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WO2010057582A1 - Procédé pour la récupération du rhodium à partir de solutions aqueuses contenant des composés complexes du rhodium - Google Patents

Procédé pour la récupération du rhodium à partir de solutions aqueuses contenant des composés complexes du rhodium Download PDF

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Publication number
WO2010057582A1
WO2010057582A1 PCT/EP2009/007955 EP2009007955W WO2010057582A1 WO 2010057582 A1 WO2010057582 A1 WO 2010057582A1 EP 2009007955 W EP2009007955 W EP 2009007955W WO 2010057582 A1 WO2010057582 A1 WO 2010057582A1
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WO
WIPO (PCT)
Prior art keywords
rhodium
ion exchange
aqueous
exchange resin
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2009/007955
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German (de)
English (en)
Inventor
Wolfgang Greb
Thomas Klein
Rainer Lukas
Klaus Schmid
Wolfgang Zgorzelski
Andreas Fischbach
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Oxea GmbH
Original Assignee
OQ Chemicals GmbH
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Filing date
Publication date
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Priority to EP09756670A priority Critical patent/EP2358471B1/fr
Publication of WO2010057582A1 publication Critical patent/WO2010057582A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
    • B01J2531/985—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases in a water / organic solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
    • B01J2540/12—Carboxylic acid groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/30—Non-coordinating groups comprising sulfur
    • B01J2540/32—Sulfonic acid groups or their salts

