• 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:
    An improved rhodium catalyzed liquid recycle hydroformylation process, the improvement which comprises selectively separating and recovering phosphorus ligand from the vaporized aldehyde product stream obtained after volatilizing and separating the aldehyde product from the catalyst containing reaction product solution of the hydroformylation process.
    公开号:SU1436867A3
    申请号:SU853876801
    申请日:1985-03-29
    公开日:1988-11-07
    发明作者:Альваро Блессинг Майкл；Джозеф Дембовски Грегори；Кейт Финнелл Грегори
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for producing aldehydes Cj - C.
    The purpose of the invention is to increase the recovery of phosphorus ligand.
    Examples 1-6. A series of computational (computerized) studies were carried out, including various vapor streams containing 97.7% propionoldehyde, 0.5 wt.% Higher boiling aldehyde condensation products and various amounts (ppm) of various phosphorus ligands, the rest is impurities, namely, unreacted olefin, alkane, hydrogen and carbon monoxide; these streams are in contact at their dew point with dispersed liquid propionaldehyde (40 ° C) from the spray nozzle at different hourly quantitative rates of liquid th propionaldehyde vaporized aldehyde product at a flow rate of 409 kg 512 The calculated relative volatility of higher boiling aldehyde condensation obochnyh n products to an active phosphorus ligand as well as the weight amount vtchis- fief phosphorus ligand contained in said vapor stream as compared to the calculated weight an amount of higher boiling condensation by-product of the aldehyde contained in the said stream, which can be separated and removed from the vapor stream Nogo aldehyde product are shown in Table. one.
    Examples 7-10. A computerized (computational) research series was carried out, including various vapor flows containing 87.6 wt.% Butyraldehyde, 0.3 wt.% Higher boiling by-products. condensation of the aldehyde and various amounts (ppm) of various phosphorus ligands, the rest being impurities, namely unreacted olefin, alkane, hydrogen and carbon monoxide, indicated
    At their dew point, the streams are in contact with liquid butyraldehyde (40 ° C) dispersed from a spray nozzle at various hourly quantitative speeds of liquid butyraldehyde at a flow rate of vaporous aldehyde product 409 kg 512 g. The calculated relative volatility of higher-boiling secondary products
    o 5 0 5 0 s
    Q with
    0
    five
    the tone of aldehyde condensation to the included phosphorus ligand, as well as the calculated amounts of phosphorus ligand containing in the indicated stream, compared with the calculated amount of higher boiling aldehyde condensation by-products contained in the said vapor stream, which can be separated and extracted from the vaporous aldehyde product are given in table. 2,
    Examples 11-16. A series of computerized (calculated) studies involving various vapor flows containing 91.8% by weight of valeraldehyde, 0.5% by weight of higher-boiling condensation by-products and various amounts (ppm) of various phosphorus ligands, the remainder consists of impurities, namely unreacted olefin, alkane, hydrogen and carbon monoxide, these streams are in contact at their dew points with dispersed liquid valeralgide () dispersed from a heating nozzle at a flow rate of 409 kg 512 h of vapor flow Foot of the aldehyde product. The calculated relative volatility of the higher boiling point aldehyde condensation by-products to the phosphorus ligand, also includes the calculated amount (wt.%) Of the phosphorus ligand contained in the said vapor stream, compared to the calculated weight amount (wt.%) Of the higher boiling aldehyde condensation The content in the specified stream, which can be separated and extracted from the vaporized aldehyde product stream, is given in Table. 3
    Example 17. A continuous process of hydroformylation with liquid recycling is carried out for three days in which butene-1-hydro is formulated with a Cj -aldehyde using carbon monoxide and hydrogen in the presence of a rhodium complex catalyst, free cyclohexyl diphenylphosphine ligand and more high-boiling aldehyde condensation by-products. The liquid catalyst, a compound JJIX solution of the reaction product S-aldehyde, after removal from the reactor of hydroformylation, is evaporated to obtain a vaporous aldehyde C product containing 91.8 wt.% C. - an aldehyde mixture of valeraldehyde and 2-methyl butyraldehyde, 0.35.55%, aldehyde mixture from valeraldehyde and 2-methylbutyraldehyde, 0.35.55 .% of the higher boiling by-product condensation products of Cr -aldehyde and 100 pp of cyclohexyl-diphenylphosphine ligand, which is freed in the separator from residues of nonvolatile liquid catalyst containing the reaction solution. Said reaction solution is recycled back to the hydroformylation reactor. The relative volatility of the higher boiling point side condensation products of C 5 -aldehyde to the cyclohexyl diphenylphosphine ligand in this solution was
    6867
    the hydrated product, leaving 1 schy from the gas-liquid separator, then condense i: liquid for
    recovery sfogo With.-aldehyde product. Analysis of various samples of the Cj-aldehyde product shows that it contains about 26 ppm (wt.%) Cyclohexyldiphenylphosphine and about 0.23–0.33 wt.% More aldehyde condensation by-products. This analysis shows that the calculated 74% cyclohexyl biphenyphosphine ligand
    and about 6–34% of the higher boiling point aldehyde condensation by-products contained in the vaporized C 5 -aldehyde product, free from liquid catalyst
    the specified stream vaporous With - aldehyde product.
