TREATMENT OF RHODIUM CATALYSTS

Abstract: A process for treating an organic solution of a partially deactivated solubilized rhodium - tertiary organophosphine complex hydroformylation catalyst with an organic reagent in order to improve the extractability of rhodium therefrom into an aqueous solution containing an ionic organophosphine ligand.

Description: TKEATMENT OF RHODIUM CATALYSTS This applicataion is a Continuation-In-Part of U.S. Patent Application Serial No. 231,508 filed August 12, 1988. This invention relates to a process for treating an organic solution containing a partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst with certain organic reagents to obtain an organic solution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product which contains more rhodium correspondingly capable of being extracted into an aqueous solution containing an ionic organophosphine ligand, than contained in the organic solution starting material before said treatment. BACKGROUND OF THE INVENTION Processes using rhodium - tertiary non-ionic organophosphine complexes as homogeneous catalysts are well-known. Included in such processes are the hydrogenation of unsaturated compounds, the carbonylation o 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 rhodium from the catalyst solutions used in these process presents a particulary troublesome problem. Particularly illustrative of these homogeneous catalysis systems is the hydrofor ylation of olefinic compounds with carbon monoxide and hydrogen to produce aldehyde products in the presence of a rhodium - tertiary organophosphine complex hydroformylation catalyst. Of particular interest are those non-aqueous hydroformylation reactions designed to produce aldehydes at low pressures, such as disclosed, e.g. in U.S. Patent Numbers 3,527,809; 4,148,830; 4,247,486; and 4,731,486. Commercial experience has shown that, even in the substantial absence of extrinsic catalyst poisons, rhodium - tertiary organophosphine complex catalysts lose activity (i.e. become partially deactivated) during the course of " coritTinued ~ . "*■ "**"*" prolonged hydroformylation and such is commonly referred to as intrinsic deactivation. While it is difficult to ascertain the precise. reasons for such loss in activity, such deactivation is believed to be due in a large part to the combined effects of a number of processing conditions, e.g. reaction temperature, reactant partial pressures, the phosphine ligand, the ligand to rhodium mole ratio, and rhodium concentration employed. Since the variables significant for such catalyst instability are also variables essential for the hydroformylation, obviously such deactivation can not be totally avoided although it can be controlled or minimized. However, eventually the activity of the catalyst will decrease to such a point that it is no longer desirable to operate the hydroformylation process and the catalyst will either have to be reactivated or discharged and replaced with fresh catalyst. Another potential problem for continuous hydroformylation processes is the accumulation of aldehyde condensation by-products of low volatility relative to the organophosphine 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 low enough to be easily controlled. Thus, in the case of hydroformylating lower olefins, catalyst life mainly is limited by the rate of catalyst deactivation. 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. 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. Continuous hydroformylation of higher olefinic compounds, such as higher alpha-olefins, containing e.g., from six to thirty carbon atoms, using conventional organic (non-polar) solvent-solubilized non-ionic 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 boiling 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 raβε- ' θπpractical 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 problem of recovering the rhodium values from said overwhelmed catalyst solution that is replaced. 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. Assignee's U.S. Patent Application Serial No. 231,508, entitled CATALYTIC METAL RECOVERY FROM NON-POLAR ORGANIC SOLUTIONS filed August 12, 1988 in the names of David J. Miller and David R. Bryant (the entire disclosure of which is encompassed herein) is directed to solving the above problem by a novel method for recovering rhodium from organic solutions containing coordination complexes of rhodium and non-ionic organophosphine ligands. For example, the method encompasses contacting an organic solution containing a partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst with an aqueous solution containing an ionic organophosphine ligand to transfer the rhodium from said organic solution into said aqueous solution, and, if desired, subsequently transferring (e.g., back extracting) the rhodium from said aqueous solution into an organic solution containing a non-ionic organophosphine ligand for reuse in a hydroformylation process. While not intending to be bound by any particular explanation or theory, it appears that the organic solvent - soluble and water-insoluble partially deactivated rhodium - tertiary non-ionic organophosphine hydroformylation complex catalyst is converted into a water-soluble rhodium - tertiary ionic organophosphine ligand complex product during contact between the organic and aqueous solutions, and thus the rhodium is extracted in the form of a water-soluble coordination complex. In any event the amount of rhodium capable of being so extracted from its organic solution into the aqueous solution may depend on the degree of deactivation of the partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst present in the organic solution starting material. For example it appears that the more highly deactivated the rhodium complex catalyst, the lower the amount of rhodium capable of being so extracted. Thus obviously any method which would improve the amount of rhodium capable of being so extracted would be highly beneficial to the art. DISCLOSURE OF THE INVENTION It has now been discovered that the amount of rhodium, that is capable of being so extracted, -can _>e- * -_ιcreased or improved by pretreating the organic solution with certain organic reagents to obtain an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product. Such a method potentially has application in the wide variety of homogeneous catalysis applications noted earlier, and particularly for removing rhodium from 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. Thus it is an object of this invention to provide a process for obtaining an organic solution of an organic , reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product that contains more rhodium capable of being extracted into an aqueous solution containing an ionic organophosphine ligand, than contained in the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst containing organic solution starting material of this process invention. Other objects and advantages of this invention will become readily apparent from the following description and appended claims. The present invention is considered to have broad applicability to the recovery of rhodium from organic solutions containing partially deactivated rhodium - tertiary non-ionic organophosphine complex catalysts as for example may be formed inter alia in hydrogenating unsaturated compounds, such as in the hydrogenation of copolymers of a conjugated diene and co-poly erizable monomers as described in U.S. Patents Nos. 4,464,515 and 4,503,196, in carbonylating methanol to acetic acid, in oligomerizing olefins, in hydrocyanating butadiene to adiponitrile, in decarbonylating aldehydes and in hydrosilylating olefins. For convenience in presentation, however, this invention will be described hereinafter with specific reference to the preferred recovery of rhodiumifrom organic solutions of partially deactivated rhodium - tertiary non-ionic organophosphine complex catalysts used, for example, in hydroformylating olefinic compounds. The broad applicability of the present invention will nonetheless be appreciated and understood by those skilled in the art in view of the following description and specific examples. Accordingly a generic aspect of this invention can be described as a process for increasing the amount of rhodium capable of being extracted into an aqueous solution containing an ionic organophosphine ligand, which rhodium is present in an organic solution containing a partially deactivated rhodium - tertiary non-ionic organophosphine complex complex catalyst, said process comprising mixing under non-hydroformylation conditions, said organic solution with an organic reagent selected from the group consisting of (a) alkyne compounds having the formula R-C_≡=_C-CH 2 -X, (b) alkene compounds having the formula (R 1 )(R 2 )C=C(R 3 )-CH 2 -X, (c) diketene, (d) methyl halides, (e) methyl sulfonates, (f) propiolate compounds having the formula H HCC≡≡CC--CC(0)OR 14, and (g) oxide compounds having the formula wherein X represents a radical selected from the group consisting of halogen atoms, a hydroxy radical, a carboxylate radical of the formula Q -OC(0)R , a sulfonate radical of the formula Q -OSO- and a phosphonium radical of the formula [-P + (R 8 > 3 3 [Y-]; wherein R 8 in the above formulae for X, each individually represent a monovalent hydrocarbon radical having from 1 to 18 carbon atoms selected from the group consisting of alkyl, aryl, aralkyl, alkaryl and cycloalkyl radicals and wherein Y represents an anion; and wherein each R, R , R , R , R , R , R , R7, and R14 radical individually represents a radical selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms (e.g. alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicals), with the following provisos: that R in the above carboxylate formula can also be hydrogen; that R ,2 3 and R in the above formula for the alkene compounds can also be bonded together to form a five or six membered heterocyclic ring or monocyclic hydrocarbon ring along with the C=C group shown in 4 said formula; and wherein any two of said R , R5, R6 and R7 groups in the above formula for the oxides can be bonded together to form a five or six membered monocyclic hydrocarbon ring along with the C-C group shown in said formula; to obtain an organic solution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product that contains more rhodium correspondingly capable of being extracted into an*agueous solution containing an ionic organophosphine ligand than contained in the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst containing organic solution starting material of this process, said partially deactivated complex catalyst preferably being a hydroformylation catalyst. DESCRIPTION OF THE PREFERRED EMBODIMENTS As noted above the subject invention resides in the discovery that the amount of rhodium present in an organic solution of a partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst which is capable of being extracted into an aqueous solution containing an ionic organophosphine can be improved or increased by the process of this invention. The solubilized partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst contained in the organic solution treated in accordance