Definitions

  • the present invention relates to a process for the recovery of rhodium from rhodium complex-containing aqueous solutions.
  • the rhodium complex compounds, together with excess complex ligands used used, inter alia, a catalyst system which - as described in DE-PS 26 27 354 - for the hydroformylation of olefins is used.
  • the catalyst system is formed under reaction conditions from rhodium and a water-soluble organic phosphine, which is used in excess. Its water solubility is due to the presence of sulfonic acid groups present in the organic phosphine.
  • the phosphorus ligand is preferably used as alkali, ammonium or alkaline earth sulfonate.
  • catalyst poisons such as iron carbonyl
  • phosphine sulfides are also formed by the reduction of sulfonic acid groups.
  • EP 0 255 673 A2 deals with a process for recovering rhodium from rhodium complex-containing aqueous solutions which are used as the catalyst phase in the hydroformylation of olefins and which, after prolonged use, no longer exhibit satisfactory selectivity and productivity in the hydroformylation reaction.
  • This solution containing aqueous rhodium complex compounds is first mixed with the salt of a carboxylic acid in excess, based on rhodium, and then treated with an oxidizing agent.
  • an oxidizing agent Depending g-atom rhodium 20 to 500 and in particular 40 to 300 mol of carboxylic acid salt are added to the aqueous solution.
  • water-insoluble rhodium compounds are formed, which precipitate as an oily layer from the aqueous phase.
  • the deposited rhodium compounds are then removed, if appropriate after addition of an organic, water-immiscible solvent, by simple phase separation.
  • EP 0 255 673 A2 A further development of the rhodium recovery process known from EP 0 255 673 A2 is described in EP 0 367 957 A2. After this procedure, the oxidation step is carried out with hydrogen peroxide in combination with oxygen.
  • the rhodium recovery rate is 94 to 98% of the original rhodium present.
  • the residual rhodium remains in the aqueous solution and the prior art mentions only that this amount of rhodium can be recovered separately, without going into the recovery method for this residual amount.
  • the recovery of rhodium from the rhodium-containing streams obtained in the hydroformylation reaction or oxo synthesis by means of ion exchange resins is known in the art.
  • the hydroformylation reaction is carried out in a homogeneous, organic liquid which comprises the dissolved rhodium-phosphine catalyst and excess phosphine and also gangsolefin and reaction products formed carried out.
  • the rhodium-containing material stream obtained after aldehyde separation is concentrated, subjected to an oxidative treatment and then treated in a further reaction zone with a mixture of hydrogen and carbon monoxide in the presence of triphenylphosphine. Finally, the pretreated solution is added to an acidic ion exchange resin. For the binding of rhodium on the ion exchange resin, those having sulfonic acid groups in the protonated form have been proven.
  • the loaded ion exchange resin is treated with olefin to be reacted dissolved in a suitable organic solvent and a mixture of carbon monoxide and hydrogen.
  • the rhodium-containing, eluted liquid is then returned to the hydroformylation reactor.
  • WO 02/20451 A1 Another process for the recovery of rhodium from product streams obtained in the hydroformylation of olefins in a homogeneous organic phase is known from WO 02/20451 A1.
  • the reaction is carried out with a homogeneously dissolved, preferably not ligand-modified rhodium complex as a catalyst.
  • Rhodium is bound from the resulting streams to a basic ion exchange resin containing nitrogen-containing residues as anchor groups.
  • the ion exchange resin is burned and rhodium is removed from the ash residues.
  • the recovery of rhodium from the organic product streams of the oxo reaction takes place by means of basic ion exchange resins.
  • the non-ligand-modified rhodium carbonylate homogeneously dissolved in the organic medium is bound to a basic ion exchange resin.
  • the loaded resin is treated with a mixture of lower alkanols, water and water-soluble aliphatic amines in the presence of molecular acid. treated.
  • the rhodium-containing eluate is evaporated and rhodium worked up to a form suitable for the oxo reaction.
  • an aqueous, rhodium-containing solution can be treated with a basic or acidic ion exchange resin in order to bind rhodium.
  • the known method first requires to modify the ion exchange resin with an ionic organophosphorus compound, for example with triphenylphosphine monosulfonic acid.
  • an organophosphorus compound for example triphenylphosphine
  • rhodium can be eluted from the modified ion exchange resin.
  • the aqueous solution likewise contains a comparatively high salt concentration of sulfonated phosphine oxides which form during the oxidation step through the decomposition of the rhodium-phosphine complex and through the oxidation of the excess sulfonated phosphines.
  • a water-soluble salt of an excess of carboxylic acid is added with respect to rhodium. According to the teaching of EP 0 255 673 A2, however, excessively high salt concentrations make rhodium recovery more difficult.
  • the invention therefore consists in a process for recovering rhodium from rhodium complex-containing aqueous solutions which are used as catalyst phase in the hydroformylation of olefins, in which the aqueous catalyst solution is treated with an oxidizing agent and separated as rhodium separated in water insoluble compound. It is characterized in that the aqueous solution obtained after separation of the deposited rhodium compound is treated with an ion exchange resin.
  • the residual amounts of rhodium present in the aqueous solution can be effectively precipitated on the ion exchange resin by treatment with an ion exchange resin.
  • the treatment is generally carried out at normal pressure, although the use of higher pressures, for example up to 0.5 MPa is also possible.
  • no special precautions have to be taken, such as working under synthesis gas or additional, targeted modification of the ion exchange resins with complexing agents that bind the rhodium.
