• 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:
    The invention relates to catalytic chemistry, in particular to the preparation of a catalyst for the hydroformylation of propylene. The goal is to obtain a catalyst with an increased service life. The catalyst is prepared by mixing the rhodium carboxylate salt as a solution in a hydrocarbon solvent with an aqueous solution of triphenylphosphine and treatment with carbon monoxide and hydrogen at 70-80 ° C and a pressure of 0.4-0.7 MPa with stirring either before mixing with triphenylphosphine, or after mix it up The method makes it possible to obtain a catalyst with an increased service life — until a conversion drops below 85%, 420 days are working (against 350 days according to the prototype).
    公开号:SU1530084A3
    申请号:SU874202540
    申请日:1987-05-12
    公开日:1989-12-15
    发明作者:Бах Ганс-Вильгельм；Барманн Гельмут；Корнильс Бой；Конколь Вернер；Вибус Эрнст
    申请人:Рурхеми А.Г. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the manufacture of catalysts, in particular, to methods of preparing rhodium-containing catalysts for hydroformylation of olefins.
    The aim of the invention is to obtain a catalyst with an extended service life due to the use of triphenylphosphine in the form of its aqueous solution and a certain temperature regime of treatment with carbon monoxide and hydrogen.
    PRI me R 1. In the autoclave, triphenylphosphine trisulfonate in water (approximately 30% salt, by weight of the solution) and 2-ethylhexanoate of rhodium in toluene (content of rhodium approximately 10 g / l) are fed into at 80 ° C and pressure
    0.4 MPa is treated with synthesis gas (CO: H2 1: 1). The transition of the dissolved salt in toluene to rhodium to the aqueous phase is continuously determined by analyzing the organic solvent. Approximately after 5 hours, rhodium is no longer found in the organic phase, but the content of the rod in the aqueous phase corresponds to the amount of rod originally used. When this process is stopped. The hydroformylation catalyst thus obtained, which is a complex compound of the rhodium salt and triphenylphosphine trisulfonate, can be used directly to produce aldehydes from olefins, and during the initial phase of the process
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    00

    cm
    315
    no relocation was observed. In addition, the conversion of the olefin is as high as during the further course of the process.
    Example2. A solution of hexane rhodium in toluene (content of rhodium, 5 g / l) is fed to the autoclave and stirred at a temperature of 70 ° C and a pressure of 0.7 MPa is treated with synthesis gas (CO: H.1: 1). After 3 hours, a solution of triphenylphosphine trisulfonate in water (approximately 28% salt by weight of the solution) is added to the solution of the rhodium compound, which provides a triphosphine to rogen ratio of approximately 100: 1. Continue to stir for 60 minutes. The analysis confirms the complete transfer of rhodium from the organic to the aqueous phase. When this process is stopped. The hydroformylation catalyst thus obtained, which is a complex compound of the rhodium salt and triphenylphosphine trisulfonate, can be used directly to produce aldehydes from olefins, and no rhodium removal is observed during the initial phase of the hydroformylation process. In addition, the conversion of the olefin is as high as during the rest of the process,
    EXAMPLE 3 Example 1 is repeated with the difference at temperature
    0.6 MPa and over t, 6 hours. The hydroformylation catalyst thus obtained, which is a complex compound of the rhodium salt and triphenylphosphine trisulfonate, can be used directly to produce aldehydes from olefins, and during the initial phase of the hydrofomilylation no birth . In addition, olefin conversion is equally high.
    that the process is carried out at 75 ° C and pressure
    0
    s
    0
    five
    0
    five
    0
    12 5 ° С
    45
    as during the rest of the process.
    An example. 2.5 g of the catalyst prepared in examples 1-3 are fed to a 1 liter reactor equipped with a stirrer, and at a temperature and total pressure of 50 bar, 50 g of propylene is reacted with an equimolar mixture of carbon monoxide and hydrogen. The conversion of propylene is 89.3%, 89.1% and VE%, respectively. In all experiments, a crude product of the following composition is obtained, wt%: iso-butanal 3, {{n-butanal, 2, iso-butanol 0.1; n-butanol, 0.8; 2-ethylhexenal 0.3, ethylhexenal 0.1; ethyl hexanal 0.1; aldol Cg 0,3; high boiling OJ components. In addition, it contains 1.5% of the catalyst (in terms of its initial amount). The service life of the catalyst obtained in Examples 1-3, BEFORE the conversion drops below 85%, is | 420 days.
