• 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:
    Process for preparing hydridocarbonyltris-(triorganophosphorus) rhodium compounds.
    公开号:SU1722230A3
    申请号:SU823423050
    申请日:1982-01-06
    公开日:1992-03-23
    发明作者:Биллиг Эрнст；Роберт Брайэнт Дэвид；Дин Джэмерсон Джеки
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to an improved process for the preparation of complex rhodium catalysts which can be used in the chemical industry.
    The purpose of the invention is to simplify the method.
    The indicated amounts are calculated for free metal. The symbol PR in the formulas denotes the phenyl radical.
    Example. Spent hydroformylation reaction medium (obtained from a continuous process of hydroformylation of propylene with carbon monoxide and hydrogen in the synthesis of oil aldehyde in the presence of a rhodium complex catalyst consisting of a rhodium complex with carbon monoxide and triphenylphosphine, and free triphenylphosphine, and this medium contains rhodium less than 400 h. / million, whose catalytic activity has decreased to 30% of the activity
    fresh catalyst) is concentrated in a thin film evaporator to remove by distillation butyric aldehyde present in this medium more than 90% by weight of aldehyde condensation products, whose boiling point is lower than the boiling point of said free tri-organophosphorus ligand present in said medium. In the distillation residue, a highly viscous concentrate of the rhodium complex is obtained, comprising less than 6% by weight of the indicated medium and containing 8000 ppm. Rhodi and a small amount of free triphenylphosphine linand (about 2.7 wt.% calculated on the total mass of the specified concentrate), and the rest of the specified concentrate is mainly high boiling by-products of aldehyde condensation (more than 35 wt.% of said condensation by-products with a point
    boiling is higher than the boiling point of said free triphenylphosphine ligand) and phosphine oxide. 675 g of the specified concentrate of the rhodium complex are oxidized with air at a temperature of about 90 ° C for about 24 hours (this oxidative treatment was sufficient to convert the entire free phosphine ligand present in the specified concentrate to the corresponding phosphine oxide).
    675 g of the indicated oxidized concentrate of the rhodium complex (according to the analysis it contains 5.55 g of rhodium) is mixed with 200 ml (about 34 mol-equiv. Calculated per specified amount of rhodium) of N, N-dimethylformamide, 70.8 g (about 5 mol- equivalent to a specified amount of rhodium) triphenylphosphine and 13 ml (3 mol-equiv per calculated amount of rhodi) of concentrated hydrochloric acid in a three-necked flask equipped with a magnetic stirrer, thermometer and reflux condenser, which is heated to boiling and boiled under reflux with stirring during the night (at 149-180 ° C) with access of air.
    After cooling to room temperature, this suspension is diluted with 1 l of methanol and then filtered to obtain 5.12 g (wet) of the indicated desired C1 Hp (CO) (Ft3) 2 greenish solid product. The amount of rhodium remaining in the filtrate is determined by atomic absorption analysis, it is 1.19 g or 34% by weight of the amount contained in the oxidized concentrate of the parent metal. The amount of rhodium isolated as solid CIRh (CO) (RIS) 2 is 66%. Elemental analysis, IR spectra and 31P NMR confirm that the isolated solid product is indeed chlorocarbonylbis (triphenylphosphine) rhodium, of the indicated formula.
    Examples 2-6. A series of samples of 100 g of the concentrate of the rhodium complex obtained in Example 1 are oxidized with air, as indicated in the table.
    The air treatment used in each case is sufficient to convert almost all of the free phosphine ligand present in the concentrate to the corresponding phosphine oxide.
    These samples of oxidized concentrate weighing 100 g (according to the analysis, each contains 0.81 g of rhodium) are then mixed with 3 mol equiv. Of various concentrated hydrohalic acids per specified amount.
    rhodium, 5 mol-equivalent of free triphenylphosphine ligand per specified amount of rhodium, and 35 ml of N, N-dimethylformamide, after which the reaction solution is refluxed overnight (149-180 ° C), as described in example 1. The number of selected rhodium in the form of solid HalRh (CO) (Phs) 2, the structure of which is confirmed by the data
    PC spectra are listed in the table.
