Catalytic metal recovery from polar organic solutions

Abstract: A method for recovering a transition metal, e.g., rhodium, from a polar solution containing a polar solvent-soluble coordination complex of a transition metal and a polar solvent-soluble ionic organophosphine ligand comprising: (i) treating the polar solution with a conditioning reagent to reduce the amount of said polar solvent-soluble ionic organophosophine ligand capable of forming a coordination complex with the transition metal in the polar solution; and (ii) contacting the polar solution produced in accordance with step (i) with a non-polar organic solvent containing non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand capable of forming a coordination complex with the transition metal to transfer said transition metal from said polar solution into said non-polar organic solvent.

Description: This invention broadly relates to a method for recovering for subsequent use Group VIII transition metals from a polar solution containing a polar solvent-soluble coordination complex a Group VIII transition metal and a polar solvent-soluble ionic organophosphine ligand. This invention particularly relates to a method for recovering rhodium from a corresponding solution, especially rhodium which exhibits catalytic activity in hydroformylation reactions. Processes using transition metal-ligand complexes as homogeneous catalysts are well-known. Included in such processes are the hydrogenation of unsaturated compounds, the carbonylation of methanol to acetic acid, olefin dimerization and oligomerization processes, the hydrocyanation of butadiene to adiponitrile and olefin hydrosilylation reactions. Still other processes are known to those skilled in the art. Oftentimes, recovery of the transition metal from the catalyst solutions used in these process presents a particularly troublesome problem. Particularly illustrative of these homogeneous catalysis systems is the hydroformylation of olefinic compounds with carbon monoxide and hydrogen to produce aldehydes in the presence of a coordination complex of a Group VIII transition metal and an organophosphorus ligand dissolved in an organic (non-polar) solvent. US-A-3,527,809, for example, teaches selectively hydroformylating alpha-olefins with certain rhodium-triorganophosphine and triorganophosphite ligand catalyst complexes to produce oxygenated products rich in normal aldehydes. US-A-4,148,830 and 4,247,486 disclose hydroformylation processes which use rhodium triarylphosphine ligand catalyst complexes. US-A-4,283,562 discloses that branched-alkyl-phenylphosphine or cycloalkylphenylphosphine ligands can be employed in a rhodium catalyzed hydroformylation process in order to provide a more stable catalyst. US-A-4,400,548 discloses that bisphosphine monoxide ligands can be employed for hydroformylation and such ligands provide rhodium catalyst complexes of improved thermal stability. Other patents describing hydroformylation processes and catalysts include US-A-4,599,206; 4,668,651; 4,717,775; 4,737,588; and 4,748,261. Rhodium complex catalyzed hydroformylation processes preferably are carried out in a non-aqueous hydroformylation reaction medium containing an organic (non-polar) solvent and both organic solvent-soluble catalyst complex and soluble free ligand, i.e., ligand not tied to or bound to the rhodium catalyst complex. Organic (non-polar) solvents which do not interfere with the hydroformylation process can be employed. Included in the group of suitable non-polar organic solvents are compounds belonging to the general classes of alkanes, ethers, aldehydes, ketones, esters, amides, and aromatics. Aldehyde compounds corresponding to the desired aldehyde products and especially higher boiling liquid aldehyde condensation by-products (oligomers) produced in situ during the hydroformylation process are particularly useful as non-polar organic solvents in rhodium-catalyzed hydroformylation. In this regard, the aldehyde product and the corresponding aldehyde trimers are preferred for start-up of a continuous hydroformylation process. However, as hydroformylation proceeds, the solvent typically will comprise both aldehyde products and higher boiling liquid aldehyde condensation by-products due to the nature of such continuous processes. Methods for the preparation of such aldehyde condensation by-products are more fully described in US-A-4,148,830 and 4,247,486. It may be preferred to separate and recover the desired aldehyde product from the non-polar hydroformylation reaction medium containing the catalyst complex by vaporization or distillation. Hydroformylation systems using both continuous gas recycle and liquid recycle are known. In a continuous liquid catalyst recycle operation such as described in US-A-4,148,830, liquid aldehyde condensation by-products including aldehyde trimers and higher oligomers, produced under hydroformylation conditions from the desired aldehyde product, are employed as the reaction solvent for the catalyst. This process has been used widely to hydroformylate lower olefinic compounds containing from two to five carbon atoms, particularly lower alpha-olefins, to produce aldehydes containing from three to six carbon atoms. In general, it is preferred to separate the desired aldehyde product from the rhodium containing product solution by selective vaporization of the aldehyde under reduced pressure and at temperatures below about 150°C, preferably below about 130°C. Commercial experience has shown that the rhodium catalyst complexes used in hydroformylating olefinic compounds are deactivated by the presence in the feedstock of extrinsic catalyst poisons, such as sulphurous compounds (e.g. H₂S, COS and CH₃SH) or halogen compounds (e.g. HCl), which can react with the rhodium of the catalyst to form inactive species which are not destroyed under the mild hydroformylation conditions employed. Hence great care is taken to purify the various feedstocks. Deactivation of the rhodium hydroformylation catalyst also occurs, however, even in the substantial absence of extrinsic poisons. This deactivation is referred to as intrinsic deactivation and is believed to be due, inter alia , to the effects of temperature, reactant partial pressures, specific organo- phosphorus ligands employed, and the rhodium concentration. The extent of catalyst deactivation (or the catalyst activity) is determined at any particular time by comparing the conversion rate of reactants to aldehyde product at that particular time, to the conversion rate obtained using fresh catalyst. Another potential problem for continuous hydroformylation processes is the accumulation of aldehyde condensation by-products of low volatility relative to the organophosphorus ligand. Since commercial processes rely on vaporization or distillation to separate the reaction product medium containing the rhodium-ligand complex from the desired aldehyde hydroformylation products, the accumulation of high boiling aldehyde condensation by-products having a low volatility must be accounted for when designing the hydroformylation process. When continuously hydroformylating lower olefinic compounds, the accumulation rate of high boiling aldehyde condensation by-products normally is sufficiently low that it can be easily controlled. Thus, in the case of hydroformylating lower olefins, catalyst life mainly is limited by the rate of catalyst deactivation. In present commercial plants, it is not unusual to operate the process for upwards of one year or more during which time any decline in catalyst activity or catalyst loss may be easily offset by addition of fresh catalyst or catalyst precursor, together with fresh organophosphorus ligand if desired. However, in such systems when the level of deactivated rhodium species rises to undesirable values and it is no longer considered economical to continue the hydroformylation process, it may become expedient simply to replace the catalyst charge completely, even though it may still contain a significant proportion of active rhodium catalyst complex. Because rhodium is an expensive metal, however, it is uneconomical