst according to the inventor of silver oxalate is used in
    complex with diamine ethylene and to which cesium hydroxide is added. After
    hot air treatments impregnated
    products contain 28 wt.% silver
    (from the total mass of the catalyst) and
    48 ma.h. cesium per 1 mln. kata lysator in general.
    The catalyst thus obtained is used to produce ethylene oxide from ethylene and oxygen. The CDL is a 40 cm long, cylindrical steel reactor with a cross section of 5 mm filled with catalyst particles of approximately 1 mm in size. The reactor 25 is placed in a fluidized bath
     a layer containing particles of silicon oxide and aluminum oxide. A gas of the following composition is passed through the reactor, mol%: ethylene 30; oxygen 8.5; carbon dioxide 7j nitrogen 54.5, and 5.5 parts per 1 ppm. vinyl chloride gas as a moderator. The volumetric rate is 3300-1,% pressure of 15 bar, and the temperature depends on the set value of the oxygen conversion. Measuring equipment connected to the reactor is connected to a computer for a precise control of the conversion process and temperature. The concentration of the components involved in the reaction is determined by gas chromatography and mass spectroscopy. After 24 hours, the reaction temperature is measured at 40% Oxygen Conversion, it is equal to 212 C. A similar test for a standard catalyst S 839 shows that
    thirty
    for standard
    catalyst S 839 under the same reaction conditions.
    Example 3. 4.21 g of tin sulfate and 0.89 g of cesium fluoride in 150 ml of water are mixed with 132.3 g of aluminum oxide () by adding an aqueous solution of tin sulfate - cesium fluoride in aluminum oxide for 1 min, the mixture is stirred in the flow of yu m is in the mixer and is extruded. The obtained figured pieces are dried for 12 hours at 121) C, followed by firing with a gradual increase in temperature. Calcination starts at a temperature that rises at a rate of 200 C / h to 500 ° C. The firing is continued for 1 h at, after which the temperature is increased for 2 h before and continued firing for 1 h at 1500 C. The pore volume of the figured alumina pieces is 0.41 ml / g and the average pore diameter is 1.66 μm. The cesium / aluminum atomic ratio with weighing was 0.003, and the atomic ratio 10 HEAD / aluminum was 0.01. Photoelectron X-ray spectroscopy of the carrier surface shows that the atomic ratio of cesium / aluminum is 0.042 and the atomic ratio of tin / aluminum is .0.034.
    The resulting shaped pieces are impregnated with an aqueous solution of oxalate-45 ribs, to which cesium hydroxide is added. The impregnation is carried out for 10 minutes in a vacuum atmosphere, after which the figured pieces are separated from the growth thief and placed in a stream of hot air with a temperature of 250-270 ° C for 10 minutes to convert the silver salt into metallic silver. The silver oxalate concentration in the aqueous solution is 28% by weight of silver in an aqueous solution in which silver oxalate is combined with ethylenediamine and -B which solution 1: cesium hydroxide is added. After being treated with hot air, soaked in this way.
    35

    40
    T 236 ° C. It turned out
    4c
    THAT is 40 for a silver containing catalyst at lower T 4 for a standard S 839 catalyst under the same reaction conditions.
    Example 2 A silver containing catalyst was prepared analogously to example 1, except that in the preparation of the carrier, a quantity of tin sulfate (30.5 g) was used. A catalyst containing 18 wt.% Silver and 290 h / min cesium.

    four
    at 50% oxygen conversion. The silver particle size on the catalyst surface is 60 nm. The reaction conditions are the same as in Example 1, except that the gas passed through the reactor did not contain carbon dioxide.
    It turned out that T f content.1senii 17 C below ,,
    go silver catalyst according to the invention
    five
    0
    for standard
    catalyst S 839 under the same reaction conditions.
    Example 3. 4.21 g of tin sulfate and 0.89 g of cesium fluoride in 150 ml of water are mixed with 132.3 g of hydroxy. Yes aluminum () by adding an aqueous solution of tin sulfate - cesium fluoride to alumina for 1 minute, the mixture is stirred for 10 minutes in a mixer and extruded. The obtained figured pieces are dried for 12 hours at 121) C, followed by firing with a gradual increase in temperature. Calcination starts at a temperature that rises at a rate of 200 C / h to 500 ° C. The firing is continued for 1 h at, after which the temperature is increased for 2 h before and continued firing for 1 h at 1500 C. The pore volume of the figured alumina pieces is 0.41 ml / g and the average pore diameter is 1.66 μm. The atomic ratio of cesium / aluminum at weighing is 0.003, and the atomic ratio of 10FOR / aluminum is 0.01. Photoelectron X-ray spectroscopy of the carrier surface shows that the atomic ratio of cesium / aluminum is 0.042 and the atomic ratio of tin / aluminum is .0.034.
