• 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:
    A method for recovering a transition metal, e.g., rhodium, from a non-polar organic solution containing non-polar organic solvent-soluble and polar solvent-insoluble coordination complex of the transition metal and a non-polar organic solvent-soluble and polar solvent-insoluble ligand, e.g., an organophosphorus ligand, by contacting the non-polar organic solution with a polar solution of an ionic organophosphine ligand. The transition metal then can be transferred back into a non-polar organic solution for reuse. In one embodiment rhodium is rendered amenable for back-extraction by treating the polar solution with a suitable conditioning reagent.
    公开号:SU1757459A3
    申请号:SU894742043
    申请日:1989-08-11
    公开日:1992-08-23
    发明作者:Джеймс Миллер Дэвид；Роберт Брайант Дэвид
    申请人:Юнион Карбайд Кемикалз Энд Пластикс Компани, Инк. (Фирма)；
    IPC主号:
    专利说明:

    The goal is achieved by a method of extracting rhodium from a nonpolar organic solution containing a rhodium coordination complex and a nonpolar ligand, where the amount of rhodium is 179-8100 ppm and the unpolar ligand is selected from the group including: tribenylphosphine, triphenylphosphine, cyclohexyldiphenylphosphine, bis- (diphenylphosphino) ethane, N-butyldiphenylphosphine and 2-tert-4-methoxy (3, 3 -di-tert-butyl-5,5-dimethoxy-1,1-biphenyl-2 , 2 -diyl) phosphite ligand, and the distinguishing feature is that the non-polar organic matter is in contact A solution with an aqueous polar solution containing an ionic phosphine-organic ligand selected from the group consisting of triphenylphosphine monosulfonic acid sodium salt, triphenylphosphine tri-succinic acid sodium salt and sodium bis (diphenylphosphino) ethane-m-monosulfonic acid sodium salt. with a volume ratio of non-polar organic solution to an aqueous polar solution of 0.24-10.8. The nonpolar ligand is represented by triphenylphosphine, and the ionic organophosphine ligand is represented by sodium triphenylphosphine monosulfonic acid,
    FIG. Figures 1-4 show graphically the results of Example 32 (curve of the dependence of the distribution coefficient between the nonpolar (0) and polar (A) phases on the ratio of the molar concentration of the ligand in the nonpolar and polar phases).
    Examples 1-4. The ability of polar solutions is determined, i.e. aqueous solutions having different concentrations of the ionic phosphine ligacd soluble in a polar solvent, extract active rhodium from fresh (100% active) non-polar hydroformylation reaction medium containing 10% by weight of triphenylphosphine (TTP) ligand and 300 ppm in solvent Tekhopor (Estman brand 2,2,4-trimethyl-1,3-pentadiolmonoisobutyrate). The sodium salt of trimethylphosphine monosulfonic acid (TPPMS-Na) is used as soluble in a polar solvent, i.e. water-soluble, ionic phosphine ligznda. In each example, 50 g of a sample of the reaction medium (49.25 g is used in example 4) is contacted (extracted) with three separate samples (10 g each) of an aqueous solution of ligand (only two separate samples 10 g each are used in example 4). The results are presented in table. 1 and illustrate the extraction of rhodium as a function of the concentration of water-soluble ligand.
    Examples 4 and 5. The extraction abilities of 10 wt.% Polar solution of triphenylphosphinomonosulfonic acid sodium salt (TPPMS-Na, example 4) and 10 wt.% Of the polar solution of triphenylphosphinotrisulphonic acid sodium salt (TPPTS-Na, example 5) are studied.
