• 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:
    1. A process for separating and recovering rhodium used as a catalyst without a complexing agent by extraction from an organic solution of the products of the Oxo synthesis with an aqueous solution of organic phosphines having the general formula see diagramm : EP0156253,P10,F2 as complexing reagents, where Ar**1 , Ar**2 and Ar**3 each denote a phenyl or naphthyl group, Y**1 , Y**2 and Y**3 each stand for a straight-chain or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen atom, the OH, CN, NO2 - or R**1 R**2 N group, R**1 and R**2 each standing for a straight-chain or branched alkyl group having 1 to 4 carbon atoms, X**1 , X**2 and X**3 are each a sulfonate (SO3 **- ) and/or a carboxylate (COO**- ) radical, m1 , m2 and m3 are the same or different integers from 1 to 3 and at least one number m1 , m2 or m3 is equal to or greater than 1, n1 , n2 and n3 are the same or different integers from 0 to 5 and alkali metal, alkaline earth metal, zinc, ammonium or quaternary ammonium ions of the general formula N(R**3 R**4 R**5 R**6 )**+ , R**3 , R**4 , R**5 , R**6 each denoting a straight-chain or branched alkyl group having 1 to 4 carbon atoms are contained in the sulfonates and carboxylates, characterised in that a solubiliser is added to the aqueous solution of the complexing agent.
    公开号:SU1333232A3
    申请号:SU853864247
    申请日:1985-03-15
    公开日:1987-08-23
    发明作者:Корнильс Бой；Конколь Вернер；Барманн Гельмут；Бах Гансвильгельм；Вибус Эрнст
    申请人:Рурхеми Аг (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to an improved method for recovering rhodium from a crude product of oxosynthesis.
    The purpose of the invention is to simplify the process.
    EXAMPLE 1 In a flask with a stirrer, 200 g of crude α-isooctyl aldehyde containing,%: hydrocarbons C (at a ratio of 1: 1) to saturate the mixture with carbon monoxide and hydrogen. The mass ratio of the aqueous solution: the product of oxosynthesis is 0.4: 1. Intensively stirred at 80 ° C. The stirring time and the subsequent quiescent time is 20 seconds. The aqueous phase is withdrawn through the bottom descent and the organic phase.
    15
    20
    substantially heptenes) 34.9; i-octypus is re-treated with 100 g of uca-aldehyde 62.7; isooctyl alcohol 2,2} high-boiling point substances 0.2 rhodium, 3.9 h / min, 20 g of a 0.1% aqueous solution of sodium triphenylphosphine trisulfonate (TFFTS) sodium containing O, 1 g of methyl trimethylammonium metasulfonate . The mass ratio of the aqueous solution: the product of oxosynthesis is 0.1: 1. The molar ratio of phosphorus to rhodium is 5. Both phases are vigorously stirred for 5 minutes at 50 ° C. At the end of the stirring, both phases are separated for 12 minutes without forming an emulsion. The crude oxoxy synthesis product contains 0.6 ppm of rhodium, which corresponds to a recovery rate of 85%.
    PRI mme R 2. The process is carried out as in Example 1, but using a 0.4% sodium TFPTS solution containing 0 g of dodecyl trimethyl ammonium sulphate. The mass ratio of water solution: the product of oxosynthesis is 0.1: 1. The molar ratio of phosphorus to rhodium is 20. In the organic phase, 0.6 ppm of rhodium remains, which corresponds to a recovery rate of 85%. EXAMPLE 3 The process is carried out as in Example 2, but using a 0.4% sodium TFPTS solution containing 0.1 g of pyridinium sulfate, the phases being stirred at. The mass ratio of the aqueous solution: the product of oxosynthesis is 0.1: 1. Phase separation is carried out for 9 seconds. In the raw product, 0.5 ppm of rhodium remains, which corresponds to a rhodi recovery rate of 87%.
    Example 4. In a round-bottomed column equipped with a gas descent and an inlet capillary and a stirrer, 1000 g of isooctyl aldehyde of composition indicated in example 1 are extracted with 100 g of 20% aqueous solution of sodium TFPTS containing 2% benzyl trimethylammonium sulfate. The molar ratio of phosphorus to rhodium is 37. Synthesis gas (CO / H in the
    bath solution TFPTS sodium. Extracted four times. The organic phase contains 0.3 ppm of rhodium, which corresponds to a rhodi recovery rate of 92%.
    Example5. In the apparatus specified in Example 4, 1000 g of crude propionaldehyde containing,%: propionaldehyde 96.3; n-propanol 0.2, ethylene + ethane 1.4 high boiling point substances 2.1; Rhodium, 9.6 ppm, is subjected to 5-fold extraction at 86 ° C using 100 g of 20% sodium TFTS solution at each stage, containing 2% cetyl trimethylammonium acetate. The molar ratio of phosphorus to rhodium is 18. The mass ratio of aqueous solution: the product of ocosynthesis is 0.5: 1. After the fifth
    30 extraction, the content of rhodium in the organic phase is 0.2 ppm, which corresponds to a recovery rate of rhodium and 97%.