    The resulting shaped pieces are impregnated with an aqueous solution of c-5-oxalate, to which cesium hydroxide is added. The impregnation is carried out for 10 minutes in a vacuum atmosphere, after which the figured pieces are separated from the growth thief and placed in a stream of hot air with a temperature of 250-270 ° C for 10 minutes to convert the silver salt into metallic silver. The silver oxalate concentration in the aqueous solution is 28% by weight of silver in an aqueous solution in which silver oxalate is combined with ethylenediamine and -B which solution 1: cesium hydroxide is added. After being treated with hot air, soaked in this way.
    five

    0
    0
    five
    5159533
    shaped pieces contain 15.5 wt.% Ag (based on the weight of the catalyst) and 310 parts per 1 million (impregnated) cesium on the weight of the catalyst.
    The silver catalyst prepared in this way is subjected to the test. A cylindrical steel reactor 15 cm long and 3 mm in diameter is completely filled with particles of a catalyst of about 0.3 mm in size.
    The reactor is placed in a bath in which the silica and alumina particles are in a liquefied state. A gas mixture of the following content is passed through the reactor, mol%: ethylene 30; oxygen 8.5; carbon dioxide 7; nitrogen 54.5 and 7 parts per million of vinyl chloride gas as a moderator. The space velocity is 30000-1.1 h, the pressure is 15 bar, and the temperature depends on the installation for the conversion of oxygen. The measuring equipment is connected to the reactor and to the computer. 25 Conversion and temperature are controlled with patient accuracy. The concentration of the reaction components is determined by a gas chromatograph. The stability test is carried out at an AO of 30% oxygen conversion.
    The reaction temperature at 35% oxygen conversion is determined during the entire test time. The selectivity for oxide and ethylene is also determined. After 30 days, the entire amount of ethylene oxide produced on the catalyst was established. From measurements of the reaction temperatures, the temperature rise (C) Q is calculated at the time at which 1000 g of ethylene oxide per 1 ml of catalyst (LT j) is obtained. Based on measurements of selectivity, a decrease is calculated, selectivity (mol%) at the time at which 1000 g of ethylene oxide per 1 ml of catalyst (S j) could be obtained. The same calculations and measurements were carried out during tests on a conventional catalyst .50
    The table shows the relative values of 4 S and L T for an ordinary silver catalyst.
    The particles of silver on a conventional commercial catalyst after 30 days of operation in harsh conditions have already been sintered with each other, while silver on the proposed catalyst does not detect
    35
    ABOUT
    Q 5 0

    five
    one .
    no trace of agglomeration after
    the same time of operation in harsh conditions. Therefore, the proposed catalyst has a much greater stability than the usual catalyst. It shows the loss of selectivity),% (for ethylene oxide) and the loss of activity based on a temperature increase of 2 C.
    The proposed catalyst has the values S ;, and T; 79.67a with, respectively (measured on the catalyst under normal conditions of operation according to GHSV for 330 hours -.
    EXAMPLE 4 A professional substrate is prepared from alumina with the same Sn / Al Cs / Al ratio as in Example 3 (Sn / Al 0.01; Ics / Al 0, () 06). The firing mode is analogous to Example 3, except that the product is fired for 6 hours at instead of 1500 ° C.
    1 hour
    The carrier is impregnated with an aqueous solution of silver oxalate together with diamine ethylene to which is added a solution of cesium hydroxide and ammonium fluoride. The carrier is impregnated analogously to Example 3. The catalyst contains 7.1.7 wt.% Ap, (based on the weight of the catalyst), 420 hours per 1 million of impregnated cesium and 200 hours on 1 million of fluorine (based on .1 million May catalyst parts).
    The resulting silver catalyst is used to produce ethylene oxide from ethylene and oxygen. The experiment is carried out analogously to example 3. The selectivity is 82.5%, and the value of T is 230 ° C.
    Thus, the proposed method allows to obtain a silver-containing catalyst, in which the surface is almost completely covered with part. silver, which leads to an increase in the activity of the catalyst.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for preparing a silver-containing catalyst for oxidation. ethylene to ethylene oxide by impregnating the alumina-based support: - with a mini aqueous solution of silver oxalate, containing IJJ cesium hydroxide, followed by reduction of silver oxalate to metallic silver, characterized in that.
    in order to obtain a catalyst with increased activity, a mixture prepared by mixing alumina with
    tin sulfate in the amount of 123 wt.% in water, extrusion and
    roasting at 1400-1600 ° С.