    In both cases, the non-polar hydroformylation reaction medium contains 10 wt.% Triphenylphosphine ligand (TPP) and 300 h / ml. The yield in Tehepor has an activity of 100%. In each case, two consecutive water washings (extractions) of the same amount are carried out. However, since the sample volume of the organic phase is smaller in Example 5, its organic phase / water phase (O / A) volume ratio was less. The results are presented in Table. 2
    Examples b and 7. Use 3 wt.% - aqueous (polar) solution of sodium will triphenylphosphine monosulfonic acid (Example 6) and 10 wt.% - aqueous (polar) solution of sodium salt triphenylphosphine sodium sulfonic acid (Example 7) for extraction of active rhodium from a spent hydroformylation reaction medium having an activity of 75%, a rhodium concentration of 727 ppm, a triphenylphosphine (TRP) ligand concentration of 10 wt.%, containing pentadecanol, 80 wt.%, with a balance attributable to side aldehyde condensation products. In each case, two consecutive equal-volume water washes (extraction) were used. However, since the sample size of the organic phase is smaller in Example 7, its organic / aqueous volume (O / A) volume ratio was less. In tab. 3 presents the results obtained.
    Examples 8 and 9. The capabilities of a 10 wt.% Aqueous (polar) solution of TPPMS-Na (example 8) and a 10 wt.% - aqueous (polar) solution of TPPMS-Na (example 9) are illustrated to extract active rhodium from spent hydroformylation reaction medium having an activity of 39%. a rhodi concentration of 540 ppm, a concentration of triphenylphosphine ligand (TPP) of 10 wt.%, an oil aldehyde concentration of 30 wt.% and a balance attributable to aldehyde condensation by-products. In each case, two equal volume washings (extractions) are carried out. In Example 9, use a slightly smaller sample.
    catalyst solution The results are presented in that A.
    Examples 10 and 11. The capabilities of 10% by weight aqueous (polar) solutions of TPPMS-Na (example 10) and TPPTS-Na (example 11) are illustrated to extract active rhodium from a reacted hydroformylation reaction medium having an activity of 70%, give birth concentration of 8-100 ppm the content of free triphenylphosphine (TPP) ligand is 10 wt.% and the balance attributable to high boiling aldehyde condensation by-products and triphenylphosphine oxides. In each case, 25 g of the sample of the organic phase is extracted twice twice with the aqueous phase. For Example 11, use two 35 g water washes, and to obtain a lower O / A value, use a larger amount of aqueous extractant (two 55 g samples) for Example 11 The results are presented in Table. five.
    Example 12. A 25 g sample of the reaction medium of hydroforming of unknown activity with a content of 200 ppm of rhodi, 1.5% by weight of 2-tert-4-methoxy (3,3-di-ter-butyl-5, The 5-dimethoxy-1,1-bi phenyl-2,21-diyl) phosphite ligand with a balance attributable mainly to valeric aldehyde in its condensation byproducts is sequentially extracted twice with 25-gram samples of an aqueous (polar) solution containing 5.0% by weight of TPPMS-Na; 94% rhodium was recovered in two aqueous wash fractions.
    Example 13. 10 g sample of fresh catalyst solution of hydroformylation (activity 100%), with a content of 1000 ppm of rhodium, 20% by weight of triphenylphosphine (TPP) ligand, 24% by weight of aldehyde with a balance attributable to Techapog once in contact with 5.9 g of a 3.0 wt.% - aqueous (polar) solution of TPPMS-Na. 69.7% of the parents in the aqueous phase are recovered.
    Examples 14-17. Illustrate the use of maleic acid (MA) as a conditioning reagent to reduce the amount of a polar solution, for example, in an aqueous solution soluble in a polar solvent of a phosphinorganic ligand capable of forming a coordination complex, i.e. capable of complexing with rhodium, and extraction efficiency from the polar to the non-polar phase. An aqueous solution is obtained by extraction of a non-polar catalyst solution of hydroformylation,
    containing 540 ppm give birth, 10 wt.% TPP. 30% by weight of oil aldehyde with a balance falling on the aldehyde by-products of condensation, an aqueous solution containing 5% by weight of TPPMS-Na. 20 g of samples of the resulting aqueous solution containing 5 wt.% TPPMS-Na and
    489 ppm Rhodi treated by mixing with different amounts of maleic acid at 50 ° C for 30 minutes with the transformation of the water-soluble ionic ligand in each sample into a water-soluble non-coordinating form. Samples treated with maleic acid are then back extracted using Technapog solution containing 10% by weight of triphenylphosphine (TPP).