to discard the spent catalyst and a usual practice is for the catalyst to be reactivated. US-A-4,297,239; 4,374,278 and 4,446,074, for example, describe procedures for reprocessing and reactivating spent hydroformylation catalyst. Continuous hydroformylation of higher olefinic compounds, such as higher alpha-olefins, containing six or more carbon atoms, e.g., from six to thirty carbon atoms, using conventional organic (non-polar) solvent-solubilized organophosphorus ligands, involves a further problem since aldehyde condensation by-products, having a low volatility relative to the organophosphorus ligands, accumulate at a much higher rate than encountered during the hydroformylation of lower olefins. Unfortunately the high rate of accumulation of such high boling aldehyde condensation by-products cannot be readily controlled by removing same by distillation from the catalyst solution during the hydroformylation without incurring significant energy costs and exposing the catalyst to severe temperature conditions. Thus, it may be more practical to let such hydroformylations of higher olefins to merely run their course until the accumulation of such by-products becomes so great as to overwhelm the catalyst solution and economically prevent its further usefulness, at which time the catalyst solution needs to be replaced with-a fresh catalyst solution. There remains, however, the additional problem of recovering the rhodium values, much of which may still be highly active, from said overwhelmed catalyst solution that is replaced. In fact, the hydroformylation catalyst still may exhibit over 75% and possibly even over 90% of its initial catalytic activity at this time. Again, unfortunately, due to their low volatility, the removal of such by-products from the replaced hydroformylation catalyst solution using conventional distillation techniques is plagued by the same energy-related and thermal exposure problems referenced above. Thus, there is a need in the art for a less energy intensive method for recovering rhodium from such catalyst solutions unde milder temperature conditions than possible using distillation procedures. Thus, EP-A-354 588, the patent application of the present one, discloses a method for recovering Group VIII transition metals and particularly rhodium from substantially non-polar organic solutions containing coordination complexes of the transition metals and organo-substituted ligands of a trivalent atom of a Group VA element such as organophosphorus ligands. Such a method potentially has application in the wide variety of homogeneous catalysis applications noted earlier, and particularly for removing rhodium from substantially non-polar organic solutions in which large concentrations of hard-to-remove components have accumulated, such as the high boiling aldehyde condensation by-products that accumulate during the hydroformylation of higher olefinic compounds. Said method comprises contacting the non-polar organic solution with a polar solution containing a polar solvent-soluble organo-substituted ligand of a trivalent atom capable of forming a coordination complex with the transition metal and transferring said Group VIII transition metal from said non-polar organic solution into said polar solution. On the other hand, the present invention provides a method for recovering a Group VIII transition metal from a polar solution containing a polar solvent-soluble coordination complex of a Group VIII transition metal and a polar solvent-soluble ionic organophosphine ligand comprising: (i) treating the polar solution with a conditioning reagent to reduce the amount of said polar solvent-soluble ionic organophosphine ligand capable of forming a coordination complex with the Group VIII transition metal in the polar solution; and (ii) contacting the polar solution produced in accordance with step (i) with a non-polar organic solvent containing non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand capable of forming a coordination complex with the Group VIII transition metal to transfer said Group VIII transition metal from said polar solution into said non-polar organic solvent; with the proviso that said method is not preceded by the above method of EP-A-354 588, i.e., the step of contacting a substantially non-polar organic solution containing a non-polar organic solvent-soluble and polar solvent-insoluble coordination complex of the Group VIII transition metal and a non-polar organic solvent-soluble and polar solvent-insoluble organo-substituted ligand of a trivalent atom with a polar solution containing said polar solvent-soluble ionic organophosphine ligand, thereby transfering said Group VIII transition metal from said organic solution into said polar solution and forming the polar solution to be treated according to the above steps (i) and (ii). The invention of EP-A-354 588 is based on the discovery that a substantially non-polar organic solution of a coordination complex of a Group VIII transition metal and an organo-substituted ligand of a trivalent Group VA element (also referred to herein simply as "an organosubstituted trivalent ligand"), which also may contain a large amount of free organo-substituted ligand, can be contacted with a polar solvent selected from the group consisting of water, methanol and mixtures thereof having dissolved therein an organo-substituted ligand capable of forming a complex with the Group VIII transition metal to transfer (i.e., extract) the transition metal from the substantially non-polar organic solution into the polar solvent (solution). Although not wishing to be bound by any particular explanation, it is believed that the non-polar organic solvent-soluble and polar solvent-insoluble transition metal-ligand complex is converted into a polar solvent-soluble transition metal-ligand complex during contact between the non-polar and polar solutions and thus the transition metal is extracted in the form of a polar solvent-soluble coordination complex. It is particularly surprising that transport of transition metal can be obtained from a non-polar organic solution that contains both ligand in complex coordination with the transition metal and a large amount of free ligand using as the extractant a different solution containing only a small amount of a different ligand. The present invention has broad applicability to the recovery of Group VIII transition metals, such as cobalt, nickel, rhodium, palladium, ruthenium, platinum and the like. For convenience in presentation, however, the invention will be described hereinafter with specific reference to the recovery of rhodium. The broad applicability of the present invention will nonetheless be appreciated and understood by those skilled in the art. Throughout the specification and claims the phrases "non-polar" solvents, "non-polar" solutions, "non-polar" hydroformylation reaction medium, and the like are used to describe organic solvents, organic solutions and organic reaction mediums that are essentially immiscible with water, methanol, mixtures thereof, and solutions made therefrom. Conversely, the phrases "polar" solvent, "polar" solution, and the like, used throughout the specification and claims, refer to water, methanol, mixtures thereof and solutions made therefrom. The term "organic solution" is used to describe substantially non-polar liquid compositions, or any part thereof, containing a non-polar organic solvent and free non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand. Of course it should be understood that such organic solutions, can contain additional constituents. Illustrative non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligands that may be employable in this invention include, e.g., trialkylphosphines and phosphites, dialkylarylphosphines and phosphites, alkyldiarylphosphines and phosphites, triaralkylphosphines and phosphites, dicycloalkylarylphosphines and phosphites, cycloalkyldiarylphosphines and phosphites, tricycloalkylphosphines and phosphites, triarylphosphines and phosphites, alkyl and/or aryl bisphosphines and bisphosphine mono-oxides, diorganophosphites, organobisphosphites