    Example. Another sample of rhodium concentrate of rhodium complex weighing 100 g, prepared according to example 1, is oxidized with air at a temperature of
    120 ° C for 24 hours. This air treatment was sufficient to convert all free phosphine ligand present in the concentrate to the corresponding phosphine oxide.
    Sample 100 of the acidified concentrate (according to the analysis it contains M3.77 g of rhodium) is mixed with 3 mol-equiv of concentrated hydrochloric acid per specified amount of rhodium,
    5 mol equiv. Of free triphenylphosphine ligand, based on the indicated amount of rhodium, ml of N, N-dimethylformamide, and the reaction solution is heated under reflux in
    overnight at 140 ° C, as described in Example 1. The amount of rhodium recovered in the form of solid CIRh (CO) (Ptp) 2 is 69%.
    Example Sample concentrate
    A rhodium complex weighing 100 g, prepared in Example 1, is oxidized with air at 120 ° C for 24 hours. This air treatment was sufficient for the entire free phosphine ligand,
    present in the concentrate, transferred to the corresponding phosphine oxide.
    Then the specified sample of 100 g of the oxidized concentrate (according to the analysis
    contains 0.76 g of rhodium) is mixed with 46.5 ml of diethylamine, 5 mol equiv. of free triphenylphosphine per specified amount of rhodium, and 3 mol equiv. of concentrated hydrochloric acid
    acid, based on the specified amount of rhodium, and the resulting reaction solution is stirred and heated overnight at 90 ° C in an atmosphere of gaseous carbon monoxide to obtain a suspension of the residue
    CIRh (CO) (Ppzb in solution. After cooling to room temperature, this suspension is diluted with 200 ml of methanol and then filtered. The amount of rhodium separated as solid CIRh (CO) (Ph3) 2 (3.69 g) corresponds to 72 ,four%.
    PRI me R 9. The concentrate of the rhodium complex prepared in Example 1, weighing 100 g, is oxidized with air at 120 ° C overnight, and this treatment was sufficient for the entire free phosphine ligand in the specified concentrate to be converted into the corresponding phosphine oxide.
    The indicated 100 g of the oxidized concentrate of the rhodium complex (according to the analysis data, it contains 0.79 g of rhodium) is mixed with 35 ml of N, M-dimethylformamide, 5 mol equiv. Of free triphenylphosphine ligand per specified amount of rhodium and 3 mol-equiv of concentrated hydrochloric acid in a three-necked flask equipped with a thermometer, magnetic stirrer and reflux condenser. The reaction solution is then heated to reflux and boiled overnight (149-180 ° C) with air in order to obtain a suspension of the product CIRh (CO) (Pb3) 2. Then, the suspension is cooled and diluted with 100 ml of ethanol to further desolubilize the precipitate. The diluted suspension (without precipitating it) is heated to boiling point (under reflux) and a solution of 3.2 g of sodium borohydride in 200 ml of ethanol is added for 15 minutes and then the reaction solution is refluxed for another 15 minutes to obtain a precipitate suspension of the desired product HRh (CO) (Ppz) h. After cooling, the yellowish-green solid portion of the indicated desired product HRh (CO) (Fp3) 3 was isolated by filtration, to obtain 366 g of filtrate. The amount of rhodium remaining in the specified filtrate is 0.09 g (11.4% by weight of the rhodium content in the oxidized concentrate, the starting material). The amount of rhodium, isolated in the form of HRh (CO) (Rgf, corresponds to a total yield of 88.6%. Infrared spectrometry.
    IR data confirms that the product obtained is hydrido-carbonyltris (triphenylphosphine) rhodium.