    Each treated sample is treated three times with 20 g portions of Texanol® ligand solution. The results are presented in table. 6. As can be seen from Table 6, when the ligand concentration in the aqueous phase is reduced to less than 5.0 mol of ligand per gram-atom of rhodium (which in these cases corresponds to more than about 85% removal of the ligand), reverse reverse rhodium extraction occurs,
    Examples 18-21. Illustrate the use of varying amounts of maleic acid (MA) as a conditioning reagent to reduce the amount of TPPMS-Na ligand capable of complexing with rhodium in aqueous (polar) solutions containing different amounts of rhodium, and the effect of such treatment on the efficiency of rhodium extraction. used in the examples
    18 and 20 correspond to the aqueous solutions obtained in examples b and 8, respectively. Aqueous solutions of Examples 19 and 21 half-0 were studied by extracting non-polar hydroformylation catalyst solutions containing 300 ppm of Rhodi, 10 May. D TPP and the balance attributable to Texanof® and 375 ppm of rhodium, 11% by weight TPP 6% by weight of oil aldehyde and the balance attributable to the aldehyde by-products of condensation, respectively 10% by weight of an aqueous solution TPPWIS-Na and 5 wt.% Aqueous solution of TPPMS-Na. The treated MA aqueous (polar) solutions are each subjected to threefold back-extraction using 25-gram portions of 10 solution of triphenylphosphine in Texanol®. Aqueous solutions containing injected maleic acid are heated at 50 ° C for about 30 minutes. The results are presented in table. 7 and show the effectiveness of maleic acid in conditioning the aqueous extraction solution.
    Example 22. This example illustrates the use of an organic solution of cyclohexyl diphenylphosphine (CHDPP) ligand for the extraction of rhodium from an aqueous solution of an extractant, a 25 g sample of an aqueous solution containing 5 May. TTPMS-Na used for the extraction of rhodium from the spent hydroformylation reaction medium containing 540 ppm of rhodium, 10% by weight of TPP, 30% by weight of aldehyde and the balance attributable to side aldehyde condensation products, after such Rhodi extraction contains 78 ppm Rhodi. This sample is treated at 50 ° C for about 30 minutes with 0.4 g of maleic acid and then extracted three times (in 25 g portions) using 3.0% w / w of a solution of CHDPP in Techopor solvent. Analysis of the collected organic extragents showed that 96.6% of the rhodium was transferred from the aqueous solution to the organic phase.
    Examples 23-26. Illustrate the use of strongly acidic conditioning agents for converting the TPPMS-Na ligand in aqueous (polar) solutions containing various amounts of rhodium into a form incapable of coordination, i.e. in a form that is less capable of complexing with rhodium, and the effect of such treatment on the extraction efficiency. In Example 23, an initial aqueous solution is obtained by extracting a non-polar catalyst solution of hydroformylation containing 540 ppm, rhodium, 10 wt.% TPP, 30 wt.% Aldehyde and the balance attributable to the aldehyde by-products of condensation with aqueous a solution of 5 wt.% TPPMS-Na. In examples 24 and 25, initial aqueous solutions are obtained by extracting a non-polar catalyst solution of hydroformylation, containing 1000 ppm of rhodium, 20 wt.% TPP, 24 wt.% Oil aldehyde, and the balance attributable to Techapodvod. 3% by weight of TPPMS-Na. In Example 26, the initial aqueous solution was obtained by extracting a non-polar catalytic solution of hydroformylation containing 300 ppm of rhodium, 3 wt.% TPP and Technopog balance; an aqueous solution of 5 wt.% TPPMS-Na. Acid-treated aqueous solutions (each) are sequentially extracted three times (in 25 g portions) using a 10% by weight solution of triphenylphosphine (TPP) in Technopog solvent. Aqueous solutions containing the added acid are heated at 50 ° C for 30
    min The results are presented in table. 8. They show the effectiveness of treatment with a strong acid in terms of conditioning the aqueous (polar) solution for the extraction of rhodium from the aqueous phase.