and polyphosphites. Mixtures of such ligands, as well as tertiary organophosphinite ligands, may also be employed if desired. Such organophosphines and organophosphites and/or methods for their preparation are well known in the art as disclosed e.g. in US-A-3,527,809; 4,148,830; 4,247,486; 4,260,828; 4,283,562; 4,306,087; 4,400,548; 4,429,161; 4,482,749; 4,491,675; 4,528,403; 4,593,011; 4,593,127; 4,599,206; 4,668,651; 4,694,109; 4,717,775; and 4,748,261; EP-A-96,986; 96,987; and 96,988; and PCT Applications Publication Nos. WO 80/01690 and WO 87/07600. Of course the hydrocarbon radicals of such organophosphorus ligands may be substituted if desired, with any suitable substituent that does not unduly adversely affect a hydroformylation process or this invention. Illustrative substituents that may be on the hydrocarbon radicals in addition of course to corresponding hydrocarbon radicals such as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents, may include for example silyl radicals; amino radicals; acyl radicals; acyloxy radicals; amido radicals; sulfonyl radicals; alkoxy radicals; thionyl radicals; phosphonyl radicals; as well as, halogen, nitro, cyano, trifluoromethyl, and hydroxy radicals, and the like, such as disclosed e.g. in US-A-3,527,809 and 4,717,775. Of course it is to be understood that any substituted or unsubstituted hydrocarbon groups that make up a particular given organophosphorus ligand may be the same or different. Preferred organophosphines include the tertiary organophosphines mentioned above, especially triphenylphosphine, propyldiphenylphosphine, t-butyldiphenylphosphine, n-hexyldiphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine and tribenzylphosphine. Preferred organophosphites include triarylphosphites e.g. triphenylphosphite as well as diorganophosphites such as disclosed e.g. in US-A-4,717,775, organobisphosphites such as disclosed e.g. in US-A-4,749,261 and organobis- and polyphosphites such as disclosed e.g. in US-A-4,668,651. Of course it is to be understood that the term "complex catalyst," "coordination complex" and the like means a coordination compound formed by the union of one or more electronically rich molecules or atoms capable of independent existence, with one or more electronically poor molecules or atoms each of which also is capable of independent existence. Organophosphorus ligands, whose phosphorus atom (or other hetero-atom such as oxygen) has one available or unshared pair of electrons, are capable of forming a coordinate bond with Group VIII transition metals such as rhodium. The ultimate composition of the coordination complex also may contain additional ligands which satisfy the coordination sites or nuclear charge of the complex such as carbon monoxide, hydrogen and the like. As pointed out in the identified prior art, the rhodium coordination complex employed in hydroformylation reactions as the complex catalyst may be formed initially by methods known in the art. For example, a preformed stable crystalline solid of rhodium hydridocarbonyl-tris (triphenylphosphine), may be introduced into the reaction medium of a hydroformylation process. Such a material may be formed for example, by a method disclosed in Brown et al. Journal of the Chemical Society , 1970, pages 2753-2764. Alternatively, the rhodium coordination complex catalyst present in the hydroformylation reaction medium can be derived initially from a rhodium catalyst precursor such as rhodium carbonyl triorganophosphorus (e.g. triphenyl) acetylacetonate, Rh₂O₃, Rh(OAc)₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh(NO₃)₃ or rhodium dicarbonyl acetylacetonate, and the like, which have been introduced into the reaction medium of a hydroformylation process and form, in situ , e.g. rhodium coordination complex catalyst consisting essentially of carbon monoxide and organophosphorus ligands. The terminology "consisting essentially of" when used herein in connection with a hydroformylation catalyst is not meant to exclude, but rather include, hydrogen as well as carbon monoxide and organophosphorus complexed with the rhodium, said hydrogen and carbon monoxide of course being derived from the hydrogen and carbon monoxide gases which are an integral part of any hydroformylation process if not already present in the catalyst precursor. It is not intended to limit the present invention by the above explanation as to which organophosphorus ligand (or relative amount thereof) is tied to or complexed with the rhodium, nor as to the relative proportions of free organophosphorus ligand. Rhodium coordination complex obtained upon transferring rhodium, from the polar solution initially used to remove rhodium from hydroformylation reaction medium back into a non-polar organic solution containing an organophosphorus ligand also forms an active rhodium coordination complex in the hydroformylation reaction medium under the conditions of hydroformylation. The present invention (i.e., the non-polar solution provided thereby) has particular applicability in connection with a hydroformylation reaction. A process suitable for hydroformylating higher olefinic compounds is described in US-A-4,593,127 and uses a substantially non-polar hydroformylation reaction medium comprising both the non-polar organic solvent-soluble and polar solvent-insoluble rhodium-organophosphorus ligand coordination complex catalyst and free non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand dissolved in a non-polar organic solvent. By "free ligand" is meant organophosphorus ligand that has not formed a complex with the rhodium. The olefinic hydrocarbon reactant together with carbon monoxide and hydrogen are fed into a hydroformylation reactor containing the hydroformylation catalyst. Suitable olefinic compounds can be terminally or internally unsaturated and can have straight-chain, branched-chain or cyclic structures and can also be a mixture of olefin such as obtained from the oligomerization of propene, butene and isobutene, (such as so called dimeric, trimeric or tetrameric propylene or codibutylene, as disclosed e.g. in US-A-4,518,809 and 4,528,403). Moreover, such olefinic compounds may further contain one or more ethylenic unsaturated groups and of course mixtures of two or more different olefinic compounds may be employed as the starting hydroformylation material if desired. Further such olefinic compounds and the corresponding aldehyde products derived therefrom may also contain one or more groups or substituents which do not unduly adversely affect the hydroformylation process such as carbonyl, carbonyloxy, oxy, hydroxy, oxycarbonyl, halogen, alkoxy, aryl and haloalkyl, as described e.g. in US-A-3,527,809 and 4,731,486. Illustrative olefinic unsaturated compounds are alpha-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers and alkenols, e.g., ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methyl propene (isobutylene), 2-pentene, 2-hexene, 2-heptene, propylene dimers, propylene trimers, propylene tetramers, 2-ethyl hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl butyrate, methyl methacrylate, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methyl styrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene, 1,3-disopropenyl-benzene, eugenol, iso-eugenol, safrole, iso-safrole, anethol, 4-allylanisole, indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene and linalool. As noted above, the hydroformylation reaction medium consists essentially of a non-polar organic solvent-soluble and polar solvent-insoluble coordination complex of rhodium and an organophosphorus ligand and free organophosphorus ligand both dissolved in a non-polar organic solvent. Any non-polar organic solvent which does not adversely affect the desired hydroformylation reaction can be employed, especially including those solvents known to be suitable for use in prior art hydroformylation processes as previously described. The non-polar organic solvent employed must be sufficiently immiscible with a polar solution so that the hydroformylation reaction medium forms a distinct non-polar liquid phase in the presence of the