  • the aqueous solution containing residual amounts of rhodium is applied to the air under air given commercially available ion exchange resin.
  • the ion exchange resin can be brought into contact with the rhodium-containing solution at any temperature.
  • temperatures below room temperature one must expect relatively long contact times in order to achieve sufficient rhodium deposition. If one chooses too high temperatures, damage to the ion exchange resin is to be feared because of its limited temperature stability.
  • ion exchange resins basic, acidic or functionalized ion exchange resins available as commercial products can be used.
  • the basic ion exchange resins include those containing primary, secondary, tertiary or quaternary amino groups. Particular importance has been given to polystyrene-based ion exchange resins containing tertiary amino groups or quaternary amino groups in the base form.
  • Examples of weakly to strongly basic ion exchange resins are Amberlit IR 45 or Dowex 4. Macroreticular types such as Amberlyst A21, Lewatit MP62, Lewatit MP64, Imac A20, Zerolite G, Amberlite IRA93 or Amberlyst A26 have particular technical significance.
  • Weak or strong acidic ion exchange resins include, for example, the carboxylate or sulfonic acid groups attached to a polymer matrix based on styrene-divinylbenzene copolymers.
  • the carboxylate group can be derived, for example, from aromatic carboxylic acids or aliphatic carboxylic acids and the sulfonic acid group from aromatic or aliphatic sulfonic acids.
  • a strongly acid ion exchange resin is, for example, Amberlyst 15 or Amberlyst DPT-1.
  • Such functionalized ion exchange resins are based on a polymer backbone, for example on crosslinked polystyrene, to which are bonded groups which have no pronounced acid / base properties but which have the complexing character, for example thiourea, benzylamine, imidazole, thiol , Mercaptophenylamino, aminoethylamino, aminoalkyl, mercaptoalkyl, alkylthiourea or polyamine groups.
  • Ion exchange resins having thiourea and alkylthiourea groups with C1 to C5-alkyl radicals have proved particularly suitable.
  • Such resins are commercially available, for example, under the name Lewatit Monoplus.
  • the solutions fed to the rhodium recovery process are from the oxidative workup of an aqueous solution used as the catalyst phase in the hydroformylation of olefins.
  • Working with an aqueous catalyst solution containing dissolved rhodium complex compounds and complex ligands used in excess is known for example from DE 26 27 354 C1 and this process is also referred to as a two-phase or heterogeneous hydroformylation.
  • the aqueous catalyst solution no longer exhibits satisfactory selectivity in the hydroformylation reaction. It is discharged from the process and contained rhodium is recovered, for example after an oxidative digestion, according to EP 0 255 673 A2 or EP 0 367 957 A2.
  • an aqueous solution which still contains dissolved rhodium in a residual concentration of usually from 2 to 10 ppm.
  • the residual concentration of dissolved rhodium can vary over a wide range, because of oxidative digestion of the used aqueous catalyst solution does not always give the optimal results and therefore remain fluctuating residual amounts of rhodium in the aqueous solution.
  • the aqueous solution obtained after the oxidative digestion has a comparatively high salt concentration, usually in a range from 5 to 30% by weight, calculated as dry substance and based on the aqueous solution.
  • the solid consists essentially of water-soluble carboxylic acid salts, which are added during the oxidative treatment of the used, aqueous catalyst solution generally in an amount of 20 to 500, in particular 40 to 300 mol per g-atom of rhodium, from the water-soluble complex ligand and from its water-soluble , decomposition and conversion products formed during the hydroformylation reaction, for example, phosphine sulfides, and phosphine oxides formed due to the oxidative treatment.
  • the water-soluble complex ligands are in particular phosphines of the formula
  • Ar 1 , Ar 2 and Ar 3 are each a phenyl or naphthyl group
  • Y 1 , Y 2 , Y 3 are each a straight-chain or branched alkyl group having 1 to 4 C atoms, an alkoxy group, a halogen atom, an OH CN, NO 2 or R 1 R 2 N group in which R 1 and R 2 are each a straight-chain or branched alkyl group having 1 to 4 C atoms
  • X 1 , X 2 , X 3 each represents a carboxylate (COO ' ) and / or sulfonate (SO 3 -) radical
  • ni, n 2 , n 3 are identical or different integers from 0 to 5
  • M represents an alkali metal ion, the equivalent of an alkaline earth metal or zinc ion, or an ammonium or quaternary alkyl ammonium ion of the general formula N (R 3 R 4 R 5 R 6
  • organic compounds in small amounts are also present in the aqueous solution obtained after the oxidative digestion, for example higher-boiling products such as aldols, condensation products and, if appropriate, solubilizers, if added to the aqueous catalyst solution in order to prevent the transition of the organic compounds in the hydroformylation reaction To favor reactants in the catalyst solution and the water-soluble catalyst system in the organic phase.
  • the water-insoluble rhodium compound which separates in the oxidative digestion of the spent aqueous catalyst solution is taken up in an organic solvent and the aqueous and organic phases are separated from one another.
  • Suitable organic solvents are benzene, toluene, xylene, cyclohexane, aliphatic carboxylic acids and carboxylic acid esters, aliphatic and cycloaliphatic ketones having 5 to 10 carbon atoms. Particularly suitable are toluene and xylene.
  • the organic phase is washed with an aqueous, dilute acid, wherein the volume ratio between organic phase and aqueous, dilute acid is advantageously chosen so that the phase separation is carried out without problems.
  • the separated organic phase is washed again with water, usually with the same amount.
  • the acid washing of the organic phase are inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid and water-soluble organic acids having 1 to 5 carbon atoms, such as formic acid, acetic acid, propionic acid, the various butyric acids and pentanoic acids.