    Example 27. Describes the continuous extraction of rhodium from the hydroformylation reaction medium using an extraction column with a diameter of 3/8 inch (37.5 mm), comprising five theoretical stages of a countercurrent flow of organic solution and an aqueous solution containing TPPMS-Na ligand. The rate of the combined feed stream to the extraction column (organic phase plus aqueous phase) is maintained at about 1700 g / h in all cycles and the column operates at a temperature of 35 ° C. Rhodium balance is determined for each cycle according to the flow rate and concentrations of rhodium in different streams. The data is given in Table. 9 and 10. Efficiency Extractions are calculated by determining the percentage of rhodium transferred from the organic phase to the aqueous phase, followed by normalization of the value by correlation with the catalyst activity.
    In tab. 9 illustrates the effect of reducing the amount of the starting aqueous solution as compared to the starting organic product. In these cycles, a 5 wt.% Solution of TPPMS-Na is used to extract rhodium from an organic solution with an activity of 39% as a catalyst for hydroformylation. This solution contains 1073 h, ppm of rhodium, 15% by weight of TPP, 38% by weight of oil aldehyde, 10% by weight of hexane. 10 wt.% Aldehyde with a content of 9 C atoms, the balance is the by-product of the condensation of oil aldehyde. To carry out cycle 8 (Table 10), the same catalyst solution of hydroformylation is used. The results show that as the amount of the initial aqueous product decreases (i.e., as the organic / aqueous (O / A) volume ratio increases) the extraction efficiency decreases. Due to the viscous nature of the organic solution, higher O / A ratios do not provide sufficient exposure of the rhodium in the organic phase to the aqueous phase of the extractant. In cycles 4, 6 and 7, a hydroformylation catalyst solution containing 540 ppm of rhodium, 10 wt.% TPP, May 30, is used. % aldehyde oil and the balance of aldehyde condensation by-products; cycle 9 uses a catalyst solution of hydroformylation. containing 635 ppm give birth. 12 wt.% TPP, 30 May% oil aldehyde, 20 May% hexane, 10 May% aldehyde containing 9 C atoms and the balance attributable to the by-products of oil aldehyde condensation In cycles 5 and 10 as a non-polar starting product organic solutions extracted from the extraction column were used in previous cycles 4 and 9, respectively, and cycle 10 uses a hydroformylation catalyst solution containing 312 ppm rhodi, 10 May% TPP. 80% by weight of ldehyde and aldehyde condensation by-products
    Example 28 This example illustrates the continuous extraction of rhodium from an aqueous (polar) solution containing 5% by weight of TPPMS-Na ligand and 382 ppm of rhodium. This aqueous solution corresponds to the water stream recovered from cycle 11 shown in Table 10. The same is used. equipment, as in Example 27 The aqueous solution is first treated with maleic acid to completely convert the TPPMS-Na ligand to a non-coordinating form. Then, a solution of isobutyric aldehyde containing 10% by weight of triphenylphosphine is used as a non-polar extractant. The extraction efficiency is achieved 83.0%
    Examples 29 and 30 Demonstrate the ability of an aqueous (polar) solution of sodium salt of DIPHOS — monosulfonic acid (bis-diphenylphosphinoethane-methane-monosulfonic acid, sodium salt) (S-DIPBOS-Na) to extract rhodium from the hydroformylation reaction medium. As a fresh catalyst solution containing 10% by weight of triphenylphosphine, 179 ppm of rhodi and tridecanal balance, and a catalyst of unknown activity, containing 635 ppm of rhodium, 12% of triphenylphosphine ligand, 30% by weight of aldehyde, 20 wt.% hexane, 10 wt.% aldehyde with a content of 9 atoms, and the balance attributable to the by-products of oil aldehyde condensation was treated with an aqueous solution. In each example, 1 mas.h of the organic solution is contacted for a few minutes with 1 mas.h of an aqueous solution containing 2 may% of sulphonated DIPHOS. Analysis of the aqueous extractant showed that 89% of the rhodi in the fresh catalyst and 25% of the rhodium in the spent catalyst were recovered in the aqueous phase used for contacting the fresh and the spent catalyst solutions, respectively.
    Example 31 illustrates the use of a chemical reagent to improve the extraction of rhodium from a non-polar organic solution. Spent hydroformylation catalyst solution having an activity of about 35% and containing about 22 May% triphenylphosphine (soluble in a nonpolar solvent and insoluble in polar
    0 solvent of the ligand), about 750 ppm of rhodium, about 11 May% of oil aldehyde and the balance attributable to the aldehyde condensation by-products is treated with allyl chloride to influence its extraction efficiency. The results are presented in Table 11.