polar phase. The non-polar organic solvent also preferably exhibits very little solubility in the polar solution so as to minimize any added costs associated with recovery and/or replacement of the various constituents of the polar and non-polar phases. The amount of non-polar organic solvent is not critical and need only be that amount which provides the desired rhodium and dissolved ligand concentrations. Typically, the amount of organic solvent may range from about 5 percent by weight up to about 95 percent by weight or more based on the total weight of the hydroformylation reaction medium. Hydroformylation is effected in the liquid reaction medium (non-polar organic solution) in the presence of a catalytically effective amount of the non-polar organic solvent-soluble and polar solvent-insoluble rhodium-organophosphorus ligand coordination complex. The rhodium complex concentration may range from about 1 part per million (ppm), calculated as rhodium metal, up to about 50,000 parts per million (ppm) or more, with a rhodium concentration in the range of about 10 ppm to 1,500 ppm being sufficient for most hydroformylations. Generally, there is no advantage to the hydroformylation reaction in using concentrations of rhodium in excess of about 1,000 ppm. Usually, on the grounds of expense alone, it will be preferred to operate at an active rhodium coordination complex catalyst concentration of not more than about 500 ppm, calculated as rhodium metal, while more typical operating conditions generally utilize active rhodium coordination complex catalyst concentrations of from about 50 ppm up to about 350 ppm, calculated as rhodium metal. The liquid hydroformylation reaction medium also preferably contains free non-polar organic solvent-soluble and polar solvent-insoluble ligand. Thus, preferably there are at least about 1 mol of free ligand for every gram-atom (mol) of rhodium present. Usually it will be preferred to operate in the presence of at least 2 mols of free ligand. In the case where triphenylphosphine (TPP) ligand is used, it is preferred to operate the hydroformylation reaction in the presence of at least about 75 mols, and more preferably at least about 100 mols, of free organophosphorus ligand per gram-atom of rhodium. Other organophosphorus ligands, e.g. cyclohexyldiphenylphosphine and diorganophosphites, are preferably employed in less amounts, such as e.g. from about 3 to 50 mols of ligand per mol of rhodium. Thus, the upper limit of the amount of free organophosphorus ligand is not particularly critical and is dictated mainly by the particular organophosphorus ligand employed, by the solubility thereof in the non-polar liquid reaction medium, as well of course by economic and commercial considerations. The conditions for effecting the hydroformylation reaction process may be those heretofore conventionally used. In a continuous hydroformylation, and in particular when hydroformylating higher C₆ to C₃₀ olefinic compounds, the continuous operation involves removing a portion of the liquid hydroformylation reaction medium containing aldehyde product from the hydroformylation reaction zone (hydroformylation reactor); recovering a desired amount of aldehyde product therefrom via vaporization; and recycling the remaining non-volatilized catalyst containing liquid medium back to the hydroformylation reaction zone (e.g. reactor). During such continuous hydroformylation of higher olefinic compounds using conventional non-polar solvent-soluble and polar solvent-insoluble organophosphorus ligands, aldehyde condensation by-products having a low volatility relative to the organophosphorus ligand of the rhodium hydroformylation catalyst, accumulate at a significant rate and need to be controlled or removed, if one wishes to prolong the effective life span of the catalyst in the continuous hydroformylation operation, for the reasons mentioned above For instance one could maintain the continuous hyroformylation process by treating some or all of the rhodium catalyst containing liquid hydroformylation reaction medium after its removal from the hydroformylation reaction zone (e.g. reactor) either before and/or after, preferably, after, a desired amount of aldehyde product has been recovered via volatilization or distillation from said medium, by non-polar to polar, back to non-polar extraction treatments to recover rhodium values thereof removed from such low volatile by-products and returning the non-polar back extracted rhodium-non-polar ligand complex containing organic solution to the hydroformylation reaction medium which remained in the reaction zone (e.g. reactor). Alternatively the hydroformylation or part of same could be terminated and all of the catalyst-containing non-polar hydroformylation reaction medium so-treated to recover the non-polar back extracted rhodium-non-polar ligand complex containing organic solution which can be used either as a source of rhodium for a new hydroformylation reaction medium in the reactor or as a catalytic booster for feeding to any other hydroformylation reaction medium being used in such a hydroformylation process. For example one could shut down one or more hydroformylation reactors of a series of reactors being used, and treat the catalyst containing hydroformylation reaction medium(s) after removing same from the reactor(s) and use the non-polar back extracted rhodium-non-polar ligand complex containing organic solution as disclosed above. Preferred polar solvent-soluble ionic organophosphine ligands used in the starting solutions of the method of the present invention have the general formulae (1) and (2): where R¹, R² and R³of formula (1) and R⁴, R⁵, R⁶ and R⁷ of formula (2) each individually represent a hydrocarbon radical containing from 1 to 30 carbon atoms selected from alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, where Q in formula (2) represents a divalent organic bridging group and where Y¹, Y² and Y³ of formula (1) and, Y⁴, Y⁵, Y⁶ and Y⁷ of formula (2) are substituted on the hydrocarbon radical and each individually represents an ionic radical of overall neutral charge selected from: -SO₃M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, e.g. methanol-soluble or water-soluble, -PO₃M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, e.g. methanol-soluble or water-soluble, -NR₃X' wherein each R represents a hydrocarbon radical containing from 1 to 30 carbon atoms selected from the class consisting of alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, and X' represents inorganic or organic anionic atoms or radicals selected so that the ligand is polar solvent soluble, e.g. methanol-soluble or water-soluble, and -CO₂M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, e.g. methanol-soluble or water-soluble, wherein m¹, m² and m³ of formula (1) and m⁴, m⁵, m⁶ and m⁷ of formula (2) are integers which can be the same or different and which can range from 0 to 5. At least one of m₁, m₂ and m₃ and at least one of m₄, m₅, m₆ and m₇, cannot be zero (0), i.e., must be equal to or greater than 1, and must have a value sufficient to impart solubility in the polar solvent to the ligand. The integers m₁ through m₇ indicate the number of ionic radicals of overall neutral charge substituted on each hydrocarbon radical. The hydrocarbon radicals, R¹, R² and R³ of formula (1) and R⁴, R⁵, R⁶ and R⁷ of formula (2) preferably contain from 1 to 18 carbon atoms. Hydrocarbon radicals containing from 1 to 12 carbon atoms are more preferred. Such hydrocarbon radicals include those e.g. selected from alkyl, aryl, alkaryl, aralkyl and cycloalkyl. Illustrative hydrocarbon radicals are e.g. methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl and the like. Most preferably, at least one of R¹, R² and R³ in formula (1) and at least one of R⁴, R⁵, R⁶ and R⁷ in formula (2) is a phenyl radical. Such hydrocarbon radicals may contain one or more substituents provided that they do not unduly adversely affect the use of the ligand and this invention. Suitable substituents, in addition to the necessary ionic substituent, e.g., the sulfonate or carboxylate include straight and