• 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:
    In a rhodium-catalyzed hydroformylation process which produces aldehydes from olefins, the stability of a rhodium catalyst complexed with carbon monoxide and a phosphine ligand is improved by the use of a ligand selected from a branched chain alkyldiphenylphosphine, a branched chain dialkylphenylphosphine, a cycloalkyldiphenylphosphine and a dicycloalkylphenylphosphine.
    公开号:SU1678201A3
    申请号:SU803250148
    申请日:1980-10-23
    公开日:1991-09-15
    发明作者:Биллиг Эрнст；Лерой Баннинг Дональд
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the production of C-C3-aldehydes, which are a valuable intermediate of industrial organic synthesis.
    The purpose of the invention is to simplify the process by using a more stable catalyst.
    Examples 1-11. A reactor representing a 100 ml stainless steel autoclave, equipped with a magnetic stirrer, with external heating from two 300 W heaters, is connected to a gas branched pipeline (manifold). 15-ml loading of the catalyst solution,
    containing 250 ppm of rhodium, is calculated on the pure metal and is introduced in the form of acetylacetonate Rh (CO) 2 and ligands (Table 1) (the total molar ratio of ligand to rhodium is 10: 1) in dimethylformamide used as a solvent, and introduced into the autoclave. The reactor is flushed with nitrogen and the internal temperature is adjusted and maintained at the values given in Table. 1, using a proportional temperature controller. Then under pressure
    KG
    75 psi (5.25) pref.
    unmixed feed gas consisting of CsHe: CO: H2 at a molar ratio of 1: 1: 1 is added to the reactor and at the same time
    VI 00
    yoo o

    with
    reacting the hydroformylation with a corresponding reduction in pressure. The observed hydroforming reaction rates are determined at a time when it is required to reduce the pressure by 5 pounds per square inch (0.35 kg / cm). From the dependence of the reciprocal of these rates, M / h (average r-mol / l / h), on time, the second order deactivation rate constant and the initial hydroformylation rate are determined.
    The results are shown in Table. one.
    As can be seen from the data table. 1, the n-alkylphenylphosphine ligands of examples 1–3 have relatively low deactivation rate constants, a significant stability of the catalyst, but the corresponding initial hydroformylation rates are small. The ligands of examples 4 and 11 (to a lesser extent the ligands of example 10), having relatively high hydroformylation rates, show significantly higher values of the deactivation rate constants. However, the secondary and tertiary alkylphenylphosphines and cycloalkylphenylphosphines of Examples 5-9 demonstrate a combination of high initial hydroformylation rates and good catalyst stability (although the deactivation rate constant in Example 8 is high, the initial hydroformylation rate is greatest). From all the examples it is clear that all alkyl substituted phosphines are more stable than triphenyl phosphines.
    Examples 12-15. The procedures of examples 1-11 are repeated with ligands at
    the conditions given in Table 2. The average hydroformylation rate, M / h (g-mol / l / h), is determined.
    The isomeric ratio of aldehydes is determined by gas chromatography of the reaction solution.
    The results are summarized in table. 2
    Example 12 is included for reference only. From the data table. 2 that the phosphine ligands used in the invention (Examples 13-15) provide lower ratios compared with the known triphenylphosphine ligand (Example 12).
    Thus, this method simplifies the process by using a more stable catalyst.
    权利要求:
    Claims (1)
    [1]
    The invention The method of producing C -Cb-zldehydes by hydroformylation of the corresponding olefin with carbon monoxide and hydrogen at elevated temperature and elevated pressure in the presence of a soluble complex catalyst comprising rhodium forming a complex with carbon monoxide and a phosphine ligand at a molar ratio of ligand to rhodium 10-80: 1 in the liquid phase, characterized in that, in order to simplify the process by using a more stable catalyst, the phosphine total phosphate is used as the phosphine ligand the formulas RnPPhn-3, where, when n is 1, R is isobutyl, isopropyl or cyclohexyl, and for n 2, R is cyclohexyl or isopropyl, and Ph is phenyl.
    Table 1
    Note. Ph is phenyl; Me - methyl: We - butyl; Pr - propyl Et - ethyl.
     Less than 1.00 x 10 4 Comparative examples.