  • the dilute washing acid used has an acid content of 5 to 25 wt .-%.
  • dilute sulfuric acid at a concentration of 5 to 25% by weight is used for the organic phase wash.
  • aqueous solutions which are the aqueous solution obtained after the oxidative digestion of the used aqueous catalyst solution and optionally the acidic, aqueous wash solution from the acid wash of the water-insoluble and organic solvent-absorbed rhodium compounds which precipitate during the oxidative treatment and the wash water from the subsequent water wash of the organic phase is separated or combined in any combination with an ion exchange treated with resin.
  • ion exchange resins are resins functionalized with thiourea or alkylthiourea groups with C1-C5-alkyl radicals.
  • the aqueous solution is brought into contact with the ion exchange resin in a suitable reactor.
  • the ion exchange resin may be placed in a tubular reactor as a fixed bed through which the rhodium-containing liquid flows.
  • the fixed bed volume and the size of the ion exchanger resin particles can be varied within wide limits and thus adapted to the selected reaction conditions and the process conditions, such as the desired flow rate. It has been found useful to maintain space velocities in the range from 0.1 to 2.5, in particular from 0.5 to 1.5 (V aqueous solution / [ion exchange resin ⁇ h]). These are guide values which must be observed appropriately.
  • rhodium deposition improves at lower space velocities, the deposition process itself takes a disproportionately long time. At higher space velocities, the deposition process will be accomplished in a shorter time, but the deposition of rhodium will not be complete.
  • the ion exchange resin which in this case may be very finely divided, is suspended in the rhodium-containing aqueous solution. It is convenient to continuously agitate the suspension, for example by stirring or introducing a gas, for example air or nitrogen, to achieve intimate contact between the liquid phase and the ion exchange resin.
  • the mass ratio of liquid phase to ion exchange resin can be largely free and thus adjusted according to individual requirements. It has proven useful, per 100 parts by weight of rhodium-containing aqueous solution 1 to 10, preferably 3 to 8 parts by weight of ion exchange resin.
  • stirred tanks or autoclaves are suitable for carrying out this process variant.
  • the ion exchange resin is subjected to mechanical stress, and for the mixing of aqueous phase with the ion exchange resin, the conditions are to be adjusted so as to avoid abrasion on the surface of the resin particles or even mechanical damage to the resin particles.
  • the aqueous solution may be recirculated to complete the rhodium separation by multiple treatment of the aqueous phase. It is also possible to carry out the adsorption in several stages, both batchwise and continuous reaction is possible.
  • the new process has proved to be excellent for recovering the residual amounts of rhodium remaining in the aqueous solution after the oxidative digestion of the used aqueous catalyst solution and after separating insoluble rhodium compounds. If the water-insoluble rhodium compounds are taken up in an organic solvent and the resulting organic phase is additionally subjected to washing with an aqueous, dilute acid and subsequent water washing, the amounts of rhodium which are thereby discharged into the aqueous phase can likewise be determined by the novel process be recovered.
  • aqueous, used catalyst solution which on the one hand contains only small amounts of rhodium but is loaded on the other side with a high salt load. Up to about 98% of the rhodium in the feed can be deposited on the ion exchange resin and the rhodium concentration in the treated substrate can be reduced to below 0.1 ppm. Furthermore, heavy metal compounds dissolved in the used aqueous catalyst solution, such as compounds of iron, cobalt, nickel or chromium, can be deposited on the ion exchange resin.
  • the aqueous solutions obtained after the treatment according to the invention therefore only have a very low heavy metal content and can be disposed of in a simple manner.
  • the new process is particularly suitable for working up aqueous solutions which are obtained from the hydroformylation reaction of propylene, butene-1 or mixtures comprising butene-1 and butene-2 using an aqueous catalyst solution and subsequent oxidative digestion of the used aqueous catalyst solution.
  • the rhodium-loaded ion exchange resin can be mixed with an aqueous solution containing water-soluble phosphines of the formula
  • the wastewater (A) is obtained after the oxidative digestion of the used aqueous catalyst solution, for example carried out according to the methods known from EP 0 255 673 A2 or EP 0 367 957 A2. Depositing water insoluble rhodium compounds are taken up with toluene in an amount equal to one fifth of the aqueous phase.
  • the sulfuric acid washing solution (B) is obtained by washing the toluene phase with the same amounts of a 10 wt .-%, aqueous sulfuric acid and the wash water (C) falls in the subsequent washing the washed with sulfuric acid toluene phase with the same amount of water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un procédé pour la récupération du rhodium à partir de solutions aqueuses, par traitement par une résine échangeuse d'ions. La solution aqueuse est obtenue sous forme d'une solution usée de catalyseur lors de l'hydroformylation d'oléfines, puis attaque par oxydation et séparation en composés du rhodium insolubles dans l'eau.
PCT/EP2009/007955 2008-11-18 2009-11-06 Procédé pour la récupération du rhodium à partir de solutions aqueuses contenant des composés complexes du rhodium Ceased WO2010057582A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09756670A EP2358471B1 (fr) 2008-11-18 2009-11-06 Procédé pour la récupération du rhodium à partir de solutions aqueuses contenant des composés complexes du rhodium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008057857.6 2008-11-18
DE102008057857.6A DE102008057857B4 (de) 2008-11-18 2008-11-18 Verfahren zur Rückgewinnung von Rhodium aus Rhodiumkomplexverbindungen enthaltenden wässrigen Lösungen