branched chain alkyl groups, preferably of 1 to 4 carbon atoms, alkoxy groups, halogen atoms, hydroxy, cyano, nitro and amino groups and the like. More preferably at least two, and most preferably three of R¹, R² and R³ in formula (1) are phenyl groups and at least three and most preferably four of R⁴, R⁵, R⁶ and R⁷ in formula (2) are phenyl radicals. The organic divalent bridging group represented by Q in the above formulas is a divalent radical containing from 1 to 30 carbon atoms selected from hydrocarbon radicals, oxygen containing hydrocarbon radicals (i.e. hydrocarbon radicals interrupted with an oxygen atom), sulfur containing hydrocarbon radicals (i.e. hydrocarbon radicals interrupted with a sulfur atom) and nitrogen containing hydrocarbon atoms (i.e. hydrocarbon radicals interrupted with a nitrogen atom). Preferably such radicals contain from 1 to 16 and more preferably from 1 to 12 carbon atoms. Illustrative divalent hydrocarbon radicals include alkylene radicals (e.g. methylene (-CH₂-), ethylene, propylene, isopropylene, butylene, 1,2-dimethylethylene, t-butylene, neopentylene, 2-methylproylene, hexylene, 2-ethylhexylene, dodecylene and eicosylene); arylene radicals (e.g. phenylene, substituted phenylene, diphenylene and substituted diphenylen); as well as alkylene containing arylene radicals (e.g. methylenephenylene (-CH₂C₆H₄-), ethylene-phenylethylene (-C₂H₄C₆H₄-C₂H₄-), phenylenepropylphenylene (-C₆H₄C(CH₃)₂C₆H₄-), and methylenediphenylmethylene (-CH₂C₆H₄C₆H₄CH₂-)); and alkylidene radicals (e.g. ethylidene (-CH=CH-)). Illustrative oxygen containing hydrocarbon radicals include alkyleneoxyalkylene radicals (e.g. ethyleneoxymethylene (-C₂H₄OCH₂-), propyleneoxymethylene (-C₃H₆OCH₂-), ethyleneoxyethylene (-C₂H₄OC₂H₄-), 1,2-bis(ethyleneoxy)ethane (-C₂H₄OC₂H₄OC₂H₄-), propyleneoxypropylene (-C₃H₆OC₃H₆-)), and aryleneoxyalkylene radicals (e.g. phenyleneoxymethylene (-C₆H₄OCH₂-)). Illustrative sulfur or thio containing hydrocarbon radicals include alkylenethioalkylene radicals (e.g. ethylenethioethylene (-C₂H₄SC₂H₄-), 1,2-bis(ethylenethio)ethane (-C₂H₄SC₂H₄SC₂H₄-), propylenethiomethylene (-C₃H₆SCH₂-), propylenethiopropylene (-C₃H₆SC₃H₆-)); arylenethioalkylene radicals (e.g. phenylenethiomethylene (-C₃H₆S-CH₂-)). Illustrative amino containing hydrocarbon radicals include alkylene-aminoalkylene radicals (e.g., methyleneaminomethylethylene (-CH₂N(CH₃)C₂H₄-), ethyleneaminomethylethylene (-C₂H₄N(CH₃)C₂H₄), bis(ethyleneaminomethyl)ethane (-C₂H₄N(CH₃)C₂H₄N(CH₃)C₂H₄-) and propyleneamino methylpropylene (-C₃H₆N(CH₃)C₃H₆-). Most preferably Q is a divalent hydrocarbon radical, especially a divalent alkylene radical containing from 2 to 8 carbon atoms. Particularly, suitable ionic organophosphine ligands are the ionic triarylphosphines and, in particular, the salts of sulfonated and of carboxylated triarylphosphines, as, for example, are described in US-A-4,248,802; 4,399,312; 4,668,824; 4,716,250 and 4,731,486; and EP-A-216,315. Preferred among this group are the salts of monosulfonated and of trisulfonated triphenylphosphines, and the salts of mono-carboxylated and of tricarboxylated triphenylphosphine. Another suitable class of ionic organophosphines are ionic bisdiarylphosphines such as bisdiphenylphosphinoethane monosulfonate salts. Mixtures of suitable ionic phosphine ligands also can be employed. Such polar solvent-soluble, ionic organophosphine ligands capable of forming a coordination complex with rhodium embraced by the above formulae, as well as methods for their preparation, are well-known in the art and need not be described in detail. See for example J . Chem. Soc. (1958), pp. 276-288 and US-A-4,248,802; 4,399,312; 4,483,802; 4,633,021; 4,668,824; 4,716,250 and 4,731,486. For example sulfonated ligands may be prepared by sulfonating the corresponding phosphine, e.g. triphenylphosphine, with fuming sulfuric acid (oleum) under controlled temperature conditions. The ionic phosphine ligands are present in the present invention in their polar solvent-soluble, e.g. water-soluble or methanol-soluble, salt form. As suitable counter-ions, M, for the anionic moieties of the ionic phosphine salts there can be mentioned the cations of the alkali and alkaline earth metals, e.g., lithium, sodium, potassium, cesium, rubidium, calcium, barium, magnesium and strontium, the ammonium cation and quaternary ammonium cations. Suitable anionic atoms or radicals include, for example, sulfate, carbonate, phosphate, chloride, acetate and oxalate. Of course it is understood that the number of anionic and cationic moieties in a ligand molecule also depends on the valences of the ions (ionic radical) and counter-ions (M and X') of any particular ligand. The polar solution also may include other adjuvants. For example a neutral salt, e.g., sodium sulfate or phosphate, could have been added to the polar phase to increase its density. In accordance with the present invention, the polar solution is treated with a conditioning reagent in order to reduce the amount, in the polar solution, of the polar solventsoluble ionic organophosphine ligand capable of complexing with the rhodium. In other words, the polar solution is treated so that the complex-forming ability of polar solvent-soluble ligand is rendered incapable or less capable of forming a coordination complex with rhodium. If desired, the concentration of rhodium in the polar solution can be concentrated, e.g. by vaporization, before or after treatment with the conditioning reagent. In any event, the polar solution generally will be have a rhodium concentration of from about 1 to 50,000 ppm, and more typically between about 500 and 2,500 ppm, calculated as rhodium metal. In accordance with the present invention, the polar solution can be treated with a variety of conditioning reagents in order to reduce the amount of (i.e. chemically degrade or alter) the polar solvent-soluble ionic organophosphine ligand. For example, the polar solution can be treated with an ylid precursor such as maleic acid, with a strong acid such as sulfuric acid, with an alkylating agent such as methyl iodide or with an oxidizing reagent such as hydrogen peroxide or an organic peroxide. The conditioning reagent should react with the polar solvent-soluble ligand to produce products that lack a coordinating affinity for the rhodium. Preferably, the reaction products are polar-soluble and non-polar organic solvent-insoluble so that they are not extracted into the non-polar organic solvent during subsequent treatment. Treatment with the conditioning reagent thus reduces the amount, in the polar solution, of polar solvent-soluble ligand capable of strongly coordinating with rhodium. Although not particularly critical, the polar solution preferably is treated with the conditioning reagent at a temperature of between about 0° to 250°C for a time between about 0.1 to 24 hours. In any event, the solution should be treated under conditions necessary to reduce the amount of ligand capable of complexing with the rhodium by an amount sufficient to permit extraction of rhodium into a non-polar organic solvent which contains a non-polar organic solvent-soluble and polar solvent-insoluble organosphosphorus ligand. A treatment temperature of about 25° to 60°C for a time period of one to four hours should be adequate in most cases. While the degree of reduction in the amount of the polar solvent-soluble ligand in any particular circumstance will be influenced, inter alia , by the nature and initial concentration of the polar solvent-soluble ligand itself, by the nature and amount of the non-polar organic solvent-soluble and polar solvent-insoluble ligand in the organic extractant and by the conditions of the extraction, it is preferred to reduce the amount of polar solvent-soluble ligand by at least about 70% and preferably by at least about 85%. An amount of residual polar solvent-soluble ligand of below about 10 equivalents, i.e., 10 mols of ligand per gram atom of rhodium, and preferably below about 5 equivalents is especially preferred. Best results are obtained if the rhodium-coordination ability of the polar solvent-soluble ligand is