with this invention can be any such catalyst complex resulting from the wide variety of homogeneous catalysis processes noted earlier, and particularly from a hydroformylation process directed to producing aldehydes by hydroformylating an olefinic compound with carbon monoxide and hydrogen in the presence of a rhodium - tertiary non-ionic organophosphine complex catalyst, and which process has been operated to the extent that the originally employed catalyst complex has become at least partially deactivated, i.e. a catalyst which has become less reactive than its original counterpart. The extent of such catalytic deactivation may be determined at any given time e.g., by comparing the hydroformylation conversion rate to aldehyde product based on such catalyst to the conversion rate obtained using fresh catalyst. Moreover, the organic solution starting materials that can be treated in accordance with this invention may consist of only the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst and an organic solvent for said complex catalyst. More preferably such organic solutions may comprise all or any part of the hydroformylation reaction medium and/or all or any part of the liquid catalyst recycle medium of the corresponding hydroformylation process that produced the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst. As pointed out by the above prior art, methods for hydroformylating olefinic compounds to produce aldehydes with a rhodium - tertiary non-ionic organophosphine complex catalyst are well known in the art. Thus it should be clear that the particular hydroformylation process for producing aldehydes from an olefinic compound, as well as the reaction conditions and ingredients of said hydroformylation process, which serve as a means for furnishing the solubilized partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst containing organic solution starting material of the present invention, are not critical features of the present invention. In general preferred hydroformylation processes comprise reacting an olefinic compound with carbon monoxide and hydrogen in a reaction vessel and in the presence of a non-aqueous hydroformylation reaction medium comprising aldehyde products, a solubilized rhodium - tertiary non-ionic organophosphine complex catalyst, free tertiary non-ionic organophosphine ligand and an organic -In¬ solvent for said catalyst and free ligand. In continuous hydroformylation reactions aldehyde products are constantly being removed, the rhodium - tertiary non-ionic organophosphine complex catalyst either remaining in the hydroformylation reaction medium in the reactor as in the case of a gas recycle operation (e.g. USP 4,247,486), or be ng recycled back to the reactor after removal of some of the liquid reaction medium from the reactor, and separation of aldehyde product therefrom, as in the case of a liquid catalyst recycle operation (e.g. USP 4,148,830 and USP 4,731,486). Thus the "organic solution" starting material as employed herein means any organic liquid medium comprising a partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst, and an organic solvent for said complex catalyst, and such liquid mediums may be derived from any of the wide variety of homogeneous catalysis processes noted earlier and particularly from a non-aqueous hydroformylation process. Accordingly the organic solution starting materials employable herein preferably contain at least some amount of two and preferably at least three different main ingredients or components, i.e., the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst and an organic solvent, and preferably free tertiary non-ionic organophosphine ligand, said ingredients preferably corresponding to those employed and/or produced by the hydroformylation process from whence the organic solution starting material may be derived. Preferably said organic solution starting materials also contain at least some amount of the aldehyde product corresponding to the desired aldehyde product of the hydroformylation process from whence such organic solution may be derived, although it may be possible, to remove all of such aldehyde product prior to treating the organic solution by the process of this invention. Of course it is to be further understood that the organic solution starting materials of this invention can contain minor amounts of additional ingredients such as those which have either been deliberately employed in the hydroformylation process or formed .in situ during said process. Examples of such additional ingredients that can also be present include unreacted olefin starting material, and in situ formed type products, such as unreacted isomerized olefin, hydrogenated olefin (e.g. corresponding saturated hydrocarbons or paraffin by-products); jLn situ type by-products derived from the aldehyde products, such as high boiling aldehyde condensation by-products (as described e.g. in USP 4,148,830 and USP 4,247,486) and in situ type alkyl substituted phosphine ligand by-product (such as described e.g. in USP 4,260,828). Moreover, the organic solution starting materials of this invention are essentially non-aqueous, as a result of having been derived from an essentially non-aqueous, homogeneous hydroformylation process. Accordingly it should be sufficient for the purpose of this invention to understand that whatever compounds are present during the process from which the organic solution starting materials of this invention can be derived, may also be correspondingly present in said organic solution starting materials of this invention. Thus the particular partially deactivated rhodium tertiary no -ionic organophosphine complex catalyst present in " the organic solution starting material to be treated in accordance with this invention can be any such corresponding conventional rhodium hydroformylation catalyst which has been employed in a hydroformylation reaction to the extent that it has become partially deactivated. Accordingly the particular partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst, as well as its amount in a given organic solution starting material of this invention may obviously correspond to and merely be dependent upon the particular rhodium - tertiary non-ionic organophosphine complex catalyst employed in and/or formed under the reaction conditions of the particular hydroformylation reaction from whence the organic solution starting material to be treated according to this invention has been derived. For example illustrative rhodium - tertiary non-ionic organophosphine complex catalysts and hydroformylation reactions, include e.g. those disclosed in U.S. Patents 3,527,809; 4,148,830; 4,247,486; 4,283,562; 4,400,548; 4,482,749; 4,491,675; 4,593,127; PCT Application, Publication No. WO 80/01690 (published August, 1980); and the like, the entire disclosures of which are incorporated herein by reference thereto. Of course mixtures of different catalysts and non-ionic organophosphine ligands can be employed if desired. Moreover, as noted in said references, the hydroformylation processes are generally and preferably carried out in the presence of free tertiary non-ionic organophosphine ligand i.e. ligand that is not complexed with the rhodium complex catalyst employed. While it is generally preferred that the free ligand be the same as the tertiary non-ionic organophosphine ligand of the rhodium - tertiary non-ionic organophosphine complex catalyst, such is net necessary. Accordingly it is to be understood that in the case of the rhodium - tertiary non-ionic organophosphine complex catalyst, as well as in the case of the free tertiary non-ionic organophosphine ligand any conventional tertiary non-ionic organophosphine ligand, heretofore advanced for such hydroformylation purposes, such as disclosed e.g. by the above mentioned references, can be employed herein. Accordingly illustrative tertiary non-ionic organophosphines that may be employed, either as the free ligand and/or as the ligand of the rhodium complex catalyst, include e.g. trialkylphosphines, alkyldiarylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyldiarylphosphines, triaralkylphoεphines, tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryl bisphosphines and bisphosphine mono-oxides, and the like. Of course any of the hydrocarbon radicals of such tertiary non-ionic organophosphines may be substituted if desired, with any suitable εubstituent that does not unduly adversely affect the desired result of the 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 substitutents, may include for example silyl radicals such as -Sι(R 9),; ammo radicals such as -N(R9)_; acyl radicals such as -C(0)R 9, acyloxy radicals 9 such as -OC(0)R ; amido radicals such as -CON(R 9 )-, and -N(R 9 )COR 9 ; sulfonyl radicals such as -SO,R 9, alkoxy radicals such as -OR9; thionyl radicals such as -SR 9, phoεphonyl radicals 9 such as -P(0)(R ) 2 , as well as, halogen, nitro, cyano, trifluoromethyl, hydroxy radicals, and the 9 like, wherein each R individually represents the same or different monovalent hydrocarbon radical having from 1 to 18 carbon atoms (e.g., alkyl, aryl, aralkyl, alkaryl and cyclohexyl radicals), with the 9 proviso that ammo substituents such as -N(R ),, each R 9 taken together can also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, and in amido a substituents such as -C(0)N(R )- and 9 9 9 -N(R )COR each bonded to N can also be -- hydrogen. Of course it is to be understood that any of the substituted or unsubstituted hydrocarbon radicals groups that make up a particular given tertiary non-ionic organophosphine may be the same or different. Such tertiary non-ionic organophosphines and corresponding rhodium - tertiary non-ionic organophosphine complex catalysts and/or methods for their preparation are well known as seen e.g. by the above mentioned references. Preferred tertiary non-ionic organophosphines these having the formula (R ) 3 P wherein each R individually represents a monovalent hydrocarbon radical containing from 1 to 18 carbon atoms selected from the alkyl, aralkyl, alkaryl, cycloalkyl and aryl radicals, as disclosed e.g., in U.S. Patents 3,527,809 and 4,283 " ,562, and the like. Among the more preferred tertiary non-ionic organophosphines are triphenylphosphine, propyldiphenylphosphine, t-butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, cyclohexyldiphenylphoεphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, and the like. The most preferred ligand is triphenylphosphine (TPP), while the most preferred catalyεt iε a rhodium-TPP complex. As seen by the above mentioned hydroformylation references, the rhodium complex catalystε are generally considered as consiεting eεsentially of rhodium complexed with carbon monoxide and tertiary non-ionic organophosphine (generally corresponding to the free tertiary non-ionic organophosphine ligand also normally present in the reaction medium) . The catalyst terminology "consisting essentially of" is not meant to exclude, but rather include the possibility of any other ligand which does not unduly adversely affect the hydroformylation process, complexed with the rhodium such as hydrogen which is also a ligand in addition to the carbon monoxide and tertiary non-ionic organophosphine, the hydrogen being derived from the hydrogen gas of the hydroformylation reaction, if not already present in the catalyst precursor. Such hydroformylation catalysts may be formed in situ during the hydroformylation reaction or preformed by methods known in the art. For example preformed rhodium hydridocarbonyl-triε (tertiary non-ionic organophoεphineε) may be introduced into the reaction medium of the hydroformylation reaction. Alternatively rhodium catalyst precursors such as rhodium carbonyl tertiary non-ionic organophosphine acetylacetonates, Rh-,0-, Rh 4 (C0). 