    Note. Ph, Bu, Pr and - the same as in table 1. Comparative example.
    cyclohexyl.
    table 2
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1678201A3|1991-09-15|Method of preparation of @@@ aldehydes
    US4201714A|1980-05-06|Stabilized catalyst complex of rhodium metal, bidentate ligand and monodentate ligand
    US4169861A|1979-10-02|Hydroformylation process
    US4960949A|1990-10-02|Low pressure rhodium catalyzed hydroformylation of olefins
    US4201728A|1980-05-06|Hydroformylation catalyst and process
    EP0024091B1|1985-04-03|Hydroformylation process and novel transition metal catalysts
    US4328375A|1982-05-04|Process for the production of ethanol and/or acetaldehyde in the presence of metal complex catalyst systems
    US4133966A|1979-01-09|Selective formation of ethanol from methanol, hydrogen and carbon monoxide
    US4239924A|1980-12-16|Ethanol from methanol
    US4193943A|1980-03-18|Hydroformylation catalysts
    US3824221A|1974-07-16|Metallated polymers
    US4138420A|1979-02-06|Hydroformylation catalysts
    EP0073398A1|1983-03-09|Hydroformylation process using a rhodium complex catalyst with triarylphosphine and biphosphine monoxide ligands
    EP0030434B1|1984-01-25|Methanol homologation using cobalt-ruthenium catalysts
    US4480137A|1984-10-30|Trihydrocarbyl silyl substituted alkyl diaryl phosphine transition metal complexes and their use as homogeneous carbonylation catalysts
    US4155939A|1979-05-22|Hydroformylation process
    US4108905A|1978-08-22|Catalytic reactions
    US4477685A|1984-10-16|Hydroformylation process to prepare glycolaldehydes
    US4239925A|1980-12-16|Ethanol from methanol
    US4405814A|1983-09-20|Hydroformylation of formaldehyde with rhodium catalysts
    US4235744A|1980-11-25|Carbonylation of olefinically unsaturated compounds
    US4238357A|1980-12-09|Carbonylation of olefinically unsaturated compounds
    JPH0733349B2|1995-04-12|Method for producing ethylidene diacetate
    EP0013464A1|1980-07-23|Selective formation of ethanol from methanol, hydrogen and carbon monoxide
    US4357480A|1982-11-02|Process for the production of ethanol by the liquid phase hydrocarbonylation of methanol
    同族专利:
    公开号 | 公开日
    JPS5671032A|1981-06-13|
    ZA806160B|1981-09-30|
    BR8006845A|1981-04-28|
    PL227478A1|1981-07-10|
    KR840000212B1|1984-02-29|
    US4283562A|1981-08-11|
    DE3069950D1|1985-02-21|
    KR830004326A|1983-07-09|
    CA1137998A|1982-12-21|
    YU42711B|1988-12-31|
    MX155379A|1988-02-26|
    EP0028378A1|1981-05-13|
    AU6367380A|1981-04-30|
    PL129099B1|1984-03-31|
    EP0028378B1|1985-01-09|
    JPH02332B2|1990-01-08|
    AU538456B2|1984-08-16|
    IN154537B|1984-11-03|
    YU272280A|1983-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3448157A|1965-09-27|1969-06-03|Shell Oil Co|Hydroformylation of olefins|
    US3487112A|1967-04-27|1969-12-30|Monsanto Co|Vapor phase hydroformylation process|
    US3527809A|1967-08-03|1970-09-08|Union Carbide Corp|Hydroformylation process|
    US3644446A|1969-07-01|1972-02-22|Union Oil Co|Preparation of rhodium and iridium hydride carbonyl complexes|
    GB1338237A|1969-12-22|1973-11-21|Union Carbide Corp|Hydroformylation process|
    US4101588A|1973-04-07|1978-07-18|Basf Aktiengesellschaft|Production of bis- acetals of hexane dialdehydes|
    IT1005691B|1973-04-07|1976-09-30|Basf Ag|PROCESS FOR THE PREPARATION OF ALIPHATIC OR CYCLOALIPHATIC DIALDEHYDES AND OF THEIR ACETALS|
    FR2351077B1|1976-05-13|1981-01-30|Celanese Corp|
    ZA78146B|1977-01-25|1978-12-27|Union Carbide Corp|Improved hydroformylation process|
    US4215077A|1978-02-09|1980-07-29|Kuraray Co., Ltd.|Hydroformylation of olefins|US4593141A|1979-02-12|1986-06-03|Exxon Research And Engineering Co.|Hydroformylation catalysis by branched alkyl diaryl phosphine rhodium complexes|