completely destroyed. Suitable ylid precursors for use in the present invention as conditioning reagents are unsaturated compounds containing from 2 to 18 carbon atoms, preferably from 3 to 10 carbon atoms, and can be selected from unsaturated compounds having the formula wherein X is a radical selected from -CN,-Cl,-Br,-I,-NO₂, and -OR¹²;R¹¹ is a radical selected from hydrogen, alkyl, aryl, hydroxy, alkoxy, amino and halogen; R¹² is an alkyl or aryl radical; and R⁸, R⁹ and R¹⁰ individually are radicals selected from hydrogen, alkyl, aryl, X radicals as defined above and -CH₂X radicals wherein X is the same as defined above; and wherein R⁸ and R⁹ taken together can form an alkylene group having from 2 to 8 carbon atoms; and anhydrides of the carboxylic acids of the unsaturated compounds within the scope of formula (A). Maleic acid and maleic anhydride are particularly useful reagents. A strong acid conditioning reagent suitable for treating the polar solution may be an inorganic or organic acid. Such inorganic acids as hydrochloric, sulfuric, nitric, phosphoric and such organic acids such as methanesulfonic acid and para-toluenesulfonic acid are suitable. Many others will be apparent to those skilled in the art. Sulfuric acid is preferred. To an extent, treatment with a strong acid conditioning agent is reversible. Thus the complex-forming ability of polar solvent-soluble ligand previously rendered incapable of forming a coordination complex with rhodium by treatment with the strong acid, can, by subsequent treatment with an appropriate alkaline reagent, such as sodium hydroxide, be restored. Acceptable alkylating reagents for use as the conditioning reagent can be selected from the class of compounds capable of reacting with the polar solvent-soluble ionic organophosphine ligand to form a polar solvent-soluble phosphonium salt thereof. Compounds of this class are monovalent hydrocarbon halides, such as methyl iodide (see US-A-4,429,161). An oxidizing agent suitably employed in this invention as the conditioning reagent may be supplied in the form of a gas or liquid and can be selected from oxygen, hydrogen peroxide, and organic peroxides, metal oxidizing reagents and peracids which preferably form polar solvent-soluble oxidation by-products with the polar solvent-soluble organophosphine ligand. Hydrogen peroxide is a particularly suitable oxidizing agent. It is to be understood that oxygen need not be employed in its pure form, but more preferably and conveniently is employed in the form of air or in admixture with an inert gas, such as nitrogen in order to minimize any explosive hazards. The liquid organic peroxides, which may also be employed as oxidants herein, preferably encompass polar solvent-soluble organic peroxides of the formula R-O-O-R', wherein R represents a radical selected from monovalent hydrocarbon radicals of 2 to 20 carbon atoms, carboxylic acyl radicals of 2 to 20 carbon atoms, aroyl radicals of 7 to 20 carbon atoms and cycloalkoxycarbonyl radicals of 4 to 20 carbon atoms, and wherein R' represents a radical selected from hydrogen and a radical represented by R as defined above. Preferred monovalent hydrocarbon radicals represented by R and R' above are alkyl and aralkyl radicals, especially t-alkyl radicals of 4 to 20 carbon atoms and aralkyl radicals of 8 to 15 carbon atoms. Most preferably R' represents hydrogen (i.e., -H). Illustrative organic peroxides include t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide and ethylbenzene hydroperoxide. Such organic peroxides and/or methods for their preparations are well known in the art. The polar solution recovered from this treatment, having a lowered amount of rhodium complex-forming, polar solvent-soluble ionic organophosphine ligand then can be contacted extracted) with an immiscible, non-polar, organic solvent containing a non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand. The non-polar organic solvent-soluble and polar solvent-insoluble ligands previously described can be employed. The contacting typically can be done in an extraction column. Any substantially non-polar organic solvent which forms a separate, distinct phase in the presence of a polar phase, e.g., an aqueous phase, and, in the specific case of hydroformylation, which does not adversely affect (i.e., which is preferably compatible with) the desired hydroformylation reaction medium can be employed. Particularly useful non-polar solvents are those known to be suitable for use in prior art hydroformylation processes as described previously herein. The non-polar organic solution used for extraction preferably contains the same non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand which is to be used in the hydroformylation reaction medium. The non-polar organic solvent should contain an amount of the non-polar organic solvent-soluble and polar-solvent-insoluble organophosphorus ligand sufficient to extract rhodium from the treated polar solution. The necessary concentration of the non-polar organic solvent-soluble and polar solvent-insoluble ligand will depend, inter alia , on the nature and residual level of the polar-soluble ionic phosphine ligand in the polar solution (e.g., aqueous phase), on the particular non-polar organic solvent-soluble and polar solvent-insoluble ligand and its amount in the organic solvent and on the extraction conditions. Generally, routine experimentation can be used to determine the suitability of any particular non-polar solvent-soluble ligand as a back extractant, as well as to determine both a suitable ligand concentration for the non-polar solvent and suitable extraction conditions. Typically, the non-polar organic solvent will contain about 0.01 to 1.0 mols per liter of the non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand and normally will contain about 0.03 to 0.6 mols per liter. Normally to ensure a satisfactory extraction of rhodium from the polar solution, there should be sufficient non-polar organic solvent-soluble and polar solvent-insoluble ligand in the organic solvent to yield a ratio of the molar concentration of non-polar organic solvent-soluble and polar solvent-insoluble ligand in the organic solvent (non-polar ligand) to the molar concentration of residual polar solvent-soluble ionic ligand capable of forming a coordination complex with rhodium in the polar phase (polar ligand) of above about 10, preferably above about 20, and most preferably above about 30. Conditions and equipment for the extraction step can be the same as those employed in the organic-polar contacting step used to transfer rhodium from the catalyst solution to the polar solution (as described in EP-A-354 588). In the case of hydroformylation, an organic solution of ligand-rhodium complex suitable for use in a hydroformylation reaction medium is recovered as overhead from extraction column while a polar solution, e.g., an aqueous solution, with a reduced concentration of rhodium is recovered from the column's bottom. This polar solution can-be used to prepare polar solvent-soluble ionic organophosphine ligand-containing polar solution used for contacting hydroformylation reaction medium. The organic solvent containing the extracted rhodium can be used for any number of purposes as described above. In the case where hydroformylation reaction medium is treated in accordance with the present invention, applicants have found that the rhodium transferred into the ligand-containing organic solvent, using either of the alternative embodiments described above, becomes substantially active under hydroformylation reaction conditions when subsequently used for hydroformylation catalysis. The following examples are illustrative of the present invention and are not to be regarded as limitating. It should be understood that all of the parts, percentages, and proportions referred to herein and in the appended claims are by weight unless otherwise indicated. In the following examples, the ionic phosphine ligand, 3-(diphenylphosphino)- benzenesulfonic acid, sodium salt is referred to in the alternative as the sodium salt of triphenylphosphine monosulfonic