    During the process, approximately 18 hydrophoresses are carried out. The said steam-2o Pa stream containing the solution of the reaction-shaped C-aldehyde product is separated and removed from the stream into the pipeline, in which a certain amount of the finished purified (condensed and distilled) is sprayed through the spray nozzle - 25 milings with spraying of liquid liquid C, j-aldehyde product C-aldehyde product, stopping, withdrawn from the process of hydroformylation, countercurrent to the flow of a vaporous C 5 -alvdehyde product At a speed of about 10 kg of 647 g / h of liquid Cj-aldehyde supply of liquid, the crude aldehyde product contains about 100 ppm cyclohext-schiphenylphosphine and about Oj35 wt.% more than the BENCH of condensation products of aldehyde C.
    With a J-algo product for a flow rate of the vapor aldehyde product 409 kg 512 g / h.
    Liquid droplets of the C-aldehyde product evaporate, cooling the flow of the vaporous Cj-aldehyde product below its dew point to form droplets of cyclohexyl diphenylphosphine ligand and a higher boiling point of condensation by-products of the dehydrogen product. The vapors containing these condensed droplets are fed to a gas-liquid separator, in which the steam is first passed through a separator with a reflective impeller, and then a moisture separator with a filter to release the vaporized C stream from the aldehyde product from the condensed liquid, the droplets of which are collected below. the specified gas-liquid separator and recycle through the pipeline to the initial separator, in which the evaporated C, -aldehyde product is freed from a non-volatile liquid catalyst containing solution of the reactive product. Released stream C 5 -alderized stream of vaporous C-aldehyde product.
    During the process, the hydrophore containing the solution of the reaction product is isolated and removed from the milling with spraying of the liquid C-aldehyde product, stopping
    The ra containing the solution of the reaction product is isolated and removed from the spraying with the spraying of the liquid C-aldehyde product, stopping
    the liquid feed, the crude aldehyde product contains about 100 ppm cyclohext-shdiphenylphosphine and about Oj35 wt.% more EYKO-BINDING by-products of aldehyde C condensation.
    Thus, the proposed method allows you to extract the ligand by 99%, which is significantly higher than in the known method.
    权利要求:
    Claims (2)
    [1]
    1. A process for preparing aldehydes C3 - Cf by gndroformilirovani olefiiov C-2 - C 4 of carbon monoxide and hydrogen in the presence of dissolved rodiyfosfornogo complex catalyst, free phosphorus ligand and higher boiling aldehyde condensation by-products to give the aldehyde product, followed by separating and recovering the aldehyde product from an aldehyde product of a dissolved rhodium-phosphorus complex catalyst, free phosphorus ligand and high-boiling by-products of ald condensation The guide, which is removed from the process of hydration |) ormilirovana - or by evaporation of the aldehyde product to obtain a stream of vaporous aldehyde product.
    the vaporized phosphorus ligand and the vaporized higher boiling point condensation by-products of the aldehyde, which are sent to a separator to separate the baking solution of the reaction product containing the catalyst, which is recycled from the lower
    -24.571: 409, 512, respectively, with the condensation of the evaporated phosphoric ligand and the evaporated higher boiling point by-products of aldehyde condensation contained in the vaporous aldehyde product stream, so that the mass ratio
    parts of the separator to the hydrophore-Q condensed phosphorus ligand and milirovanie stage, differing in condensed higher boiling from the by-products of aldehyde condensation, changed from 1.3-440: 1, followed by a decrease in condensation, which, in order to increase the degree of phosphorus ligand recovery The vaporized aldehyde product stream is reacted with a dispersing 15 condensed phosphorus ligand and an aldehyde in the form of droplets condensed by higher aldehyde condensation products.