    US4687874A|1980-02-12|1987-08-18|Exxon Research And Engineering Company|Selective hydroformylation process using alkyl diaryl phosphine rhodium carbonyl hydride catalysts|
    US4687866A|1980-02-12|1987-08-18|Exxon Research And Engineering Company|Ligand exchange process for producing alkyl diaryl phosphine rhodium carbonyl hydrides|
    US4450299A|1980-10-01|1984-05-22|Exxon Research And Engineering Co.|Homogeneous hydroformylation catalysis with silyl substituted alkyl diaryl phosphine metal complexes|
    US4400548A|1981-08-17|1983-08-23|Union Carbide Corporation|Hydroformylation process using bisphosphine monooxide ligands|
    US4491675A|1981-08-17|1985-01-01|Union Carbide Corporation|Hydroformylation process using triarylphosphine and bisphosphine monooxide ligands|
    US4593011A|1981-08-17|1986-06-03|Union Carbide Corporation|Hydroformylation process using triarylphosphine and bisphosphine monooxide ligands|
    US4522933A|1981-08-17|1985-06-11|Union Carbide Corporation|Hydroformylation catalyst containing bisphosphine monooxide ligands|
    IT1140319B|1981-12-04|1986-09-24|Consiglio Nazionale Ricerche|CATALYST CONTAINING CHIRAL STEROID PHOSPHINS ASYMMETRICAL CATALYTIC PRECESSES THAT USE THEM|
    US4595753A|1982-05-03|1986-06-17|Exxon Research And Engineering Co.|Heterocycle-substituted alkyl diaryl phosphine rhodium caronyl hydride complex hydroformylation catalyst compositions|
    US4668809A|1982-05-03|1987-05-26|Exxon Research And Engineering|Transition metal complex catalysts|
    DE3372361D1|1982-06-11|1987-08-13|Davy Mckee London|Hydroformylation process|
    US4668823A|1983-12-30|1987-05-26|Union Carbide Corporation|Process for the preparation of bulky alkyldiarylphosphines and unsymmetrical aryldialkyl phosphines|
    US4737588A|1984-12-28|1988-04-12|Union Carbide Corporation|Transition metal complex catalyzed reactions|
    US4599206A|1984-02-17|1986-07-08|Union Carbide Corporation|Transition metal complex catalyzed reactions|
    US5110990A|1984-03-30|1992-05-05|Union Carbide Chemicals & Plastics Technology Corporation|Process for recovery of phosphorus ligand from vaporized aldehyde|
    US4593127A|1985-01-11|1986-06-03|Union Carbide Corporation|Hydroformylation process|
    US4625068A|1985-03-20|1986-11-25|Exxon Chemical Patents Inc.|Rhodium catalyzed hydroformylation of internal olefins|
    US4642388A|1985-08-30|1987-02-10|Exxon Chemical Patents Inc.|Rhodium catalyzed hydroformylation of alpha-substituted alpha-olefins|
    AT66668T|1986-07-01|1991-09-15|Davy Mckee London|METHOD FOR PRODUCING ALDEHYDES BY HYDROFORMYLATION.|
    US4716250A|1986-07-10|1987-12-29|Union Carbide Corporation|Hydroformylation using low volatile/organic soluble phosphine ligands|
    US4731486A|1986-11-18|1988-03-15|Union Carbide Corporation|Hydroformylation using low volatile phosphine ligands|
    US5113022A|1988-08-05|1992-05-12|Union Carbide Chemicals & Plastics Technology Corporation|Ionic phosphites used in homogeneous transition metal catalyzed processes|
    US5059710A|1988-08-05|1991-10-22|Union Carbide Chemicals And Plastics Technology Corporation|Ionic phosphites and their use in homogeneous transition metal catalyzed processes|
    JPH031927U|1989-05-26|1991-01-10|
    US5001274A|1989-06-23|1991-03-19|Union Carbide Chemicals And Plastics Company Inc.|Hydroformylation process|
    US5516965A|1995-01-18|1996-05-14|Exxon Research And Engineering Company|Unsaturates recovery and recycle process|
    US5520722A|1995-01-18|1996-05-28|Exxon Research And Engineering Company|Multiunsaturates removal process|
    US5675041A|1995-01-18|1997-10-07|Exxon Research & Engineering Company|Direct hydroformylation of a multi-component synthesis gas containing carbon monoxide, hydrogen, ethylene, and acetylene|
    US6265619B1|1996-01-17|2001-07-24|Exxon Chemical Patents Inc.|Oxygenates and processes for their manufacture|