     And p and mep 6. 450 g residue from
    The Tg of hydroformylation of the mixture of α-olefins with a rhodium content of 17 h / ml at 100 ° C is extracted in an autoclave with a 20% solution of TFPTS containing 2.5% lactate of tetradecyl trimethyl ammonium. The molar ratio of phosphorus is. To about 23. The mass ratio is the aqueous solution: the product of oxosynthesis is 0.5: 1. After cooling and phase separation, the content of rhodium in the organic phase is 0.2 ppm, which corresponds to a recovery rate of rhodium of 99%.
    Pr im. p 7. In a flask with a stirrer, to 200 g of crude isononyl aldehyde containing,%: isononyl aldehyde 71.0; diisobutylene 22.0; isononyl alcohol 2.0j isooctane 4.0; high boiling point 1.0; rhodium 3.9 ppm Adding 20 grams of a 0.8% aqueous solution
    55 sodium TFFTS containing 0.5 g cetid trimethylammonium meta sulfonate. The mass ratio of the aqueous solution: the product of oxosynthesis is 0.11: 1. Mole ratio of fq scopa to rhodium
    50
    1: 1 ratio to saturate the mixture with carbon monoxide and hydrogen. The mass ratio of the aqueous solution: the product of oxosynthesis is 0.4: 1. Intensively stirred at 80 ° C. The stirring time and the subsequent quiescent time is 20 seconds. The aqueous phase is withdrawn through the bottom descent and the organic phase.
    zoo re-process 100 g
    bath solution TFPTS sodium. Extracted four times. The organic phase contains 0.3 ppm of rhodium, which corresponds to a rhodi recovery rate of 92%.
    Example5. In the apparatus specified in Example 4, 1000 g of crude propionaldehyde containing,%: propionaldehyde 96.3; n-propanol 0.2, ethylene + ethane 1.4 high boiling point substances 2.1; Rhodium, 9.6 ppm, is subjected to 5-fold extraction at 86 ° C using 100 g of a 20% sodium TFPTS solution at each stage containing 2% cetyltrimethylammonium acetate. The molar ratio of phosphorus to rhodium is 18. The mass ratio of aqueous solution: the product of oxosynthesis is 0.5: 1. After the fifth
    extraction, the rhodium content in the organic phase is 0.2 ppm, which corresponds to a rhodi recovery rate of 97%.
     And p and mep 6. 450 g residue from
    hydroformylation of a mixture of o-olefins with a rhodium content of 17 ppm at 100 ° C is extracted in an autoclave with a 20% TFPTS solution containing 2.5% tetradecyl trimethyl ammonium lactate. The molar ratio of phosphorus to rhodium is 23. The mass ratio of aqueous solution: the product of oxosynthesis is 0.5: 1. After cooling and phase separation, the content of rhodium in the organic phase is 0.2 ppm, which corresponds to a recovery rate of 99% rhodium.
    Pr im. p 7. In a flask with a stirrer to 200 g of crude isononyl aldehyde, containing,%: isononyl aldehyde 71.0; diisobutylene 22.0; isononyl alcohol 2.0j isooctane 4.0; high boiling point 1.0; rhodium 3.9 ppm Add 20 g of a 0.8% aqueous solution.
    Sodium TFPT containing 0.5 g cetidryl methylammonium meta-sulfonate. The mass ratio of the aqueous solution: the product of oxosynthesis is 0.11: 1. Molar ratio of fqcfopa to rhodium
    313
    40. Both phases are intensively stirred for 5 min at. At the end of the stirring, both phases are separated within 12 minutes without forming an emulsion. The crude oxoxy synthesis product phase contains 0.2 ppm of rhodium, which corresponds to a recovery rate of 94.9%.
    The proposed method allows to achieve rhodi recovery rates of 99% and to carry out the process with a low rhodium content (0.00039%) in the initial product as compared with the rhodium content in the original product according to the known method (wt.%). In this connection, there is no need to concentrate the solution containing rhodium, which greatly simplifies the process technology.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of regeneration of rhodium from the final product of oxosynthesis by extraction with an aqueous solution; containing reagent and nitrogen-containing organic compound, at 50-100 ° C, With the subsequent separation of the organic and aqueous phases.

    differing in that
    Editor P.Geershi
    Compiled by R. Margolin
    Tehred L. Serdyukova Proofreader L. Pilipenko
    Order 3853/58 Circulation 371 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    In order to simplify the process, the sodium salt of triphenylphosphine sodium sulfonic acid is used as a reagent, the content of which in aqueous solution is 0, 1–20 wt.% and the process is carried out at a molar ratio of phosphorus to rhodium equal to (5–40): 1, and As a nitrogen-containing organic compound, a compound of the general formula is used.