2 , Rh-(CO) 16 , Rh(NO_) 3 or rhodium dicarbonyl acetylacetonate, and the like, may be introduced into the reaction medium of the hydroformylation reaction. In any event an active rhodium complex hydroformylation catalyst is preεent in the hydroformylation reaction medium under the conditions of hydroformylation. However, it is to be noted that the successful practice of this invention does not depend and is not predicated on any explanation as to the exact structure-.or nature of the active rhodium complex catalyst species or as to the exact structure or nature of the partially deactivated rhodium catalyst species formed during the hydroformylation. Indeed such exact structures are not known with certainty. Clearly for the purpose of understanding this invention, it is sufficient to εimply point out that the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalysts present in the organic solution starting materials of this invention can be any such partially deactivated catalyst mixture resulting from the use of a corresponding active rhodium - tertiary non-ionic organophosphine complex catalyst in the hydroformylation reaction medium of the hydroformylation process from whence the particular organic solution starting material employable in the process of this invention is derived. The amount of the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst present in the organic solution starting materials of this invention may range from about one part per million (ppm), up to about 50,000 parts per million (ppm) or more, calculated as rhodium metal. In general the amount of such partially deactivated rhodium complex catalyst present in the organic solution starting material of this invention preferably correspondε to the amount of the rhodium - tertiary non-ionic organophosphine complex catalyst employed in the hydroformylation reaction medium of the hydroformylation process from whence the organic solution starting material may be derived and such amounts are commonly expressed in terms of the amount of rhodium present calculated as rhodium metal. In the more preferred low pressure non-aqueous hydroformylation processes, rhodium hydroformylation concentrations preferably do not exceed 500 ppm, calculated as rhodium metal, with concentrations of from about 50 up to 300 ppm. calculated aε rhodium metal being even more preferred. Of courεe the organic solution starting materials of this invention may contain higher concentrationε of rhodium than preεent in the hydroformylation reaction medium, and such may be readily obtained e.g. simply by concentrating the rhodium catalyst containing hydroformylation medium prior to employing same as the organic solution starting material of this invention. Such concentration procedures e.g., may range from merely removing some of the aldehyde product on up to preparing very viscouε rhodium containing concentrates such as taught e.g. in U.S.P. 4,297,239. Rhodium concentrationε in the range of from about 5 to about 10,000 ppm, and more preferably from about 10 to about 1000 ppm, of rhodium, calculated aε rhodium metal, should be sufficient for most hydroformylation processes and such corresponding amounts are preferably present in the organic solution starting materials of this invention. As noted above the tertiary non-ionic organophosphine ligands defined herein are employed in this invention as both the ligand of the rhodium- tertiary non-ionic organophosphine complex catalyst as well as, the free tertiary non-ionic phosphine ligand that is also present in the organic solution starting materials of this invention. In a given situation such rhodium-phosphine complexes and free phosphine ligands of course ' will correspond to those employed in * the hydroformylation procesε from which said organic solutions may be derived. In addition, it is to be understood that while the tertiary non-ionic organophosphine of the rhodium complex catalyst and free tertiary non-ionic organophosphine ligand preεent in the reaction medium of a given hydroformylation process are normally the same, different tertiary non-ionic organophoεphine ligandε, as well as, mixtures of two or more different tertiary non-ionic organophosphine ligands may be employed for each individual purpose, if desired. As in the case with the amounts of rhodium complex catalyst employed, the amount of free tertiary non-ionic organophosphorus ligand present in a given organic solution starting material of this invention will in general correspond to that amount of corresponding free ligand present in the hydroformylation process from which said liquid medium may be derived. For instance, since the hydroformylation procesε may be carried out in any exceεs amount of ' free tertiary non-ionic organophosphine ligand desired e.g., at least one mole of free tertiary non-ionic organophosphine ligand per mole of rhodium present in the reaction medium, the amount of free tertiary non-ionic organophosphine ligand present in a given organic solution starting material of this invention can also be any corresponding excesε amount e.g., at least one mole of free tertiary non-ionic organophosphine ligand per mole of rhodium metal present in the liquid medium starting material. In general an amount of free tertiary non-ionic organophosphine ligand of from about 2 to about 300, and preferably from about 5 to about 200 moles per mole of rhodium metal present in the reaction medium should be εuitable for most hydroformylation proceεεeε. Accordingly, corresponding amounts of free tertiary non-ionic organophosphine ligand may be present in the organic solution starting materials of this invention. . The organic solution starting materialε of this invention also contain an organic εolvent generally corresponding to that employed for εolubilizing the rhodium - tertiary non-ionic organophosphine complex catalyst and free tertiary non-ionic organophosphine ligand present in the reaction medium of the hydroformylation process from which said organic solution εtarting materials of this invention may be derived. Any suitable organic solvent which does not adversely interfere with the intended hydroformylation proceεε or this invention can be employed. Such organic solvents are well known in the art and encompass both polar and non-polar organic solventε, εuch as compoundε belonging to the general classes of alkanes, ethers, aldehydes, ketones, eεterε, amideε and aromatics. Illustrative suitable organic solventε include those described e.g. in U.S. Patents 3,527,809; '4,148,830; and 4,731,486. Of course, mixtures of one or more different solvents may be employed if desired. Moreover, the preferred solvents are aldehyde compounds corresponding to the aldehyde products of the hydroformylation process and/or higher boiling aldehyde condensation by-products such as described e.g. in U.S.P. 4.148,830 and * 4,247,486. The amount of organic solvent present in the organic solution starting materials need only be that amount sufficient to solubilize the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst and free ligand present in said starting material. In general such amounts of organic solvent may correspond to those amounts of solvent present in the reaction medium or catalyst containing recycle medium of the hydroformylation process from whence the organic solution starting materials of this invention may be derived. Thus in general the amount of organic solvent present in the organic solution starting materials of this invention may range from about 5 to about 95 parts by weight based on the total weight of said organic solution starting material. Finally as noted above, the organic solution starting materials of the procesε of thiε invention also preferably contain at least some amount of aldehyde product corresponding to the aldehyde product obtained by the hydroformylation procesε from whence εaid organic solution starting materials may be derived. Such aldehydes may contain from 3 to 31 carbon atoms and encompass the corresponding hydroformylation aldehyde products obtained upon hydroformylating olefinic compounds containing from 2 to 30 carbon atoms. Such olefinic compounds can be terminally or internally unsaturated and be of straight-chain, branched chain or cyclic structures, as well as be olefin mixtures, such as obtained from the oligomerization of propene, butene, isobutene, etc., (such aε so called dimeric, trimeric or tetra eric propylene, and the like, as disclosed e.g. in U.S. Patents 4,518,809 and 4,528,403). Moreover such olefinic compounds may further contain one or more ethylenic unsaturated groupε 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 procesε or the procesε of this invention such as described e.g., in U.S. Patents 3,527,809; 4,731,486 and the like. Illustrative olefinic unεaturated compounds are alpha-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols, and the like e.g., ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, l-eicosene, 2-butene, 2-methyl propene (isobutylene) , 2-pentene, 2-hexene, 2-heptene, propylene dimers, propylene trimerε, propylene tetramers, 2-ethyl hexene, 2-o_tene, styrene, 3-phenyl-l-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-l-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- ethyl styrene, 1,3-diisopropenyl-benzene, eugenol, iso-eugenol, safrole, iso-εafrole, anethol, 4-allylaniεole, indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene, linalool, and the like. Accordingly illustrative aldehyde products include e.g, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-methyl-l-butyraldehyde, hexanal, 2-methyl valer ldehyde, hept;anal, 2-methyl-l-hexanal, octanal, 2-methyl-l-heptanal, nonanal, 2-methyl-l-octanal, 2-ethyl-l-heptanal , 3-propyl-l-hexanal, decanal, 2-methyl-l-nonanal, undecanal, 2-methyl-l-decanal , dodecanal, 2-methyl-l-undecaήal, tridecaήal, 2-methyl-l-tridecanal, 2-ethyl-l-dodecanal, 3-propyl-l-undecanal, pentadecanal, 2-methyl-l-tetradecanal, hexadecanal, 2-methyl-l-pentadecanal, heptadecanal, 2-methyl-l-hexadecanal, octadecanal, 2-methyl-l-heptadecanal, nonadecanal, 2-methyl-l-octadecanal, 2-ethyl-l-heptadecanal , 3-propyl-l-hexadecanal, eicosanal, 2-methyl-l-nonadecanal, heneicosanal, 2-methyl-l-eicosanal, tricosanal, 2-methyl-l-docosanal, tetracosanal, 2-methyl-l-tricosanal, pentacosanal, 2-methyl-l-tetracosanal, 2-ethyl-l-tricosanal, 3-propyl-l-docosanal, heptacosanal, 2-methyl-l-octacosanal, nonacosanal, 2-methyl-l-octacosanal, hentriacontanal, 2-methyl-l-triacontanal, and the like. Of course it is understood that the aldehyde product of an alpha olefin will normally be a mixture of the normal straight chain aldehyde and its branched chain aldehyde isomer obtained upon hydroformylating