    Example 32 illustrates the effect of the relative amount soluble in a non-polar organic solvent and
    0 insoluble in a polar solvent ligand in the non-polar phase in relation to the amount of polar ion-soluble ionic ligand in the polar phase for the distribution of birth between two phases5 Fresh catalyst solutions of hydroformylation (non-polar organic solutions) containing 300 ppm Rhodium is prepared by mixing Dicapbonylacetylacetonate on Day 0 of TechnoP with such an amount of ligand soluble in a nonpolar solvent that is sufficient to obtain molar concentrations of the ligand. Before carrying out various extractions fresh
    5, catalyst solutions are activated (condensed) as a result of using them for 24 hours in a continuous hydroformylation reactor, where the hydroformylation of propylene takes place in oil aldehyde.
    Catalyst solutions are prepared using triphenylphosphine (TPP) at a molar concentration of about 0.324 mol / l; cyclohexyl dife5 nilphosphine (CHDPP) in a molar concentration of approximately 0.032, 0.095, 0.13 and 0.15 mol / l; n-butyldiphenylphosphine (BDPP) in molar concentrations of approximately 0.07 and 0.14 mol / l; and bis-diphenylphosphinoethane
    0 (DIPHOS) in molar concentrations of about 0.02, 0.06, 0.11 and 0.21 mol / L.
    . Molar extractants are prepared by preparing aqueous solutions of the following ionic ligands in various molar concentrations: sodium triphenylphosphine monosulfonate (TPPMS-Na) sodium salt in molar concentrations from about 0.002 to 0.3 mol / l; sodium salt of triphenylphosphinotrisulfonate (TPPTS-Na) in molar concentrations from about
    0.002 to 0.1 mol / L, and sodium salt-sulfonated bis-diphenylphosphinoethane (S-DTPHOS-Na) in a molar concentration of 0.02 mol / L. The extraction is carried out by agitating different amounts of non-polar organic solutions and polar (aqueous) solutions in standard laboratory glassware for 4 hours and then separating the non-polar and polar phases by centrifuging.
    The results are presented below in table. 12-20, which illustrate the ratio of the concentration of rhodium in the organic phase and the concentration of rhodium in the aqueous phase after extraction of the Rh ratio (O / A) as a function of the types of ligands; and the ratio of the ligand soluble in the nonpolar solvent (non-polar ligand) and the polar ligand soluble in the polar solvent (ionic ligand) in these two phases. Conditions that give low Rh ratios (less than 1.0) are favorable for extraction into the non-polar (aqueous) phase, while conditions that give high ratios Rh (more than 1.0) are favorable for extraction in incomplete rnu organic phase. The results are presented in the form of curves in FIG. 1-4.
    Example 33. A 10-gram sample of a freshly prepared catalyst solution of hydroformylation (100% activity) containing 300 ppm of native, 1.5% by weight tribenylphosphine ligand and the balance attributable to Techapor is contacted once with 5.0 g of 5 May. % aqueous (polar) solution of ion ligand TTPMS-Na. An analysis of the water wash showed that 67% of the rhodi was recovered in the aqueous phase.
    The proposed method is applicable for the extraction and reuse of rhodium-ligand coordination complex soluble in a non-polar organic solvent from non-polar organic solutions used for hydroformylation of higher olefins, and especially for solutions that may become uneconomical. For subsequent use due to the accumulation of high boiling aldehyde by-products condensation products, as well as for the extraction of transition metals of group VII of the periodic system of elements from any non-polar orbit anicheskogo
    solution containing soluble in a non-polar organic solvent and insoluble in a polar solvent coordination complex of a transition metal and free phosphororganic ligand soluble in a non-polar organic solvent, regardless of whether there is a driving force that causes the removal of clusters of some by-products difficult to remove of
    organic solution, whether there is a gradual deactivation of the catalyst or any other phenomena.