acid and as TPPMS-Na, the ionic phosphine ligand tri(sulfophenyl) phosphine, sodium salt is referred to in the alternative as the sodium salt of triphenylphosphine trisulfonic acid and as TPPTS-Na; finally the ionic phosphine ligand bisdiphenylphosphino-ethane m-monosulfonic acid, sodium salt, is referred to in the alternative as the sodium salt of DIPHOS-monosulfonic acid and as S-DIPHOS-Na. Rhodium concentrations were determined using atomic absorption spectroscopy (AAS), non-polar organic solvent-soluble ligand concentrations were determined using vapor phase chromotography (VPC), while the ionic phosphine - ligand concentrations were determined using high performance liquid chromotography (HPLC). Such procedures are well-known to those skilled in the art. EXAMPLE 1 (reference example) In this example a 3% by weight aqueous (polar) solution of the sodium salt of triphenylphosphine monosulfonic acid was used to extract active rhodium from spent hydroformylation reaction medium having an activity of 75%, a rhodium concentration of 727 ppm, a triphenylphosphine (TPP) ligand concentration of 10% by weight, 80% by weight pentadecanal and the balance hydroformylation aldehyde condensation by-products. In each case, two sequential, equally sized aqueous washes (extractions) were used. Table 1 presents the results obtained. EXAMPLE 2 (reference example) This example reports the ability of a 10% by weight aqueous (polar) solution of TPPMS-Na to extract active rhodium from a spent hydroformylation reaction medium having an activity of 39%, a rhodium concentration of 540 ppm, 10% by weight triphenylphosphine (TPP) ligand, 30% by weight butyraldehyde and the balance aldehyde condensation by-products. Two equally sized aqueous washes (extractions) were used. The results are presented in Table 2. EXAMPLES 3-6 These examples illustrate the use of maleic acid (MA) as a conditioning reagent for reducing the amount in a polar solution, e.g., in an aqueous solution, of the polar solvent-soluble organophosphine ligand capable of forming a coordination complex, i.e. capable of complexing, with rhodium and the effect on the polar to non-polar extraction efficiency. The aqueous solution was obtained by extracting a non-polar hydroformylation catalyst solution containing 540 ppm rhodium, 10% by weight TPP, 30% by weight butyraldehyde and the balance aldehyde condensation by-products with an aqueous solution containing 5% by weight TPPMS-Na. Twenty gram samples of the resultant aqueous solution containing 5% by weight TPPMS-Na and 489 ppm rhodium were treated by mixing with various amounts of maleic acid at a temperature of 50°C for 30 minutes to convert water-soluble ionic ligand in each sample to a water-soluble non-coordinating form. The maleic acid-treated samples then were back extracted using a Texanol® solution containing 10% by weight tri-phenylphosphine (TPP). Each treated sample was washed three times with 20 gram portions of the Texanol® ligand solution. The results are presented in Table 3. As shown, by reducing the ligand concentration in the aqueous phase to less than 5.0 mols of ligand per gram-atom of rhodium (which in these cases also corresponded to greater than about 85% ligand removal), excellent back-extraction of the rhodium was realized. EXAMPLES 7-10 These examples illustrate the use of different levels of maleic acid (MA) as a conditioning reagent for reducing the amount of TPPMS-Na ligand capable of complexing with rhodium in aqueous (polar) solutions containing various amounts of rhodium and the effect of such treatment on rhodium extraction efficiency. The aqueous solution used in Examples 7 and 9 correspond to the aqueous solutions obtained in Examples 1 and 2 respectively; while the aqueous solutions for Examples 8 and 10 were obtained by extracting non-polar hydroformylation catalyst solutions containing 300 ppm rhodium, 10% by weight TPP and the balance Texanol®, and 375 ppm rhodium, 11% by weight TPP, 6% by weight butyraldelhyde and the balance aldehyde condensation by-products respectively with 10% by weight aqueous solution of TPPMS-Na and a 5% by weight aqueous solution of TPPMS-Na. The MA-treated aqueous (polar) solutions were each back-extracted three times using 25 gm portions of a 10% by weight solution of triphenylphosphine in Texanol®. The aqueous solutions containing the added maleic acid were heated at 50°C for about 30 minutes. The results are presented in Table 4, and demonstrate the effectiveness of maleic acid in conditioning the aqueous solution for extraction. EXAMPLE 11 This Example illustrates the use of an organic solution of cyclohexyldiphenylphosphine (CHDPP) ligand for extracting rhodium from an aqueous extractant solution. A 25 gram sample of an aqueous solution containing 5% by weight TPPMS-Na, used to extract rhodium from spent hydroformylation reaction medium containing 540 ppm rhodium, 10% by weight TPP, 30% by weight butyraldehyde and the balance aldehyde condensation by-products, contained 78 ppm rhodium after such extraction. The sample was treated at 50°C for about 30 minutes with 0.4 grams of maleic acid and then was extracted three times (25 gram portions) using a 3.0% by weight solution of CHDPP in Texanol® solvent. Analysis of the cumulative organic extractants showed that 96.9% of the rhodium was transferred from the aqueous solution into the organic phase. EXAMPLE 12-15 These examples illustrate the use of strong acid conditioning reagents for converting TPPMS-Na ligand in aqueous (polar) solutions containing various amounts of rhodium to a non-coordinating form, i.e. less capable of complexing with rhodium, and the effect of such treatment on extraction efficiency. In Example 12, the original aqueous solution was obtained by extracting a non-polar hydroformylation catalyst solution containing 540 ppm rhodium, 10% by weight TPP, 30% by weight butyraldehyde and the balance aldehyde condensation by-products with an aqueous solution of 5% by weight TPPMS-Na; in Examples 13 and 14 the original aqueous solutions were obtained by extracting a non-polar hydroformylation catalyst solution containing 1000 ppm rhodium, 20% by weight TPP, 24% by weight butyraldehyde and the balance Texanol® with aqueous solutions of 3% by weight TPPMS-Na, and in Example 15, the original aqueous solution was obtained by extracting a non-polar hydroformylation catalyst solution containing 300 ppm rhodium, 3% by weight TPP and the balance Texanol® with an aqueous solution of 5% by weight TPPMS-Na. The acid-treated aqueous solutions were each sequentially extracted three times (25 gm portions) using a 10% by weight solution of triphenylphosphine (TPP) in Texanol® solvent. The aqueous solutions containing the added acid were heated at 50°C for about 30 minutes. The results are presented in Table 5 and demonstrate the effectiveness of strong acid treatment for conditioning the aqueous (polar) solution for extraction of rhodium from the aqueous phase. EXAMPLE 16 (reference example) This example describes the continuous extraction of rhodium from hydroformylation reaction medium using a 3/8 inch diameter extraction column having five (5) theoretical stages and counter current flow of the organic solution and an aqueous solution containing TPPMS-Na ligand. The combined feed rate to the extraction column (organic phase plus aqueous phase) was maintained at about 1700 gm/hour in all the runs and the column was operated at about 35°C. A rhodium balance was determined for each run from the feed rates and rhodium concentrations of the various streams and is reported in Tables 6 and 7. Extraction efficiencies were calculated by determining the percentage of rhodium transferred from the organic phase to the aqueous phase and then normalizing the value by dividing it with the catalyst activity. The results are presented in Tables 6 and 7. Table 6 illustrates the effect of reducing the amount of the aqueous feed relative to the organic feed. In these runs a 5.0% by weight polar solution of TPPMS-Na was used to extract rhodium from an organic solution having a 39% activity as a hydroformylation catalyst and containing 1073 