said olefin. Moreover, mixtures of totally different aldehyde products can be present in the organic solution starting materials employable in this invention, e.g., when such organic solutions are derived from a process that hydrofor ylates mixtures of totally different olefinic compounds, such as e.g., mixtures of alpha olefins and internal olefins or mixtures of two different alpha olefins. The preferred aldehyde products present in the hydroformylation reaction product compositions employable in this invention are those derived from hydroformylating alpha olefins, internal olefins and mixtures of such alpha and internal olefins. The more preferred olefin starting materials are alpha olefins having from 2 to 20 carbon atoms and more preferably from 3 to 14 carbon atoms. As employed herein the term "alpha olefin" means unsubstituted olefins, thus excluding substituted olefins such as alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols, and the like. Of course it is to be understood that commercial alpha olefins containing 4 or more carbon atoms may contain minor amounts of corresponding internal olefins and/or their corresponding saturated hydrocarbon and that such commercial olefins need not necessarily be purified from same prior to being hydroformylated. The amount of aldehyde product present in the organic solutions employable as the starting materials of this invention may range from 0 to about 90 percent by weight or higher of the liquid medium. Such amounts are not narrowly critical and will of course in general merely be dependent upon the particular reaction conditions and efficiency of the hydroformylation process from whence the organic solution starting materials of this invention may be derived. In general, preferred hydroformylation processeε are those capable of producing a hydroformylation reaction-product medium containing from about 10 to about 80 percent by weight of aldehyde product. Preferably the amount of aldehyde product present in the...l qui > d-_J_'edium εtarting aterialε employable in this invention may range from 0 to about 80 percent by weight, and more preferably from about 1 to 60 percent by weight, of the organic solution. More preferably the organic solution starting materialε of this invention correspond to all or a part of the reaction medium of a hydroformylation procesε aε outlined herein or correεpond to all or a part of the liquid catalyst containing recycle medium of such a hydroformylation process (i.e. that liquid catalyst containing residue obtained, after the removal of that desired amount of aldehyde product from the hydroformylation reaction product medium outside of the hydroformylation reactor or hydroformylation zone), which is recycled to the reactor in order to establish a continuous hydroformylation catalyst recycle process. Of course it is to be further understood that the organic solution starting materials of this invention may also contain additional ingredientε correεponding to thoεe which have either been deliberately employed in the hydroformylation process from which said organic solution starting materials may be derived or which have been formed in situ during the hydroformylation process. For instance, obviously since an olefin starting material is being hydroformylated, the organic solution starting materials of this invention may contain some unreacted olefin starting material . The amount of such unreacted olefin present in any said organic solution starting material will be in general governed by the efficiency of the hydroformylation process. In general amounts of unreacted olefin may range from about 0 to about 20 percent by weight of the organic solution. Likewise, minor amounts of in situ type by-productε that may be formed during the hydroformylation process may also be correspondingly present in the organic solution starting materialε of this invention, e.g., in situ type by-products derived from the olefinic starting materials, such as unreacted isomerized olefin, hydrogenated olefin (e.g., corresponding saturated hydrocarbons or paraffin by-products); in situ type by-products derived from the aldehyde products, such as high boiling aldehyde condensation by-products (as described e.g. in USP 4,148,830 and said USP 4,247,486 discussed above); and possibly even some in situ type alkyl substituted phosphorus ligand by-product. Further minor amounts of other additional co-solvent type diluents or additives, if employed in the hydroformylation procesε, may correεpondingly be preεent in the organic εolution starting materials of this invention. Accordingly, it should be sufficient for the purpose of this invention to understand that whatever compounds are preεent in the hydroformylation reaction medium of the hydroformylation proceεε from which the organic εolution starting material of this invention is derived, may also b'e correspondingly present in said .organic solution εtarting materialε. Likewise, the reaction conditionε for effecting εuch hydroformylation proceεεes may be conventionally used and may comprise a reaction temperature of from about 45°C to about 200°C and preεεureέ ranging from about 1 to 10,000 pεia. The total gas preεεure of hydrogen, carbon monoxide and olefinic unsaturated starting compound of such hydroformylation processes may range from about 1 to about 10,000 psia, while it iε preferred " that the procesε be operated at a total gaε preεsure of hydrogen, carbon monoxide and olefinic unstaurated εtarting compound of less then about 1500 psia and more.preferably less than about 500 psia. The partial pressure of the reactants is not particularly critical and depends predominatly on the amount and nature of the reactants employed and the desired result to be obtained. For instance, in non-aqueous hydroformylation processes the carbon monoxide partial pressure is preferably from about 1 to about 120 psia and more preferably from about 3 to about 90 psia, while the hydrogen partial pressure is preferably about 10 to about 200 psia and more preferably from about 20 to about 160 psia. In general the H 2 :C0 molar ratio of gaεeous hydrogen to carbon monoxide may range from about 1:10 to 100:1 or higher, the more preferred hydrogen to carbon monoxide molar ratio being from about 1:1 to about 10:1. Further, it is more preferred to employ a hydroformylation reaction temperature of from about 60°C to about 140°C. It iε to be further underεtood that while the subject invention iε preferably directed to treating a organic solution that has been directly obtained from a hydroformylation procesε, the organic solution starting materials of this invention also encompasε any εubsequent organic solution derived from such an initial liquid medium so obtained, provided said subεequently derived organic solution also contains at least some amount of each of the two and preferably three main ingredients defined above i.e., the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst and an organic solvent for said complex catalyst and preferably the free tertiary non-ionic organophosphine ligand and more preferably also at least some amount of the aldehyde product. As noted above the organic reagents employable in the process of this invention can be any such reagent selected from the group consisting of (a) alkyne compounds having the formula R-CSC-CH.-X, (b) alkenes having the formula (R 1 )(R 2 )C=C(R 3 )-CH 2 -X, (c) diketene, (d) methyl halides, (e) methyl sulfonateε, (f) propiolate compounds having the formula (g) oxide compounds having the formula wherein R, R 1 , R 2 , R 3 , R , R 5 , R 6 , R 7 . R 14 and X are the same as defined above. More preferably each R, R 1, R2, and R3 radical representε hydrogen. Illuεtrative monovalent hydrocarbon radicalε having from 1 to 18 carbon atomε 1 3 4 5 repreεented by the R , R , R , R , R , R 6, R7, and R14 radicalε in the above formulae include alkyl radicalε such aε methyl, ethyl, propyl, butyl, tertiary butyl, hexyl , etc.; aryl radicalε such as phenyl, naphthyl, etc.; aralkyl radicals such as phenylethyl, benzyl, etc.; alkaryl radicals such as tolyl, xylyl, etc.; and cycloalkyl radicals, such aε cyclohexyl, etc. Preferred monovalent hydrocarbon radicals are those containing from 1 to 8 carbon atoms, and more preferably they are phenyl or alkyl radicals, especially alkyl. Of course it is to be further * understood that such hydrocarbon radicals represented by the radicals R through 7 and 14 may also be substituted with one or more substitutents that do not unduly adversely affect the desired purpose of this invention. Illustrative subεtitutentε that may be preεent on such hydrocarbon radicalε, in addition of courεe to additional correεponding hydrocarbon radicalε εuch aε alkyl, aryl, aralkyl, alkaryl and cyclohexyl εubεtitutentε, may include for example silyl radicalε εuch as -Si(R ),; amino radicalε such as -N(R 9),; acyl radicals such as -C(0)R 9; acyloxy radicals such as -OC(0)R9; amido radicals εuch aε -CON(R )_ and -N(R 9)COR9; εulfonyl radicalε εuch aε -SO_,R 9; alkoxy radicalε εuch aε -OR9; thionyl radicalε such as -SR 9; phosphonyl radicalε εuch aε 9 -P(0)(R )„, as well as, halogen, nitro, cyano, trifluoromethyl, hydroxy radicals, and the like, 9 wherein each R individually representε the εame or different monovalent hydrocarbon radical having the same meaning as defined for R to R above, with the proviso that amino εubεtituents such aε 9 9 -N(R ) 2 > ea ch R taken together can alεo represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, and in 9 amido substituents such as -C(0)N(R ) 2 and -N(R 9 )C0R 9 each R 9 bonded to N can also be hydrogen. Of course it is to be understood that any substituted or unsubstituted hydrocarbon groups that make up a particular given organic reagent may be the same or different. As noted above X may represent a hydroxy radical, i.e., - OH, or a halide atom. Illustrative halide atoms represented by X in the above formulae include chlorine, bromine and iodine, especially chlorine. Illustrative monovalent hydrocarbon radicalε having from 1 to 18 carbon atoms represented by R in the above formula for X include alkyl radicals, such as methyl, ethyl, propyl, butyl, tertiary butyl, hexyl, etc.; aryl radicals εuch aε phenyl, naphthyl, etc.; aralkyl radicalε εuch aε benzyl, phenylethyl, etc.; alkaryl radicalε, εuch aε tolyl, xylyl, etc. and cycloalkyl radicals such as cyclohexyl, etc. Preferred monovalent hydrocarbon radicals are those containing from 1 to 8 carbon atoms εuch aε benzyl or phenyl radicalε, and more preferably alkyl radicalε, eεpecially methyl. Of course it iε to be further Q understood that such hydrocarbon radicalε of R may alεo be εubεtituted with one or more εubstitutentε that do not unduly adversely affect the desired purpose of this invention. Illustrative substitutents that may be present on such R hydrocarbon radicals, in addition of course to corresponding hydrocarbon radicals such as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substitutents, may include for example silyl radicals such as -Si(R ,9,) 3 ; amino radicals such as -N(R ) 2 ; acyl radicals such as -C(0)R ; acyloxy radicals 9 such as -OC(0)R ; amido radicals such aε -CON(R 9 ), and -N(R 9 )COR 9 ; sulfonyl radicals such as -SO-R 9; alkoxy radicals