    [2]
    2. The method according to p. 1, I distinguish
    boiling point lower than the boiling point of high boiling point byproducts, with mass
    that phosphorus lishch and and with
    The 1 g ratio of vaporous-20 flow is triphenylphosphine or the aldehyde product to the dispersion cyclohexyldiphenylphosphine.
    the vaporous aldehyde product) the relative volatility of the by-products of conditiousness to the use of convalescence; Prilidifeks osfin (100 pp;); cyclohexyldifekaphosphon (50 pp); triphenylphosphine (30 ppm).
    -24.571: 409, 512, respectively, with the condensation of the evaporated phosphoric ligand and the evaporated higher boiling point by-products of aldehyde condensation contained in the vaporous aldehyde product stream, so that the mass ratio
    -440: 1, followed by the attraction of condensed phosphorus ligand and condensed higher boiling aldehyde condensation products. 2. The method according to p. 1, I distinguish
    the fact that the phosphorus table 1
    Notes. - kg / h of the liquid used, the flow rate of 409 kg 512 g
    evaporated aldehyde product; - relative volatility of side. products of allegide condensation of the used league 11 DU - .. PDPP - procpdiphenylphosphine (t2S.) f TP - triphenylphosphine (50 ppm) -, h
    yechani - kg / h liquid used for vapor flow
    aldehyde product at a rate of 409 kg 512 g; - relative volatility of cocdenswini by-products
    aldegna to used, to the Yuma phosphoric ligand; PDPP - propyl diphenylphosphine C150 ppm) CHDPP - cyclohexyl diphenylphosphine (100 ppm); TPP - triphenylphosphine (80 phr).
    t a b l i a a
    Table
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    同族专利:
    公开号 | 公开日
    KR890003784B1|1989-10-04|
    IN163936B|1988-12-10|
    EP0157755B1|1987-10-28|
    HUT42046A|1987-06-29|
    AU4047085A|1985-10-03|
    RO91100A|1987-03-30|
    KR850007053A|1985-10-30|
    ES541724A0|1985-12-01|
    CA1259331A|1989-09-12|
    FI84258B|1991-07-31|
    FI851287A0|1985-03-29|
    HU199382B|1990-02-28|
    AT30411T|1987-11-15|
    NO162960B|1989-12-04|
    ZA852419B|1985-11-27|
    ES8602579A1|1985-12-01|
    BR8501434A|1985-11-26|
    CS232385A3|1992-06-17|
    FI84258C|1991-11-11|
    JPS60218350A|1985-11-01|
    PL143746B1|1988-03-31|
    AU579855B2|1988-12-15|
    DK145085D0|1985-03-29|
    JPS6346056B2|1988-09-13|
    MX163335A|1992-04-22|
    PL252661A1|1985-11-19|
    DE3560823D1|1987-12-03|
    CS276451B6|1992-06-17|
    YU44060B|1990-02-28|
    EP0157755A1|1985-10-09|
    FI851287L|1985-10-01|
    NO851286L|1985-10-01|
    DK145085A|1985-10-01|
    YU51585A|1987-10-31|
    SG22789G|1990-10-26|
    NO162960C|1990-03-14|
    RO91100B|1987-04-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB2074166B|1980-04-16|1984-02-29|Union Carbide Corp|Process for removing triorgano phosphine from an organic liquid|
    CA1202326A|1982-06-18|1986-03-25|Donald L. Bunning|Refining of crude aldehyde product|US4599206A|1984-02-17|1986-07-08|Union Carbide Corporation|Transition metal complex catalyzed reactions|
    DE3625261A1|1986-07-25|1988-02-04|Basf Ag|METHOD FOR CONTINUOUS HYDROFORMYLATION OF OLEFINICALLY UNSATURATED COMPOUNDS|
    DE3640615A1|1986-11-27|1988-06-09|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|
    US5001274A|1989-06-23|1991-03-19|Union Carbide Chemicals And Plastics Company Inc.|Hydroformylation process|
    JP2893902B2|1989-10-19|1999-05-24|三菱化学株式会社|Hydroformylation of olefins|
    US7667079B2|2005-04-21|2010-02-23|Oxea Corporation|Processes for recovery of a triarylphosphine from a group VIII metal catalyst complex mixture|
    JP2013515061A|2009-12-22|2013-05-02|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|Control of normal: isoaldehyde ratio in mixed ligand hydroformylation process|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US59540884A| true| 1984-03-30|1984-03-30|
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