    US5763679A|1995-12-06|1998-06-09|Union Carbide Chemicals & Plastics Technology Corporation|Metal-ligand complex catalyzed processes|
    US5892119A|1996-11-26|1999-04-06|Union Carbide Chemicals & Plastics Technology Corporation|Metal-ligand complex catalyzed processes|
    JP3864669B2|2000-05-08|2007-01-10|三菱化学株式会社|Hydroformylation process|
    BRPI0411948B1|2003-07-03|2014-03-25|Dow Technology Investments Llc|Method for minimizing the production of one or more phosphonium ion binder degradation products and process for minimizing the formation of one or more phosphonium ion binder degradation products|
    DE10349343A1|2003-10-23|2005-06-02|Basf Ag|Stabilization of hydroformylation catalysts based on phosphoramidite ligands|
    DE10352261B4|2003-11-08|2006-08-24|Celanese Chemicals Europe Gmbh|Process for the preparation of TCD-dialdehyde|
    ES2671380T3|2004-08-02|2018-06-06|Dow Technology Investments Llc|Stabilization of a hydroformylation procedure|
    KR101331473B1|2005-03-16|2013-11-22|페르스토르프 스페셜티 케미컬즈 에이비|Hydroformylation process with improved iso-selectivity|
    US8466306B2|2008-01-15|2013-06-18|Dow Global Technologies Llc|Sulfonated organophosphine compounds and use in hydroformylation processes|
    DE102009004655B4|2009-01-15|2013-02-14|Oxea Gmbh|Process for the preparation of aldehydes|
    DE102009016652A1|2009-04-07|2010-10-14|Oxea Gmbh|Process for working up a liquid hydroformylation discharge|
    DE102009016651B4|2009-04-07|2011-11-17|Oxea Gmbh|Process for the preparation of aldehydes|
    US9428529B2|2011-09-30|2016-08-30|Dow Technology Investments Llc|Process for purification of trivalent phosphorous ligands that can be used for preparation of catalysts|
    EP2794537B1|2011-12-20|2016-01-06|Dow Technology Investments LLC|A hydroformylation process|
    US8710276B2|2012-05-24|2014-04-29|Lg Chem, Ltd.|Catalyst compositions for hydroformylation reaction and hydroformylation process using the same|
    DE102012105878A1|2012-07-02|2014-01-02|Oxea Gmbh|Process for the preparation of isopentane derivatives|
    DE102012014395B3|2012-07-13|2013-08-22|Oxea Gmbh|Isononylamines starting from 2-ethylhexanol, process for their preparation and their use|
    DE102012014396B4|2012-07-13|2018-01-11|Oxea Gmbh|Process for the preparation of a vinyl ester mixture from a mixture of positionally isomeric aliphatic Isononansäuren starting from 2-ethylhexanol|
    DE102012013969B4|2012-07-13|2017-09-14|Oxea Gmbh|Process for the preparation of a mixture of positionally isomeric aliphatic isononanoic acids starting from 2-ethylhexanol|
    DE102012013968A1|2012-07-13|2014-04-03|Oxea Gmbh|Carboxylic acid ester of isononanoic acid starting from 2-ethylhexanol, process for their preparation and their use|
    CN104248860A|2013-06-27|2014-12-31|陶氏技术投资有限责任公司|Heat management process|
    DE102013113724A1|2013-12-09|2015-06-11|Oxea Gmbh|Process for the preparation of pentane derivatives and derivatives of alpha, beta-unsaturated decenals from propylene|
    EP3414220B1|2016-02-11|2021-10-13|Dow Technology Investments LLC|Processes for converting olefins to alcohols, ethers, or combinations thereof|
    TW201904924A|2017-06-23|2019-02-01|美商陶氏科技投資有限公司|Hydroformylation reaction process|
    KR20210013702A|2018-05-30|2021-02-05|다우 테크놀로지 인베스트먼츠 엘엘씨.|How to slow the deactivation of the catalyst and/or slow the use of tetraphosphine ligands in the hydroformylation process|
    CN112088153A|2018-05-30|2020-12-15|陶氏技术投资有限责任公司|Method for controlling a hydroformylation process|
    JP2021525166A|2018-05-30|2021-09-24|ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー|Catalytic compositions containing a combination of monophosphine and tetraphosphine ligands, and hydroformylation processes using them|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/088,827|US4283562A|1979-10-26|1979-10-26|Hydroformylation process using stable rhodium catalyst|
    [返回顶部]