    FORUMAWLAH AND ISLANDS
    权利要求:
    Claims (2)
    [1]
    1. A method of extracting rhodium from a nonpolar organic solution containing a rhodium coordination complex and a nonpolar ligand, where the amount of rhodium is 179-8100 ppm and nonpolar
    The ligand is selected from the group consisting of: tribenismphosphine, triphenylphosphine, cyclohexyldiphenylphosphine, bis- (diphenylphosphino) ethane, N-butyldiphenylphosphine, and 2-tert-4-methoxm (3,3-di-tert-but-5,5 - dim sum
    etoxy-1,1-biphenium -2,2-diyl) phosphite ligand, characterized in that, in order to increase the degree of extraction of the rhomes, the inorganic organic solution is contacted with an aqueous solution containing
    ionic phosphine organic ligand. selected from the group including: sodium salt of triphenylphosphine monosulfonic acid, sodium salt of triphenylphosphine trisulfonic acid and sodium salt
    bis- (diphenylphosphino} -ethane-m-monosulfonic acid, and the process is carried out with a volume ratio of a non-polar organic solution to an aqueous polar solution of 0.24-10.8.
    [2]
    2. A method according to claim 1, characterized in that the non-polar ligand is triphenylphosphine, and the ionic phosphine-organic ligand is sodium triphenylphosphine monosulfonic acid.
    Table 1
    Table 2
    Tabl and Caz
    Tabl and ca4
    to
    TableB
    15
    Table
    Table
    Ta lb and tsa 8
    E table
    Table 10
    Table11
    ten
    Table 12
    СНРРРиТРМЗ-Na
    Molecular ratio of non-polar ligand to ionic ligand
    0.25 0.38 0.69 1.2 11.5 15.4 23.3 46.2
    Continued table 12
    Table 13
    Table 14
    Rh (O / A) ratio
    0.24 0.47 0.25 0.42
    1.1
    4.4
    10.2
    17.5
    Table 15
    tfu something-. H i t r -i i I H 10 20 30 40 50 wo 70 70 80 BO 100
    Fig 1
    Table 17
    Table 18
    Table 19
    Table 20
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1757459A3|1992-08-23|Method of rhodium extraction
    SU898951A3|1982-01-15|Method of regenerating rhodium-containing catalyst for olefin hydroformylation
    Charlesworth1981|Separating the Platinum Group Metals by Liquid‐Liquid Extraction
    US4504588A|1985-03-12|Process for the recovery of water-soluble hydroformylation catalysts containing rhodium
    HU204249B|1991-12-30|Process for producing aldehydes withcatalytic hydroformilizing olephines
    CN100569724C|2009-12-16|A kind of preparation of alkyl aromatic aldehyde and separation method
    SU1279532A3|1986-12-23|Method of producing sulfonated triphenylphosphines
    US4990639A|1991-02-05|Novel recovery process
    PL135114B1|1985-09-30|Method of obtaining hydrides of carbonylotris /triorganophosphoro/ rhodium
    EP0367957B1|1992-01-08|Process for recovering rhodium
    US6641734B2|2003-11-04|Process for purifying an organic acid
    US4623490A|1986-11-18|Process for the purification of sulfonated aryl phosphines
    JP2820977B2|1998-11-05|Removal of iodine or iodide impurities
    EP0348833B1|1992-08-05|Process for the separation and recuperation of rhodium from oxysynthesis products
    CA2185089A1|1997-03-13|Process for the recovery of catalysts in adipic acid production
    JPH0755834B2|1995-06-14|Method for recovering rhodium from distillation residue of oxo synthesis product
    JPH078336B2|1995-02-01|Method for recovering rhodium from distillation residues of products of oxo synthesis
    JP2530985B2|1996-09-04|Method for separating cresol isomers
    US5206000A|1993-04-27|Process for the recovery of rhodium from aqueous solutions containing rhodium complexes