    15.5 31П 20 20 Conventional catalyst 100 100
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    同族专利:
    公开号 | 公开日
    KR940000864B1|1994-02-03|
    US4701437A|1987-10-20|
    TR22699A|1988-04-08|
    DE3663518D1|1989-06-29|
    CA1283899C|1991-05-07|
    AU5928986A|1987-01-08|
    DK161016C|1991-10-28|
    AU580175B2|1989-01-05|
    EP0207542B1|1989-05-24|
    MX165322B|1992-11-05|
    CS266590B2|1990-01-12|
    CS476186A2|1989-04-14|
    DK161016B|1991-05-21|
    DK304086D0|1986-06-26|
    BR8602941A|1987-02-17|
    ZA864758B|1987-02-25|
    PL158085B1|1992-08-31|
    CN86104390A|1986-12-24|
    JPH0761447B2|1995-07-05|
    EP0207542A1|1987-01-07|
    CN1009828B|1990-10-03|
    DK304086A|1986-12-29|
    JPS624443A|1987-01-10|
    KR870000100A|1987-02-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1133484A|1965-05-18|1968-11-13|Ici Ltd|Improvements in and relating to catalysts|
    CH529586A|1970-09-16|1972-10-31|Montedison Spa|Catalyst for the production of ethylene oxide from ethylene|
    US3962136B1|1972-01-07|1983-11-15|
    US4092372A|1975-04-03|1978-05-30|Takeda Chemical Industries, Ltd.|Catalyst for the production of isoprene|
    FR2412538B1|1977-12-22|1980-10-10|Ugine Kuhlmann|NL8502992A|1985-11-01|1987-06-01|Dow Chemical Nederland|METHOD FOR LOADING A MOLDED CARRIER MATERIAL WITH A CATALYTICALLY ACTIVE MATERIAL OR WITH A PRECURSOR OF A CATALYTICALLY ACTIVE MATERIAL AND FORMED CATALYST OBTAINED USING THE METHOD|
    NL8502991A|1985-11-01|1987-06-01|Dow Chemical Nederland|METHOD FOR PREPARING A SILVER-ON-CARRIER CATALYST|
    NL8502993A|1985-11-01|1987-06-01|Dow Chemical Nederland|SILVER CATALYST AND METHOD FOR THE PREPARATION THEREOF.|
    GB8618325D0|1986-07-28|1986-09-03|Shell Int Research|Catalyst|
    GB8716653D0|1987-07-15|1987-08-19|Shell Int Research|Silver-containing catalyst|
    US5102848A|1990-09-28|1992-04-07|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst composition for oxidation of ethylene to ethylene oxide|
    DE19935185C2|1999-07-27|2003-02-27|Qualitrans Transp Gmbh|Transport device for rail car walls|
    JP2007503304A|2003-08-22|2007-02-22|ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション|Modified alumina support and silver-based catalyst for alkylene oxide production|
    CN101146604A|2005-03-22|2008-03-19|国际壳牌研究有限公司|A reactor system and process for the manufacture of ethylene oxide|
    US8017546B2|2006-09-15|2011-09-13|Nippon Shokubai Co., Ltd.|Catalyst for producing alkylene oxide, method for producing the same, and method for producing alkylene oxide using said catalyst|
    US8173574B2|2006-09-20|2012-05-08|Basf Corporation|Catalysts to reduce NOx in an exhaust gas stream and methods of preparation|
    CN101595059A|2006-09-21|2009-12-02|托库森美国股份有限公司|The temperature production method of the TiO 2 particles of nanometer size|
    US9012345B2|2010-03-26|2015-04-21|Dioxide Materials, Inc.|Electrocatalysts for carbon dioxide conversion|
    US10975480B2|2015-02-03|2021-04-13|Dioxide Materials, Inc.|Electrocatalytic process for carbon dioxide conversion|
    US10173169B2|2010-03-26|2019-01-08|Dioxide Materials, Inc|Devices for electrocatalytic conversion of carbon dioxide|
    US9815021B2|2010-03-26|2017-11-14|Dioxide Materials, Inc.|Electrocatalytic process for carbon dioxide conversion|
    JP5570277B2|2010-03-31|2014-08-13|株式会社日本触媒|Catalyst for producing ethylene oxide and method for producing ethylene oxide|
    US10774431B2|2014-10-21|2020-09-15|Dioxide Materials, Inc.|Ion-conducting membranes|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL8501863|1985-06-28|
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