    /,
    Rtt

    Where
    R (-. R,
    C, -C alkyl or benzip
    R is each methyl or together with the nitrogen atom form a pyridine ring5 R, is sulfate, acetate, metasulfate or lactate,
    the content of which in an aqueous solution is 0.2-2.5 wt.%, and the process is carried out at a mass ratio of aqueous solution: product of oxosynthesis,
    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    HU198214B|1989-08-28|
    JPH0356095B2|1991-08-27|
    EP0156253A2|1985-10-02|
    DE3579018D1|1990-09-13|
    CS189885A2|1991-02-12|
    RO90827B|1987-01-31|
    EP0156253A3|1987-10-21|
    ES8608529A1|1986-08-01|
    AU4035185A|1985-10-03|
    CS274653B2|1991-09-15|
    KR850006995A|1985-10-30|
    ES540668A0|1986-08-01|
    AT55280T|1990-08-15|
    BR8501338A|1985-11-19|
    KR890002153B1|1989-06-21|
    HUT39704A|1986-10-29|
    AU566540B2|1987-10-22|
    JPS60212233A|1985-10-24|
    DE3411034C2|1992-08-06|
    RO90827A|1987-01-30|
    PL252444A1|1986-02-25|
    ZA852052B|1985-11-27|
    DE3411034A1|1985-09-26|
    PL149283B1|1990-01-31|
    EP0156253B1|1990-08-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4248802A|1975-06-20|1981-02-03|Rhone-Poulenc Industries|Catalytic hydroformylation of olefins|
    US4292196A|1979-12-10|1981-09-29|Uop Inc.|Catalyst recovery|
    GB2085874B|1980-09-04|1984-08-08|Johnson Matthey Plc|Hydroformylation of olefins|DE3443474A1|1984-11-29|1986-05-28|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR RECOVERY OF RHODIUM FROM REACTION PRODUCTS OF THE OXOSYNTHESIS|
    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|
    DE3822037A1|1988-06-30|1990-01-04|Hoechst Ag|METHOD FOR SEPARATING AND RECOVERING RHODIUM FROM OXOSYNTHESIS PRODUCTS|
    US4935550A|1988-08-12|1990-06-19|Union Carbide Chemicals And Plastics Company Inc.|Catalytic metal recovery from non-polar organic solutions|
    US5114473A|1988-08-25|1992-05-19|Union Carbide Chemicals And Plastics Technology Corporation|Transition metal recovery|
    DE3903909A1|1989-02-10|1990-08-16|Hoechst Ag|METHOD FOR REMOVING METALLIC CORROSION PRODUCTS FROM A POLLUTED CATALYST SOLUTION RESULTING FROM CARBONYLATING METHANOL AND / OR METHYL ACETATE AND / OR DIMETHYL ETHER|
    US5099047A|1989-11-17|1992-03-24|Mitsubishi Kasei Corporation|Method for recovering a group viii metal solid complex and hydroformylation method|
    DE4135049A1|1991-10-24|1993-05-06|Hoechst Ag, 6230 Frankfurt, De|METHOD FOR THE RECOVERY OF RHODIUM FROM THE REACTION PRODUCTS OF THE OXOSYNTHESIS|
    DE4427428A1|1994-08-03|1996-02-29|Basf Ag|Process for the preparation of aldehydes|
    DE19940249A1|1999-08-25|2001-03-01|Celanese Chem Europe Gmbh|Process for the preparation of aldehydes|
    DE19940250B4|1999-08-25|2005-06-16|Celanese Chemicals Europe Gmbh|Process for the regeneration of used water-soluble hydroformylation catalysts|
    DE10005084C1|2000-02-04|2001-09-13|Celanese Chem Europe Gmbh|Recovery of rhodium from rhodium complexes, for reuse as a hydroformylation catalyst, comprises extraction with a phosphate or phosphonate, oxidization and treatment with an arylphosphine.|
    FR2813305B1|2000-08-23|2004-02-13|Inst Francais Du Petrole|IMPROVED HYDROFORMYLATION PROCESS USING A COBALT AND / OR RHODIUM-BASED CATALYST IN A NON-AQUEOUS IONIC SOLVENT|
    FR2838431B1|2002-04-11|2005-05-06|Inst Francais Du Petrole|HYDROFORMYLATION PROCESS USING COBALT CATALYST IN NON-AQUEOUS IONIC LIQUID WITH ENHANCED CATALYST RECYCLING|
    CN102336638A|2011-07-20|2012-02-01|南京荣欣化工有限公司|Technical method for producing propyl aldehyde through hydroformylation of ethylene|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19843411034|DE3411034C2|1984-03-26|1984-03-26|
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