    CA2080747A1|1993-04-25|Process for recovering rhodium from the reaction products of the oxo synthesis
    WO2003059863A1|2003-07-24|Process for puriying an organic acid
    US5200559A|1993-04-06|Process for producing sorbic acid
    US3475495A|1969-10-28|Removing palladium compounds from aqueous glyoxal solutions
    EP0245632B1|1990-09-26|Method of purification of the oxalic acid diamide
    US4559182A|1985-12-17|Method for purifying cresidine sulfonic acid by resin extraction
    同族专利:
    公开号 | 公开日
    KR910004825A|1991-03-29|
    MX164462B|1992-08-18|
    DE68910749D1|1993-12-23|
    AU621924B2|1992-03-26|
    JPH0791068B2|1995-10-04|
    EP0354588A1|1990-02-14|
    KR940004627B1|1994-05-27|
    PL162639B1|1993-12-31|
    EP0500150B1|1994-03-16|
    CN1021656C|1993-07-21|
    DE68910749T2|1994-05-05|
    US4935550A|1990-06-19|
    EP0500150A1|1992-08-26|
    CN1040825A|1990-03-28|
    ES2050550T3|1994-05-16|
    ES2045299T3|1994-01-16|
    EP0354588B1|1993-11-18|
    BR8904055A|1990-03-20|
    AU3952589A|1990-02-15|
    DE68913999T2|1994-07-28|
    JPH02145439A|1990-06-04|
    DE68913999D1|1994-04-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    IT1007026B|1974-01-23|1976-10-30|Montedison Spa|PROCEDURE FOR THE RECOVERY OF CATALYTIC SYSTEMS FROM CRUDE OF HYDROFORMILATION|
    US4248802A|1975-06-20|1981-02-03|Rhone-Poulenc Industries|Catalytic hydroformylation of olefins|
    EP0007768A3|1978-07-27|1980-02-20|DAVY McKEE LIMITED|Hydroformylation of alpha-olefinic compounds|
    DE2833469C2|1978-07-29|1986-10-09|Basf Ag, 6700 Ludwigshafen|Process for working up reaction mixtures which arise in the hydroformylation or the carbonylation|
    US4283304A|1979-05-21|1981-08-11|Union Carbide Corporation|Process for removing triorganophosphine from a liquid composition|
    US4297239A|1979-07-16|1981-10-27|Union Carbide Corporation|Hydroformylation catalyst reactivation|
    US4374278A|1980-02-28|1983-02-15|Union Carbide Corporation|Hydroformylation catalyst reactivation|
    US4292196A|1979-12-10|1981-09-29|Uop Inc.|Catalyst recovery|
    GB2085874B|1980-09-04|1984-08-08|Johnson Matthey Plc|Hydroformylation of olefins|
    JPS5850234B2|1980-10-23|1983-11-09|Mitsubishi Chem Ind|
    GB2092097B|1981-01-12|1985-06-19|Armfield Engineering Ltd|Inspection machine|
    JPS5923858B2|1981-01-22|1984-06-05|Mitsubishi Chem Ind|
    US4364907A|1981-06-18|1982-12-21|Eastman Kodak Company|Process for recovery of rhodium values|
    DE3235029A1|1982-09-22|1984-03-22|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR RECOVERY OF WATER-SOLUBLE, RHODIUM-CONTAINING HYDROFORMYLATION CATALYSTS|
    JPH0237215B2|1982-12-15|1990-08-23|Daiseru Kagaku Kogyo Kk|HIDOROHORUMIRUKASHOKUBAINOSHORIHO|
    DE3347406A1|1983-12-29|1985-07-11|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR SEPARATING AND RECOVERING RHODIUM FROM OXOSYNTHESIS PRODUCTS|
    DE3411034C2|1984-03-26|1992-08-06|
    US4731485A|1984-04-03|1988-03-15|Ruhrchemie Aktiengesellschaft|Process for hydroformylation with rhodium catalysts and the separation of rhodium therefrom|
    DE3443474A1|1984-11-29|1986-05-28|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR RECOVERY OF RHODIUM FROM REACTION PRODUCTS OF THE OXOSYNTHESIS|
    DE3534314A1|1985-09-26|1987-04-02|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|
    US4633021A|1985-11-29|1986-12-30|National Distillers And Chemical Corporation|Olefin hydroformylation|
    US4716250A|1986-07-10|1987-12-29|Union Carbide Corporation|Hydroformylation using low volatile/organic soluble phosphine ligands|US5099047A|1989-11-17|1992-03-24|Mitsubishi Kasei Corporation|Method for recovering a group viii metal solid complex and hydroformylation method|