    The proposed method allows the process to be carried out in a homogeneous phase and thereby simplify the process.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for preparing complex rhodium catalysts of the general formula XRh (CO) (PPP) 2, where X is a halogen, by oxidation of a rhodium complex concentrate obtained by concentrating the spent hydroformylation medium to 1-10% by weight of said medium and containing a deactivated soluble complex rhodium hydroformylation catalyst, aldehyde products, high boiling aldehyde condensation products and free triphenylphosphine ligand, followed by treatment of the oxidized concentrate with triphenylphosphine and CO donor water-miscible solvent using hydrohalic acid at elevated temperature, characterized in that, in order to simplify the process, a concentrate is used which is removed from at least 50% by weight of high-boiling condensation products with a boiling point lower than that of free triphenylphosphine ligand of this medium, and at least 50 wt.% of said free triphenylphosphine ligand present in said medium, and at least substantially all aldehyde products, which are oxidized in spirit at 90-175 ° C to until the entire free triphenylphosphine ligand not find a corresponding phosphine oxide as CO and donor solvent is dimethylformamide and the treatment is carried out at 130-190 ° C in the presence of a hydrohalic acid.
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    同族专利:
    公开号 | 公开日
    JPH0132231B2|1989-06-29|
    CA1196005A|1985-10-29|
    DE3261861D1|1985-02-21|
    US4446074A|1984-05-01|
    EP0083094B2|1992-02-05|
    EP0083094A1|1983-07-06|
    EP0083094B1|1985-01-09|
    JPS58116495A|1983-07-11|
    KR840002849A|1984-07-21|
    KR870000645B1|1987-04-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3965192A|1967-05-29|1976-06-22|Union Oil Company Of California|Hydrocarbonylation process|
    US3527809A|1967-08-03|1970-09-08|Union Carbide Corp|Hydroformylation process|
    US3547964A|1968-07-24|1970-12-15|Union Oil Co|Group viii noble metal catalyst recovery|
    US3560539A|1968-08-21|1971-02-02|Union Oil Co|Selective catalyst recovery|
    US3857895A|1969-05-12|1974-12-31|Union Oil Co|Recovery of catalyst complexes|
    US3644446A|1969-07-01|1972-02-22|Union Oil Co|Preparation of rhodium and iridium hydride carbonyl complexes|
    US3859359A|1970-04-27|1975-01-07|Ethyl Corp|Compound and method|
    US3641076A|1970-08-24|1972-02-08|Union Oil Co|Catalyst recovery|
    DE2045416C3|1970-09-15|1979-10-25|Basf Ag, 6700 Ludwigshafen|Process for the elution of rhodium, which is bound as rhodium carbonylate on a basic ion exchanger|
    DE2448005C2|1974-10-09|1983-10-20|Basf Ag, 6700 Ludwigshafen|Process for the regeneration of catalysts containing rhodium or iridium from distillation residues of hydroformylation mixtures|
    DE2614799C2|1976-04-06|1986-02-27|Basf Ag, 6700 Ludwigshafen|Process for the regeneration of rhodium-containing catalysts by treating rhodium-containing distillation residues from hydroformylation mixtures|
    US4221743A|1976-07-07|1980-09-09|Union Carbide Corporation|Hydroformylation process|
    US4201714A|1977-08-19|1980-05-06|Celanese Corporation|Stabilized catalyst complex of rhodium metal, bidentate ligand and monodentate ligand|
    JPS6217596B2|1979-01-08|1987-04-18|Toyo Soda Mfg Co Ltd|
    US4297239A|1979-07-16|1981-10-27|Union Carbide Corporation|Hydroformylation catalyst reactivation|
    US4363764A|1980-12-30|1982-12-14|Union Carbide Corporation|Preparation of rhodium complex compounds|
    JPS5923858B2|1981-01-22|1984-06-05|Mitsubishi Chem Ind|US4594463A|1985-01-28|1986-06-10|Union Carbide Corporation|Synthesis of aldehydes from alcohols|
    US4873213A|1988-08-12|1989-10-10|Puckette Thomas A|Low pressure rhodium catalyzed hydroformylation of olefins|
    JP3349542B2|1993-03-31|2002-11-25|ダイセル化学工業株式会社|Stabilization of rhodium compounds|
    KR0134494B1|1993-10-20|1998-04-20|성재갑|Preparing method of hydridocarbonyltris- rhodium|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/334,198|US4446074A|1981-12-24|1981-12-24|Preparation of rhodium complex compounds|
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