such as -OR9; thionyl radicals such as -SR 9; phosphonyl radicals 9 such as -P(0)(R ) 2 , as well as, halogen, nitro, cyano, trifluoromethyl, hydroxy radicals, and the like, wherein each R individually represents the same or different monovalent hydrocarbon radical having the same meaning as defined for R above, with the proviεo that amino subεtituentε εuch aε -N(R9) 2 , each R9 taken together can alεo represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, and in 9 amido substituents such as -C(0)N(R )_ and 9 9 9 -N(R )C0R each R bonded to N can also be hydrogen. Preferred substituents include e.g., cyano and -C(0)CH_. Illustrative anions repreεented by Y in the above phoεphonium radical formula include halogen e.g., chlorine, bromine, etc.; εulfonic acidε; acetic acids; and the like. Preferred organic reagents are those of the above formulae for said propiolate compounds and said alkyne and alkene compounds wherein X representε a halide, hydroxy, carboxylate or sulfonate radical, more preferably the alkyne and alkene compounds. Illustrative alkyne compounds that may be employed as the organic reagent of the procesε of thiε invention include e.g., propargyl formate, propargyl acetate, propargyl propionate, propargyl butyrate, propargyl cyanoacetate, propargyl acetoacetate, propargyl chloride, propargyl bromide, propargyl iodide, propargyl benzene sulfonate, propargyl triphenylphosphonium bromide, propargyl alcohol, and the like. The preferred alkyne compounds are alkyne alcohols and halides (e.g. wherein X in the above formula is a hydroxy radical or a halide radical) especially propargyl alcohol and propargyl halides, e.g. propargyl chloride, and those of the formula RC__=CCH,OC(0)R 8 wherein R and R are the same aε defined above, especially propargyl acetate. Illustrative alkene compounds that may be employed as the organic reagent of the procesε of thiε invention include e.g. allyl acetate, allyl propionate, allyl butyrate, allyl methacrylate, furfuryl acetate, allyl trifluroacetate, benzyl bromide, benzyl acetate, allyl chloride, aUlyl bromide, allyl iodide, allyl benzene εulfonate, allyl cyanoacetate, allyl triphenylphoεphonium bromide, and the like. The preferred alkene compounds are those of the formula R 1 R 2 C=C(R 3 )-CH,-X wherein R 1 , R 2 , and R 3 are the same as defined above and X representε Q halogen or a carboxylate of the formula -0(CO)R a wherein R iε the εame aε defined above, and more preferably allyl halides and carboxylates, eεpecially allyl acetate and allyl chloride. Illustrative propiolate compounds that may be employed as the organic reagent of the procesε of this invention include e.g., methyl propiolate, ethyl propiolate, propyl propiolate, butyl propiolate, isobutyl propiolate, pentyl propiolate, hexyl propiolate, phenyl propiolate, and the like. The preferred propiolate compoundε are those having the above formula wherein R 14 representε a monovalent hydrocarbon radical aε defined above, especially alkyl. The more preferred propiolate compoundε are methyl and ethyl propiolates. Illustrative methyl halides and methyl sulfonate organic reagents that may be employable in the process of this invention include e.g., methyl chloride, methyl bromide, methyl benzene εulfonate, and the like. Illustrative oxide compounds that may be employable in the process of this invention, include e.g., cyclohexene oxide, cyclopentene oxide, ethylene oxide, propylene oxide, styrene oxide, and the like. The diketene organic reagent may be depicted by the formula: H 2 More particularly, the treatment of the organic solution starting material of this invention, which is conducted under non-hydroformylation conditions, i.e., in the essential absence of syn gas (CO+H 2 ), can be accomplished by mixing an organic reagent of choice with the desired organic solution starting material to obtain an organic solution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product. The manner of said mixing of the organic reagent with the organic solution starting material and the order of addition is not critical and such can be carried out in any conventional fashion using any suitable equipment and technique, the preferred result merely being a through inclusion of the organic reagent in the organic solution. In general merely adding the organic reagent to the organic εolution and gently stirring the solution should be sufficient to accomplish the desired reεult. Moreover in view of the fact that the subject invention is directed to obtaining at least some desired improvement, with regard to increasing the amount of rhodium of the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst contained in the organic solution to be treated, that is correspondingly capable of being extracted into an aqueous solution of an ionic organophosphine l'igand and because the partially deactivated catalysts in said organic solution starting materials can vary both in ' terms of their nature and concentrations it is apparent no εpecific valueε can be arbitrarily given to such treatment conditions as e.g., the amount of reagent, pressure, temperature and contact time for said treatment that will encompass every given situation. Such conditions can vary greatly and are not narrowly critical and obviously need only be at least sufficient to obtain the result desired. For instance, in some caseε a particular organic reagent may be more reactive than another and thuε a smaller amount of the more reactive reagent may be beneficial, while in other circu εtanceε a larger amount of the less reactive reagent may prove more desirable. Likewise treatment conditions εuch as temperature, pressure and contact time may also vary greatly and any suitable combination of such conditions may be employed herein. For instance, a decrease in any one--of such conditions may be compensated for by an increase in one or both of the other conditions, while the opposite correlation iε also true. In general the organic reagent may be added to and mixed with the organic εolution εtarting material at liquid temperatures ranging from about 10°C to about 180°C, while temperatures ranging from about 20°C to about 130°C may be suitable in most instances. It is generally preferred to carry out said treatment at atmospheric (ambient) pressure, although higher or lower presεureε may be employed if desired. Of course it is obvious that the contact time of the organic reagent and organic εolution involved will be directly related to the particular partially deactivated rhodium - tertiary non-ionic organophoεphine complex catalyεt and particular organic reagent involved, as well as to εuch treatment conditionε εuch as temperature, etc. and such contact time may vary from a matter of minutes to a few hours. Experience will determine the preferred temperature and contact time. However, said treatment of the organic solution starting material with the organic reagent according to this invention must be under non-hydroformylation conditions, which is to say that of the process of this invention must be carried out in the essential absence of syn gaε (C0+H 2 ), thus preventing any adverse simultaneous hydroformylation of the organic reagent and other compounds present in the organic solution starting material that is being employed. Preferably said addition and mixing is carried out under a nitrogen atmosphere, although mixtures of nitrogen and any other gas (except syngas) may be employed provided they do not unduly adversely affect the desired purpose of this invention. For example, hydrogen may be employed. Of course the amount of organic reagent employed in of this invention need only be that minimum amount necessary to help achieve the desired end reεult of this invention. In general it is considered that the amount of organic reagent employed may range from about 0.1 up to about 1000 moles or higher per mole of rhodium, calculated as rhodium metal, in the organic solution εtarting material, although it iε recommended to employ at least one mole of the organic reagent per mole of said rhodium. More preferably it is recommended that an excess molar amount of the organic reagent be employed although no added benefit is seen in employing very large excess amounts and very large excess amounts could be more detrimental than positive. In general it is considered that amounts of organic reagents ranging from about 0.5 to 500 moles per mole of rhodium, calculated aε rhodium metal, in the organic εolution starting material should be sufficient for most purposes, with preferred amounts being from about 1 to about 300 moles per mole of rhodium, calculated as rhodium metal. In any event it is sufficient for the purpose of this invention to understand that the organic reagent is added and mixed with the organic solution starting material of this invention to obtain an organic solution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product, which containε more rhodium correspondingly capable of being extracted into an aqueouε εolution containing an ionic organophoεphine ligand than contained in the partially deactivated rhodium - tertiary non-ionic organophoεphine complex catalyεt in said organic solution starting material. Thus it should be clear that while the selection of the optimum conditions of this invention to achieve the best results desired will be dependent upon one's experience in the utilization of the subject invention, in view of the discloεure and examples of this specification, only a certain measure of routine experimentation should be necesεary in order to aεcertain thoεe conditions which are optimum for a given situation. However, it should also be clear that one of the beneficial factors involved in this invention as employed herein is the wide processing latitude that one has in εelecting the proper combination of conditionε that will be oεt uεeful in obtaining or at leaεt best approaching a particular deεired reεult or need. Of courεe it is to be understood that the procesε of the εubject invention is not directed to increasing the actual amount of rhodium over that contained in the organic solution starting material, but rather increasing the amount of rhodium correspondingly capable of being extracted into an aqueous solution containing an ionic organophosphine ligand. For instance, in any given organic solution of a partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst, X amount of rhodium can be extracted into a given aqueouε solution containing an ionic organophosphine ligand by a given εet of extraction conditions. This X amount of rhodium is referred to herein as the amount of rhodium capable of being extracted into an aqueous solution containing an ionic phosphine. However when said given organic solution of partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst is treated with an organic reagent according to this invention, X + Y amount of rhodium can be correεpondingly extracted from the organic solution of the organic reagent treated solubilized partially deactivated rhodium - tertiary non-ionic organophoεphine complex product into said given aqueouε εolution containing ionic organophoεphine ligand by said given set of extraction conditions. This X + Y amount of rhodium then is evidence of the fact that the subject process of this