    权利要求:
    Claims (1)
    [1]
    Thus, the proposed method allows to obtain a catalyst with an extended service life — until the conversion drops below 85%, the prototype runs for 350 days for 350 days. Invention Formula
    The method of preparing a catalyst for hydroformylation of propylene by mixing the rhodium carboxylic acid salt as a solution in a hydrocarbon solvent with triphenylphosphine and treatment with carbon monoxide and hydrogen at elevated temperature and pressure 0, A-0.7 MPa with stirring, so that In order to obtain a catalyst with a prolonged service life, triphenylphosphine is used in the form of its aqueous solution, and treatment with carbon monoxide and hydrogen is carried out at 70-8 ° C either before mixing with triphenylphosphine, or when it is barely mixed.
    类似技术:
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    同族专利:
    公开号 | 公开日
    DE3616057A1|1987-11-19|
    HU202467B|1991-03-28|
    AT72221T|1992-02-15|
    CA1268776A|1990-05-08|
    JPS6322046A|1988-01-29|
    JPH0544934B2|1993-07-07|
    YU82487A|1988-04-30|
    YU46200B|1993-05-28|
    AU7273387A|1987-11-19|
    HUT44474A|1988-03-28|
    ES2031848T3|1993-01-01|
    DE3776402D1|1992-03-12|
    KR870011075A|1987-12-19|
    US4795727A|1989-01-03|
    BR8702396A|1988-02-17|
    AU597652B2|1990-06-07|
    ZA873242B|1987-10-29|
    KR890003783B1|1989-10-04|
    EP0246475A3|1989-04-26|
    EP0246475A2|1987-11-25|
    EP0246475B1|1992-01-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US31812A|1861-03-26|Stump-extractor |
    US3937742A|1970-03-06|1976-02-10|Atlantic Richfield Company|Hydroformylation process using catalyst comprising platinum group metal on support having separate alumina phase|
    HU177239B|1974-10-15|1981-08-28|Monsanto Co|Process for preparing n-acetamido-l-alanine derivatives by means of the asymmetric catalytic hydrogenation of alpha-acetamido-acrylic acid derivatives|
    US4197253A|1978-06-30|1980-04-08|Union Carbide Corporation|Catalytic process for producing polyhydric alcohols|
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    EP0173219B1|1984-08-30|1988-05-11|Ruhrchemie Aktiengesellschaft|Process for making aldehydes|
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    US4947003A|1988-11-28|1990-08-07|Virginia Tech Intellectual Properties, Inc.|Process for the hydroformulation of olefinically unsaturated organic reactants using a supported aqueous phase catalyst|
    EP0668287B1|1988-12-02|2000-05-24|Celanese Chemicals Europe GmbH|Sulfonated phenyl phosphine-containing complexes|
    US5215667A|1991-08-20|1993-06-01|Exxon Chemical Patents Inc.|Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    US5288818A|1991-08-20|1994-02-22|Exxon Chemical Patents Inc.|Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    US5360938A|1991-08-21|1994-11-01|Union Carbide Chemicals & Plastics Technology Corporation|Asymmetric syntheses|
    DE4242725A1|1992-12-17|1994-06-23|Hoechst Ag|Process for the production of higher, predominantly unbranched, primary alcohols|
    BE1007052A3|1993-05-06|1995-02-28|Dsm Nv|Method for the preparation of 5-formylvalerianic acid ester|
    KR100299588B1|1993-05-06|2001-11-22|윌리암 로엘프 드 보에르|Process for producing linear aldehyde organic compound|
    DE4427428A1|1994-08-03|1996-02-29|Basf Ag|Process for the preparation of aldehydes|
    EP0823282B1|1996-05-15|2001-11-14|Celanese Chemicals Europe GmbH|Aldehydes preparation process|
    CZ283697A3|1996-09-11|1998-04-15|Mitsubishi Chemical Corporation|Process for preparing solution of rhodium complex and the use thereof|
    US5958197A|1998-01-26|1999-09-28|De Nora S.P.A.|Catalysts for gas diffusion electrodes|
    DE10133072A1|2001-07-07|2003-02-06|Celanese Chem Europe Gmbh|Production of aldehydes by hydroformylating olefinically unsaturated compounds using a rhodium catalyst comprises adding extra rhodium in preformed catalyst form|
    DE10164720B4|2001-07-07|2013-12-19|Oxea Gmbh|Process for the preparation of aldehydes|
    WO2005049202A1|2003-11-20|2005-06-02|Mitsubishi Chemical Corporation|Method for recovering rhodium complex catalyst|
    CN106103536A|2014-01-14|2016-11-09|陶氏环球技术有限责任公司|Produce the method for polyolefin ionomers and consequent ionomer|
    EP3770144A1|2019-07-24|2021-01-27|OQ Chemicals GmbH|Continuous hydroformylation process with catalyst substitution|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19863616057|DE3616057A1|1986-05-13|1986-05-13|METHOD FOR PRODUCING ALDEHYDES|
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