Publications (1)

Publication Number Publication Date
WO2010057582A1 true WO2010057582A1 (fr) 2010-05-27

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EP (1) EP2358471B1 (fr)
KR (1) KR101604242B1 (fr)
DE (1) DE102008057857B4 (fr)
TW (1) TWI402103B (fr)
WO (1) WO2010057582A1 (fr)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113735910A (zh) * 2020-05-27 2021-12-03 中国石油化工股份有限公司 乙酰丙酮三苯基膦羰基铑废剂的处理方法和乙酰丙酮三苯基膦羰基铑催化剂
CN116477679A (zh) * 2023-06-19 2023-07-25 山东有研国晶辉新材料有限公司 利用氧化铝载体铱催化剂回收提纯制备氯铱酸的方法

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* Cited by examiner, † Cited by third party
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CN102924726B (zh) * 2012-11-13 2015-05-20 北京化工大学 树状分子封装铑纳米粒子催化nbr加氢胶液中铑的回收方法

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Publication number Priority date Publication date Assignee Title
DE2627354C3 (de) 1975-06-20 1980-12-04 Rhone-Poulenc Industries, Paris Verfahren zur Herstellung von Aldehyden
EP0255673A2 (fr) 1986-08-06 1988-02-10 Hoechst Aktiengesellschaft Procédé pour récupérer du rhodium de solutions aqueuses contenant des composés de complexes du rhodium
EP0355837A2 (fr) 1988-08-25 1990-02-28 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Obtention de métaux de transition
EP0367957A2 (fr) 1988-10-01 1990-05-16 Hoechst Aktiengesellschaft Procédé de récupération de rhodium
US6180838B1 (en) 1994-09-30 2001-01-30 Shell Oil Company Process for preparing alkanediols

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DE2045416C3 (de) 1970-09-15 1979-10-25 Basf Ag, 6700 Ludwigshafen Verfahren zur Elution von Rhodium, das als Rhodiumcarbonylat auf einem basischen Ionenaustauscher gebunden ist
ID17582A (id) * 1996-07-15 1998-01-15 Atochem North America Elf Proses hidroformilasi yang ditingkatkan dengan pemisahan daur-ulang katalisator rhodium aktif
GB0021715D0 (en) 2000-09-05 2000-10-18 Ici Plc Recovery of metals
GB0113079D0 (en) 2001-05-30 2001-07-18 Kvaerner Process Tech Ltd Process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2627354C3 (de) 1975-06-20 1980-12-04 Rhone-Poulenc Industries, Paris Verfahren zur Herstellung von Aldehyden
EP0255673A2 (fr) 1986-08-06 1988-02-10 Hoechst Aktiengesellschaft Procédé pour récupérer du rhodium de solutions aqueuses contenant des composés de complexes du rhodium
EP0355837A2 (fr) 1988-08-25 1990-02-28 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Obtention de métaux de transition
EP0367957A2 (fr) 1988-10-01 1990-05-16 Hoechst Aktiengesellschaft Procédé de récupération de rhodium
US6180838B1 (en) 1994-09-30 2001-01-30 Shell Oil Company Process for preparing alkanediols

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735910A (zh) * 2020-05-27 2021-12-03 中国石油化工股份有限公司 乙酰丙酮三苯基膦羰基铑废剂的处理方法和乙酰丙酮三苯基膦羰基铑催化剂
CN113735910B (zh) * 2020-05-27 2023-09-26 中国石油化工股份有限公司 乙酰丙酮三苯基膦羰基铑废剂的处理方法和乙酰丙酮三苯基膦羰基铑催化剂
CN116477679A (zh) * 2023-06-19 2023-07-25 山东有研国晶辉新材料有限公司 利用氧化铝载体铱催化剂回收提纯制备氯铱酸的方法
CN116477679B (zh) * 2023-06-19 2023-10-10 山东有研国晶辉新材料有限公司 利用氧化铝载体铱催化剂回收提纯制备氯铱酸的方法

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EP2358471B1 (fr) 2012-08-08
DE102008057857B4 (de) 2014-09-11
KR20110086709A (ko) 2011-07-29
KR101604242B1 (ko) 2016-03-17
DE102008057857A1 (de) 2010-05-27
EP2358471A1 (fr) 2011-08-24

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