invention has increased the amount of rhodium that is capable of being correεpondingly extracted into an aqueouε solution containing an ionic organophosphine ligand over that contained in the correspondingly untreated organic solution starting material. While not intending to be held to any specific chemical theory or mechanistic discourεe on juεt exactly how the beneficial deεired result of the process of this invention is achieved, it is considered that intrinsic deactivation of the rhodium - tertiary non-ionic organophosphine catalyst is due at least in part to the in situ formation of rhodium complex clusters during the hydrofor ylation proceεε, which cluεterε apparently decreaεe the amount of rhodium valueε capable of being extracted into an aqueouε solution containing an ionic organophosphine ligand. It is further conεidered that in the proceεε of thiε invention the organic reagent reactε with the rhodium of such clusterε to form new rhodium complex species in the treated ' organic solution, which are apparently more suεceptible to εaid extraction. In any event it haε been found that the process of this invention reεultε in obtaining an organic εolution of an organic reagent treated rhodium - tertiary non-ionic organophoεphine complex product that containε more rhodium correεpondingly capable of being extracted into an aqueouε εolution containing an ionic organophoεphine ligand than contained in the untreated partially deactivated rhodium - tertiary non-ionic organophoεphine complex catalyst containing organic solution εtarting material of this invention. Accordingly confirmation of such an improvement, obtainable by the procesε of this invention, can be witnessed by merely comparing the amount of rhodium extracted from a untreated organic solution containing a partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst into an aqueous solution containing an ionic organophosphine ligand via contacting the organic and aqueous solutions followed by phase separation of the organic and aqueous phases, against the amount of rhodium extracted from the corresponding organic solution of an organic reagent treated solubilized partially deactivated rhodium - tertiary non-ionic organophosphine product of this invention via the εame extraction process, which procedure is illustrated in the following working examples given below. Moreover, method of extracting rhodium from the organic solution of the organic reagent treated partially deactivated solubilized rhodium - tertiary non-ionic organophosphine complex product of this invention into an aqueous solution of an ionic organophoεphine ligand is fully detailed in Aεεignee'ε U.S. Patent Application Serial No. 231,508, entitled CATALYTIC METAL RECOVERY FROM NON-POLAR ORGANIC SOLUTIONS filed Auguεt 12, 1988 in the names of David J. Miller and David R. Bryant (the entire discloεure of which iε encompaεsed herein by reference thereto). Thus said rhodium extraction process may comprise contacting all or part of said organic solution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophoεphine complex product of thiε invention with an aqueouε solution of an ionic organophosphine ligand capable of forming a coordination complex with the rhodium to transfer rhodium from said organic solution into said aqueous solution. For instance a suitable arrangement involves contacting the organic solution from which rhodium is to be extracted with an aqueous solution of the ionic phosphine ligand in any conventional extraction vessel. In the extraction vessel, the organic εolution is contacted intimately with the aqueous solution containing free water-soluble ionic organophosphine ligand capable of forming a coordination complex with the rhodium. A wide variety of such ionic organophosphine ligands potentially can be used. Suitable water-εoluble ionic organophoεphine ligands that may be employed are those having the general formulae (1) and (2): R 2 - ( Y 2 ) 2 (1) m where R 1, R2 and R3 of formula (1) and R4, R 5, R6 and R7 of formula (2) each individually represent a hydrocarbon radical containing from 1 to 30 carbon atoms selected from the group consiεting of alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, where Q in formula (2) represents a divalent organic bridging group and where Y 1, Y2 and Y 3 of formula (1) and Y 4 , Y 5 , Y 6 , and Y of formula (2) are are substituted on the hydrocarbon radical and each individually represents an ionic radical of overall neutral charge selected from the group consisting of: -S0 3 M wherein M represents inorganic or organic cationic atoms or radicals selected so that the ligand is water-soluble, -P0-.M wherein M representε inorganic or organic cationic atomε or radicals selected so that the ligand is water-soluble, -NR,X' 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 radicalε, and X' representε inorganic or organic anionic atomε or radicals selected so that the ligand iε water-soluble, -C0 2 M wherein M repreεentε inorganic or organic cationic atoms or radicals selected so that the ligand is water-soluble, Wherein m 1, m2 and m3 of formula (1) and m of formula (2) are integers which can be the same or different and which can range from 0 to 5. At least one of m , m 2 and m3 and at least one-of m4, m5, m6 7 and m 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 aqueous solution the ligand. The integers m through m indicate the number of ionic radicals of overall neutral charge substituted on each hydrocarbon radical. The hydrocarbon radicals, R 1, R2 and R 3 of formula (1) and R 4 , R 5 R 6 , and R 7 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 the group consiεting of 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 R 1, R2 and R3 in formula (1) and at least one of R 4, R5, R6 and R7 in formula (2) is a phenyl radical. Such hydrocarbon radicalε may contain one or more substitutentε provided that they do not unduly adverεely affect the uεe of the ligand and this invention. Suitable substitutentε, in addition to the neceεεary ionic εubstitutent, e.g., the sulfonate, carboxylate and the like, 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 R 1, R2 and R3 in formula (1) are phenyl groups and at least three and most preferably four of R , R , R and R 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 the group consisting of 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 atomε. Illustrative divalent hydrocarbon radicals include alkylene radicals (e.g. methylene (-CH 2 ), ethylene, propylene, iεopropylene, butylene, 1,2-dimethylethylene, t-butylene, neopentylene, 2-methylpropylene, hexylene, 2-ethylhexylene, dodecylene, eicoεylene, and the like); arylene radicalε (e.g. phenylene, substituted phenylene, diphenylene, substituted diphenylene, and the like); as well as alkylene containing arylene radicals (e.g. methylenephenylene (-CH 2 C g H.-) , ethylenephenylethylene (-C 2 H 4 C 6 H 4 -C 2 H 4 -), phenylenepropylphenylene (-C 6 H 4 C(CH 3 ) 2 C 5 H 4 -), ' - • - • _ methylenediphenylmethylene (-CH 2 0 C C 6H4.C C 6H4,CH2-,-), and the like: alkylidene radicals (e.g. ethylidene (-CH=CH-) , and the like); and the like. Illustrative oxygen containing hydrocarbon radicals include alkyleneoxyalkylene radicals (e.g. ethyleneoxymethylene (-C j H.OCH-,-) propyleneoxymethylene (-C 3 H g O H 2 -) , ethyleneoxyethylene (-C 2 H 4 0C 2 H.-) , 1,2-bis(ethyleneoxy)ethane (-C 2 H 4 0C 2 H 4 0C 2 H 4 -), propyleneoxypropylene (-C 3 H g OC 3 H g -) and the like); aryleneoxyalkylene radicals (e.g. phenyleneoxymethylene (-CgH.OCH,,-) , and the like); and the like. Illustrative sulfur or thio containing hydrocarbon radicalε include alkylenethioalkylene radicals (e.g. ethlenethioethylene (-C 2 H 4 SC 2 H 4 ~) , 1,2-bis(ethylenethio)ethane (-C 2 H 4 SC 2 H 4 SC 2 H 4 -), propylenethiomethylene (-C 3 H,SCH 2 -) , propylenethiopropylene (-C 3 H_SC 3 H g -) , and the like); arylenethioalkylene radicals (e.g. phenylenethiomethylene (-C 3 H g S-CH 2 -) , and the like); and the like. Illustrative amino containing hydrocarbon radicals include alkyleneammoalkylene radicals (e.g. methyleneaminomethylethylene (-CH 2 N(CH 3 )C 2 H 4 -), ethyleneneaminomethylethylene (-C 2 H 4 N(CH 3 )C 2 H 4 -), bis(ethyleneaminomethyl)ethane (-C 2 H 4 N(CH 3 )C 2 H 4 N(CH 3 )C-,H 4 -) , propyleneaminomethylpropylene (-C 3 H 6 N(CH 3 )C 3 H 6 -) and the like and the like. Moεt 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 saltε of sulfonated and carbbxylated triarylphosphines, as, for example, are described in U.S. Patents 4,248,802; 4,399,312; 4,668,824; 4,716,250 and 4,731,486; and European Patent Application Pub. No. 216,315 (published April, 1987). Preferred among this group are the salts of monosulfonated and of trisulfonated triphenylphosphines, and the salts of monocarboxylated and of tricarboxylated triphenylphosphine. Another suitable clasε of ionic organophoεphineε are ionic bisdiarylphosphineε such as biεdiphenylphosphinoethane monoεulfonate salts. Mixtures of suitable ionic phosphine ligands also can be employed. Such water-soluble, ionic organophoεphine ligandε capable of forming a coordination complex rhodium embraced by the above formulae, aε well aε methodε for their preparation, are well-known in the art and need not be deεcribed in detail. See for example J^ Chem. Soc. (1958), pp. 276-288 and U.S. Patent Noε. 4,248,802; 4,399,312; 4,483,802; 4,633,021; 4,668,824; 4,716,250 and 4,731,486, all incorporated herein by reference. For example sulfonated- liquids may be p " fep " areliπby sulfonating the corresponding phosphine, e.g. triphenylphosphine, with fuming sulfuric acid (oleum) under controlled temperature conditionε. The ionic ' phosphine ligands are used in their water-soluble salt form. As suitable counter-ions, M, for the anionic moieties of the ionic phosphine saltε there can be mentioned the cationε of the alkali and alkaline earth metalε, e.g., lithium, sodium, potasεium, cesium, rubidium, calcium, barium, magnesium and strontium, the ammonium cation and quarternary ammonium cations. " Suitable anionic atoms or radicals include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate and the like. 