ppm rhodium, 15% by weight TPP, 38% by weight butyraldehyde, 10% by weight hexane, 10% by weight C₉ aldehyde and the balance butyraldehyde condensation by-products. This same hydroformylation catalyst solution also was used for run number 8 in Table 7. The results show that as the amount of aqueous feed is reduced (i.e. as the organic/aqueous (O/A) volume ratio increases) the extraction efficiency decreased. Due in part to the viscous nature of the organic solution, larger O/A ratios do not permit sufficient exposure of the rhodium in the organic phase to the aqueous extractant phase. Table 7 presents the remaining data. Run Nos. 4, 6 and 7 employed a hydroformylation catalyst solution containing 540 ppm rhodium, 10% by weight TPP, 30% by weight butyraldehyde and the balance aldehyde condensation by-products; run number 9 employed a hydroformylation catalyst solution containing 635 ppm rhodium, 12% by weight TPP, 30% by weight butyraldehyde, 20% by weight hexane, 10% by weight C₉ aldehyde and the balance butyraldehyde condensation by products; run numbers 5 and 10 employed as the non-polar feed material the organic solutions recovered from the extraction column in prior run numbers 4 and 9 respectively, and run number 10 employed a hydroformylation catalyst solution containing 312 ppm rhodium, 10% by weight TPP, 80% by weight butyraldehyde and aldehyde condensation by-products. EXAMPLE 17 This example illustrates the continuous extraction of rhodium from an aqueous (polar) solution containing 5% by weight TPPMS-Na ligand and 382 ppm rhodium. This aqueous solution corresponds to the aqueous stream recovered from run number 11 reported in Table 7. The same equipment employed in Example 16 was used. The aqueous solution first was treated with maleic acid to convert completely the TPPMS-Na ligand to a non-coordinating form. An isobutyraldehyde solution containing 10% by weight triphenylphosphine then was used as the non-polar extractant. An extraction efficiency of 83.0% was obtained. In the above formulae (1) and (2) preferred meanings of the radicals R and R¹ to R⁷ are: C₁₋₁₈-, particularly C₁₋₁₂- and most preferred C₁₋₈-alkyl; C₆₋₁₈-, particularly C₆₋₁₂-aryl, such as phenyl and naphthyl; C₇₋₁₈-, particularly C₇₋₁₂-alkaryl, such as tolyl, xylyl and ethylphenyl; C₇₋₁₈-, particularly C₇₋₁₂-aralkyl, such as benzyl and phenylethyl; C₃₋₈-, particularly C₄₋₆-cycloalkyl, such as cyclopentyl and cyclohexyl; m¹ to m⁷ preferably are integers of from 0 to 3, particularly 0 or 1. Preferred meanings for the various groups mentioned with respect to formula (A) above are: alkyl and aryl radicals as defined for R¹ to R⁷ above, including the particularly preferred meanings; alkoxy groups containing alkyl groups as defined above, including the particularly preferred alkyl groups; provided that the total number of carbon atoms in formula (A) does not exceed 18.

Claims: A method for recovering a Group VIII transition metal from a polar solution containing a polar solvent-soluble coordination complex of a Group VIII transition metal and a polar solvent-soluble ionic organophosphine ligand comprising: (i) treating the polar solution with a conditioning reagent to reduce the amount of said polar solvent-soluble ionic organophosphine ligand capable of forming a coordination complex with the Group VIII transition metal in the polar solution; and (ii) contacting the polar solution produced in accordance with step (i) with a non-polar organic solvent containing non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand capable of forming a coordination complex with the Group VIII transition metal to transfer said Group VIII transition metal from said polar solution into said non-polar organic solvent; with the proviso that said method is not preceded by the step of contacting a substantially non-polar organic solution containing a non-polar organic solvent-soluble and polar solvent-insoluble coordination complex of the Group VIII transition metal and a non-polar organic solvent-soluble and polar solvent-insoluble organo-substituted ligand of a trivalent atom with a polar solution containing said polar solvent-soluble ionic organophosphine ligand, thereby transfering said Group VIII transition metal from said organic solution into said polar solution and forming the polar solution to be treated according to the above steps (i) and (ii). The method of claim 1 wherein said Group VIII transition metal is rhodium. The method of any one of claims 1 and 2 wherein said polar solution is an aqueous solution. The method of claim 1 wherein said polar solvent -soluble ionic organophosphine ligand is selected from compounds having the general formulae (1) and (2): wherein R¹, R² and R³ of formula (1) and R⁴, R⁵, R⁶ and R⁷ of formula (2) each individually represent a hydrocarbon radical containing from 1 to 30 carbon atoms selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, where Q in formula (2) represents a divalent organic bridging group and where Y¹, Y² and Y³ of formula (1) and Y⁴, Y⁵, Y⁶ and Y⁷ of formula (2) are substituted on the hydrocarbon radical and each individually represents an ionic radical of overall neutral charge selected from the group consisting of; -SO₃M wherein M represent inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, -PO₃M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, -NR₃X' wherein each R represents a hydrocarbon radical containing from 1 to 30 carbon atoms selected from the class consisting of alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, and X' represents inorganic or organic anionic atoms or radicals selected so that the ligand is polar solvent soluble, and -CO₂M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is polar solvent soluble, wherein m¹, m² and m³ of formula (1) and m⁴, m⁵, m⁶ and m⁷ of formula (2) are integers which can be the same or different and which can range from 0 to 5, and wherein at least one of m₁, m₂ and m₃ in formula (1) and at least one of m₄, m₅, m₆ and m₇ in formula (2) is equal to or greater than 1, sufficient to impart solubility in a polar solvent to the ligand. The method of any one of claims 1 to 4 wherein said conditioning reagent is selected from the group consisting of an ylid precursor, a strong acid, an alkylating agent or an oxidizing reagent. The method of claim 5 wherein said ylid precursor is an unsaturated compound containing from 2 to 18 carbon atoms and is selected from the group consisting of compounds having the formula wherein X is a radical selected from the group consisting of -CN,-Cl,-Br,-I,-NO₂, and -OR¹²;R¹¹ is a radical selected from the group consisting of hydrogen, alkyl, aryl, hydroxy, alkoxy, amino and halogen; R¹² is an alkyl or aryl radical; and R⁸, R⁹ and R¹⁰ individually are radicals selected from the group consisting of hydrogen, alkyl, aryl, X radicals as defined above and -CH₂X radicals wherein X is the same as defined above; and wherein R⁸ and R⁹ taken together can form an alkylene group having from 2 to 8 carbon atoms; and anhydrides of the carboxylic acids of the unsaturated compounds within the scope of formula (A). The method of claim 6 wherein said ylid precursor is maleic acid or maleic anhydride. The method of any one of claims 1 to 7 wherein said non-polar organic solvent-soluble and polar solvent-insoluble organophosphorus ligand is selected from triarylphosphines and cycloalkyldiarylphosphines, particularly from triphenylphosphine and cyclohexyldiphenylphosphine. The method of claim 8 wherein said polar solvent-soluble ionic organophosphine ligand is selected from ionic triarylphosphines and ionic bisdiarylphosphines, particularly from sulfonated triphenylphosphines and sulfonated bisdiphenylalkylphosphines. The method of claim 2 wherein said rhodium exhibits catalytic activity in hydroformylation.

Inventors: BRYANT DAVID ROBERT, MILLER DAVID JAMES, BRYANT, DAVID ROBERT, MILLER, DAVID JAMES
Applicants: UNION CARBIDE CHEM PLASTIC, UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (A NEW YORK CORPORATION)
Application year: 1992
Main classification: B01J31
IPC codes: B01D11, C07B61, C01G55, B01J31, C07C47, C07C45, B01J38