    US5215667A|1991-08-20|1993-06-01|Exxon Chemical Patents Inc.|Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    US5288818A|1991-08-20|1994-02-22|Exxon Chemical Patents Inc.|Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    US5208194A|1992-02-25|1993-05-04|Arco Chemical Technology, L.P.|Recovery of group VIII transition metals from organic solutions using acidic ion-exchange resins|
    DE4228724A1|1992-08-28|1994-03-03|Hoechst Ag|Process for the recovery of rhodium from the distillation residues of products of oxosynthesis|
    US5395979A|1993-02-25|1995-03-07|Exxon Chemical Patents Inc.|Method for separating catalyst from a hydroformylation reaction product using alkylated ligands|
    US5290743A|1993-03-22|1994-03-01|Arco Chemical Technology L.P.|Process for regenerating a deactivated rhodium hydroformylation catalyst system|
    US5424467A|1993-07-14|1995-06-13|Idaho Research Foundation|Method for purifying alcohol esters|
    US5691422A|1994-03-07|1997-11-25|Exxon Chemical Patents Inc.|Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof|
    US5674950A|1994-03-07|1997-10-07|Exxon Chemical Patents Inc.|Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereof|
    TW319771B|1994-04-05|1997-11-11|Mitsubishi Chem Corp|
    FR2743010B1|1995-12-29|1998-02-20|Rhone Poulenc Fibres|PROCESS FOR THE PREPARATION BY HYDROGENATION OF CATALYSTS BASED ON TRANSITIONAL METAL AND PHOSPHINE|
    DE19609337C2|1996-03-11|1998-11-19|Hoechst Ag|Process for the preparation of aldehydes using a rhodium and substituted diphenyldiphosphanes containing catalyst system|
    DE19619527A1|1996-05-15|1997-11-20|Hoechst Ag|Catalyst systems based on rhodium complex compounds with diphosphine ligands and their use in the production of aldehydes|
    US5773665A|1996-07-01|1998-06-30|Elf Atochem North America, Inc.|Hydroformylation process with separation and recycle of active rhodium catalyst|
    CZ283697A3|1996-09-11|1998-04-15|Mitsubishi Chemical Corporation|Process for preparing solution of rhodium complex and the use thereof|
    EP0985449A1|1998-09-11|2000-03-15|Dsm N.V.|Process to separate rhodium from an organic mixture|
    EP1172143A1|2000-07-14|2002-01-16|Dsm N.V.|Process for the recovery of rhodium|
    DE10213020A1|2002-03-22|2003-10-02|Ge Bayer Silicones Gmbh & Co|Organopolysiloxane-containing composition, process for their preparation and their use|
    KR100615399B1|2002-08-29|2006-08-25|주식회사 우영|Direct light type flat light|
    CN101443302B|2006-05-15|2013-04-10|陶氏环球技术有限责任公司|Hydroformylation process and product separation with improved recovery of rhodium|
    US20080108986A1|2006-08-28|2008-05-08|Nanette Meneses|Apparatus and methods for relief of abdominal discomfort|
    US8715388B2|2011-04-29|2014-05-06|Momentive Performance Materials|Process of precious metal recovery and color removal from an organosilicon product-containing liquid reaction medium|
    CN104245654B|2012-04-12|2016-10-12|巴斯夫欧洲公司|The method supplementing catalyst in continuous hydroformylation|
    CN103540749B|2013-09-24|2015-04-15|宁波大地化工环保有限公司|Method for recovering rhodium from rhodium octoate organic waste liquor|
    GB201410883D0|2014-06-18|2014-07-30|Johnson Matthey Plc And Anglo American Platinum Ltd|Interseparation of metals|
    CN104028311B|2014-07-02|2016-06-15|天津渤化永利化工股份有限公司|A kind of octyl alconyl oxo catalyst chemical regeneration method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US07/231,508|US4935550A|1988-08-12|1988-08-12|Catalytic metal recovery from non-polar organic solutions|
    [返回顶部]