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 water phase should contain an amount of the ionic organophosphine ligand sufficient to extract rhodium from the organic solution containing the solubilized organic reagent treated rhodium-teriary non-ionic organophosphoruε complex product. If the solubility of the coordination complex formed as a result of the contacting is greater in the organic phase than in the water phase, then the particular ionic organophoεphine used is not well-suited for the extraction. Generally, routine experimentation can be used to determine the suitability of any particular ionic ligand as an extractant as well as to determine both a suitable concentration of the ionic ligand for the water extractant and suitable extraction conditions. Typically, the aqueous solution may contain a concentration of at least about 0.03 mol per liter of the soluble ionic organophosphine ligand and preferably at least about 0.1 mol per liter. Routine experimentation can be used to identify an optimum ratio. Normally, to ensure a satisfactory extraction of rhodium from the organic solution there should be sufficient ionic organophosphine ligand in the aqueous phase to yield a ratio of the molar concentration of organic solvent-soluble non-ionic ligand in the organic phase to the molar concentration of ionic ligand in the aqueous phase of below about 20, more generally below about 10 and most generally below about 5. For economic reasons, the highest molar concentration ratio of non-ionic ligand to ionic ligand that yields the desired extraction should be employed. The upper limit of the water-soluble ionic ligand concentration is not critical and in part is determined by the solubility of the ionic ligand in water. However, since ultimate recovery of the rhodium likely will be accompanied by some losε of ionic ligand, too large an exceεs of ionic ligand preferably is to be avoided. Generally, based on economic considerationε, a water-soluble ionic ligand concentration below about 0.3 mol per liter and, more uεually below about 0.2 mol per liter, εhould be εuitable in moεt circumεtanceε. The aqueouε solution also may include other adjivants to facilitate the transfer (extraction) of rhodium into the aqueous phase. For example a neutral * salt, e.g., sodium sulfate or phosphate, could be added to the aqueouε phase to increaεe itε denεity and thuε facilitate itε phaεe separation from the organic solvent phase. While the organic solution and aqueous solution preferably are flowed countercurrent to one another in an extraction column, any other known extraction technique also could be employed. Thus, the aqueous extraction can be accomplished using a wide variety of known techniques- and conventional equipment. Preferably, the aqueous extraction is carried out in a continuous manner using either continuous countercurrent multi-stage contacting procedures employing a series of mixer-settlers or a trayed column or by countercurrent differential contact in a packed tower, rotary-disc contacting column and the like. Equipment suitable for accomplishing the aqueous extraction will be apparent to those skilled in the art and need not be described in any detail. A volume ratio of the organic solution (0) to the aqueous εolution (A) introduced into the extractor, e.g. the extraction column, of from about 0.01 to 100 generally should be satiεfactory for tranεferring rhodium into the aqueouε phaεe, contacting (volume) ratioε (O/A) between about 1 to 10 are more typical. An optimum value for any specific set of circumstanceε can be determined uεing routine experimentation. The temperature for the contacting (aqueous extraction) also is not critical and to a certain extent depends upon the specific compositions of the organic solution and the aqueous solution. Generally, under atmospheric pressure operation, a temperature of from about ambient up to about 100°C is satiεfactory with a temperature from about ambient (e.g. 25 β C) to 60°C being preferred. In any event, any condition of temperature and preεεure at which the organic εolution and the aqueouε solution remain immiscible and in the liquid state can be employed. The contacting time also is not critical and need only be sufficient to accomplish the desired extraction of the rhodium from the organic phase. A contact time between about 1 minute and 24 hours should prove adequate in most instances. A contact time between about 3 and 30 minutes is more typical. An appropriate contacting period can be determined using routine experimentation. This contacting of the aqueous solution and the organic solution causes rhodium to transfer from the organic solution into aqueous solution. Organic εolution recovered * - from the overhead of the extraction column may contain reεidual rhodium, organic εolvent-εoluble organophoεphoruε ligand and organic εolvent, e.g., aldehyde product and higher boiling liquid aldehyde condenεation by-productε in the case of hydroformylation. If desired, this stream can be retreated separately to recover both residual organophosphoruε ligand and reεidual rhodium. The aqueouε εolution recovered from the bottom of the extraction column will contain rhodium that waε preεent in the original organic solution starting material . By appropriately treating this aqueouε εolution, it is posεible to tranεfer the rhodium, back into an organic εolvent, which in the specific case of hydroformylation should be suitable for reuse in a hydroformylation reaction medium as catalyst. For instance, the aqueous rhodium containing solution may be treated with a conditioning reagent, in order to reduce the amount, in the aqueous solution, of the water-soluble ionic organophosphine ligand capable of complexing with the rhpdium. In other words, the aqueous solution is treated so that the complex-forming ability of the ionic ligand is rendered incapable or less capable of forming a coordination complex with rhodium. If desired, the concentration of rhodium in the aqueous solution can be concentrated, e.g. by vaporization, before or after treatment with the conditioning reagent. In any event, an aqueous solution generally will be obtained having a rhodium concentration of from about 1 to 50,000 ppm, and more typically between about 5 and 10,000 ppm, calculated as rhodium metal. The aqueouε rhodium containing εolution can be treated with a variety of conditioning reagentε in order to reduce the amount of (i.e. chemically degrade or alter) the ionic organophoεphine ligand. For example, the aqueouε εolution can be treated with an_ yield precursor such as maleic acid, with a strong acid such as εulfuric acid, with an alkylating agent such aε methyl iodide or with an oxidizing reagent such aε hydrogen peroxide or an organic peroxide. The conditioning reagent εhould react with the water-soluble ionic ligand to produce products that lack a coordinating affinity for the rhodium. Preferably, the reaction products are water-soluble and organic solvent-insoluble so that they are not back-extracted into the organic solvent during subsequent treatment. Treatment with the conditioning reagent thus reduces the amount, in the aqueous solution, of ionic ligand capable of strongly coordinating with rhodium. Although not particularly critical, the aqueous 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 back-extraction of rhodium into a organic solvent which contains an organic solvent-soluble and water-insoluble non-ionic organophosphoruε ligand. A treatment temperature of about 25° to 60°C for a time period of one to four hours should be adequate in most caεeε. It is preferred to reduce the amount of water-soluble ionic ligand by at least about 70% and preferably by at least about 851. An amount of residual ionic ligand of below about 10 equivalents, i.e., 10 mols of ligand per gram atom of rhodium, and preferably below about 5 equivalentε iε eεpecially preferred. Best resultε are obtained if the rhodium coordination ability of the water-εoluble ionic ligand iε completely destroyed. Suitable yield 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 the group consisting of unsaturated compounds having the formula wherein Z is a radical selected from the group con-s-is-ting of 0 It -CRll -CN, -Cl,-Br,-I,-N0 2 , and -OR 12 ;R U is a radical selected from the group consiεting of hydrogen, alkyl, aryl, hydroxy, alkoxy, amino and halogen; R 12 is an alkyl or aryl radical; and R 8, R9 and R10 individually are radicals selected from the group consisting of hydrogen, alkyl, aryl, Z radicals as defined above and -CH,Z radicals wherein Z 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 aqueous 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 water-soluble ionic 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 water-soluble ionic organophosphine ligand to- form a water-soluble phosphonium salt thereof. Compounds of this class are monovalent hydrocarbon halides, such as methyl iodide (see U.S. Patent 4,429,161, the disclosure of which is incorporated herein by reference) . 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 peracidε which preferably form water-soluble oxidation by-products with the water-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 forηi, but more preferably and conveniently is employed in the form of air or in admixture with an inert gas * , such aε nitrogen in' order to minimize any exploεive hazardε . The liquid organic peroxides, which may also be employed as oxidantε herein, preferably encompaεε water-εoluble organic peroxides of the formula R-O-O-R' , wherein R represents a radical selected from the group consiεting of monovalent hydrocarbon radicalε of 2 to 20 carbon atomε, 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 represented by R as defined above. Preferred monovalent hydrocarbon radicals represented by R and R' above are alkyl and aralkyl radicals, especially tertiary 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, ethylbenzene hydroperoxide, and the like. Such organic peroxides and/or methods for their preparations are well known in the art. The aqueous solution recovered from this treatment having a lowered amount of rhodium complex-forming, water-soluble ionic organophosphine ligand then can be contacted (back-extracted) with an immiscible, non-polar, organic solvent containing a non-polar organic solvent-soluble and water-insoluble non-ionic organophosphorus ligand. The same non-polar organic solvent-soluble and water-insoluble non-ionic ligands previously described as being useful for hydroformylation can be employed. Aε with the firεt extraction, the contacting typically can be done in any εuitable extraction veεεel. Again, any εubεtantially non-polar organic solvent which forms a separate, distinct phase in the presence of the aqueous phase, and, in the specific case of hydroformylation, which does not adversely (i.e., which iε preferably compatible with) the deεired hydroformylation reaction medium can be employed. Particular useful non-polar solvents are those known to be suitable for use in prior art hydroformylation procesεeε aε described previously herein. The non-polar organic solution used for back .extraction preferably contains the same organic solvent-soluble, non-ionic organophosphoruε 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, non-ionic organophosphoruε ligand sufficient to back-extract rhodium from the treated aqueous εolution. The necesεary concentration of the non-polar organic solvent-soluble, non-ionic ligand will depend, interalia, on the nature and residual level of the water-soluble, ionic phosphine ligand in the aqueous phase, on the particular non-polar organic εolvent-εoluble non-ionic ligand and its amount in the organic εolvent and on the extraction conditionε. Generally, routine experimentation can be. used to determine the suitability of any particular non-polar solvent-soluble, non-ipnic ligand as a back extractant, aε well aε to determine both a εuitable ligand concentration for the non-polar εqlvent 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, non-ionic organophosphoruε ligand and normally will contain about 0.03 to 0.6 molε per liter. Normally to enεure a satisfactory extraction of rhodium from the aqueous εolution, there should be sufficient non-polar organic solvent-soluble, non-ionic ligand in the organic solvent to yield a ratio of the molar concentration of non-polar organic solvent-soluble, non-ionic ligand in the organic solvent (non-ionic ligand) to the molar concentration of residual polar water-soluble ionic ligand capable of forming a coordination complex with rhodium in the aqueous phase (ionic ligand) of above about 10, preferably above about 20, and most preferably above about 30. Conditions and equipment for the back-extraction step can be the same aε thoεe employed in the initial organic-aqueous extraction used to transfer rhodium from the catalyst solution to the aqueous εolution. Thuε the organic εolution containing organic reagent treated εolubilized rhodium - tertiary non-ionic organophoεphine complex products of thiε invention can be readily employed aε the εtarting materialε for the aqueouε extraction proceεε outlined above and disclosed in Assignee's U. S. Patent Application Serial No. 231,508. In turn the aqueous rhodium containing solutions derived therefrom can be used in the reaction mediums of aqueouε hydroformylation proceεεeε or to εerve aε a means for preparing organic εolvent containing back-extracted rhodium - tertiary non-ionic phosphines complex compositionε for use in the reaction mediums of non-aqueous hydroformylation processes. Alternatively applicants have found that organic solutions containing certain organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex products of this_ invention need not neceεsarily be extracted into an aqueous solution but can themεelveε become subεtantially active e.g., under hydroformylation conditionε when subsequently used in non-aqueous hydroformylation catalysiε as fully detailed for example in Assignee's U.S. Patent Application Serial No. 231,510 entitled REACTIVATION OF HYDROFORMYLATION CATALYSTS filed August 12, 1988 in the names of the same subject inventors of this application (the entire discloεure of which is encompassed herein by reference thereto). Said copending application Serial No. 231,510 discloses the invention of treating obtained organic solutions of the organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex products of this invention, wherein the organic reagent employed is any of the above described organic reagents employable in this invention, except alkyne and alkene compounds of the above formulae wherein X is a hydroxyl (i.e. -OH) radical, to obtain a rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst having better catalytic hydroformylation activity than the partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst employed in the organic solution starting material of this invention. The process comprises of eliminating from such organic solutions of the organic reagent treated solubilized rhodium - tertiary non-ionic organophoεphine complex product any hydroformylation catalytic inhibitor formed by the process of this invention, to obtain a rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst that is more catalytically active than the partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst in the organic solution starting material of this invention, and such may be accomplished in a number of ways. For instance, while not intending to be held to any specific chemical theory or mechanistic discourse on just exactly how such a beneficial desired result is achieved, it is considered that intrinsic deactivation of the rhodium - tertiary non-ionic organophosphine catalyst is due at least in part to the situ formation of rhodium complex clusters during the hydroformylation procesε, which are catalytically inactive or lesε active than the active rhodium complex catalyεt species, thus decreasing the amount of active rhodium values in the reaction medium. It is further considered that in the procesε of thiε invention the organic reagent reacts with the rhodium of such clusters to form new rhodium complex species in the treated organic solution. While the new rhodium complex εpecieε in the organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product has not been found to immediately exhibit improved catalytic activity over that of the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst in the organic solution starting material, it iε considered that such is due to a catalytic inhibitor formed during the organic rea ' gent tre •aatment. ' Said catalytic inhibitor is considered to be the acid moiety of the organic reagent which may be present in said treated complex product in its free form and/or as part of a new rhodium complex species formed by said treatment. In any event it has been found that the elimination of whatever form the catalytic inhibitor is present aε, results in obtaining a rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst that iε more catalytically active than the partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst in the organic εolution starting material of the process of this invention. Again while not intending to be held to any specific chemical theory or mechanistic disclosure, it is considered that during and/or as a result of the elimination of such catalyst inhibitor, the organic reagent treated solubilized rhodium complex product, is εomehow converted from an inhibited complex to a more active rhodium complex εpecieε. Accordingly εaid procesε comprises eliminating from the organic solution of the organic reagent treated solubilized rhodium - tertiary non-ionic organophoεphine complex product of thiε invention any hydroformylation catalytic inhibitor formed by the proceεε of this invention to obtain a rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyεt that iε more catalytically active, than the partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst in the organic solution starting material of thiε invention. Said elimination of such a hydroformylation catalytic inhibitor may comprise either removing or neutralizing said hydroformylation catalytic inhibitor in any suitable manner as described more fully herein below. For instance, it is to be underεtood that the particular procedure applicable may be governed and/or depend upon εuch factors as the particular organic εolution starting material as well as the organic reagent employed. One illustrative procedure may comprise removing εuch catalytic inhibitor by contacting the organic reagent treated organic εolvent-solubilized rhodium - tertiary non-ionic organophoεphine complex product of this invention with any εuitable aqueous alkaline or buffer εolution and phase separating the organic and aqueous phaseε of the reεult mixture to obtain an organic solubilized rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst product that is more catalytically active than the organic solubilized partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst contained in the organic solution starting material. It is considered that any of the above mentioned organic reagents, except for alkyne alcoholε and alkene alcohols, may be employable with this procedure, since it is considered that the catalytic inhibitor that iε formed may be eliminated (removed) along with the aqueous phase during said phase separation. The improvement in hydroformylation catalytic activity of the obtained organic solubilized rhodium - tertiary non-ionic organophosphine complex product of said phase εeparation may then be confirmed by employing same in a non-aqueous hydroformylation procesε. Of course it is to be understood that such confirmation may or may not be immediately obtained upon the start up of εuch a non-aqueous hydroformylation procesε but may come about later after the non-aqueous hydroformylation haε been continuouεly carried out for a while. Yet another and even more preferred procedure merely compriεeε continuously hydrofor ylating the organic reagent treated εolubilized rhodium - tertiary non-ionic organophoεphine complex product of this invention to obtain a solubilized rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst product that is more catalytically active than the solubilized partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyεt contained in the organic εolution starting material of this invention. This preferred procedure omits the need for the above discuεεed treatment with an aqueous alkaline or buffer solution of said product prior to such hydroformylation. However the succeεε of this procedure may be dependent upon the type of organic reagent employed. For example it has been found that when the organic reagent iε propargyl acetate, continuouε non-aqueous hydroformylation of the treated product reεulted in a hydroformylation procesε that exhibited -improved catalytic activity above that obtained with the correεponding untreated partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst in the organic εolution starting material. Accordingly it is considered that the use of mildly acidic organic reagents such as the alkyne and alkene compounds of the above formulae wherein X represents a carboxylate radical, as well as the organic reagent propiolate compounds and oxide compounds defined above, result in a relatively mild catalytic inhibitor which may be conveniently eliminated (removed) via continuous hydroformylation over time. For example it is considered that when εuch mildly acidic organic reagentε are employed the inHibitor formed may be gradually eliminated (removed) from the reaction medium of the continuous hydroformylation procesε e.g., via the recovery procedure uεed to obtain the deεired aldehyde product thuε reεulting in the deεired catalytically improved rhodium - tertiary non-ionic organophoεphine complex catalyst. Said improvement in catalytic activity may be readily determined by analyzing for same during said continuous hydroformylation. Aε noted above such confirmation of improved activity may only be exhibited after the hydroformylation has been continuouεly carried out for a while. Any suitable alkaline material may be employable for the aqueous alkaline solutions useful in the above discusεed procedure. Illuεtrative alkaline materialε that may be mentioned include e.g., the alkali metal and alkaline earth metal and ammonium salts of hydroxides, carbonates, and borohydride, such as sodium bicarbonate, sodium carbonate, sodium hydroxide, potasεium hydroxide, lithium hydroxide, ceεium hydroxide, barium hydroxide, calcium hydroxide, ammonium hydroxide, sodium borohydride, and the like, especially sodium bicarbonate. Aqueous buffer containing εolutionε may alεo be uεeful the above diεcussed procedure. Illustrative buffer mixtures include salts of inorganic oxy acids, such as phosphine acid/monobasic phoεphate/dibaεic phosphate of an alkali metal, boric acid/borate of an alkali metal, and carbonate/bicarbonate of an alkali metal; e.g., equi olar mixtures of the monobasic phosphate and the dibasic phosphate of sodium or of potasεium, or of the carbonate and the bicarbonate of sodium or of potassium. Of course it is to be understood that any suitable mixture of aqueous alkaline and buffer εolution may be employed if desired. The contacting of the organic solution of the organic reagent treated rhodium - tertiary non-ionic organophoεphine complex product of thiε invention and such aqueous alkaline or buffer solutions may be carried out in any suitable manner using any suitable equipment. Such contact is carried out under non-hydroformylating conditions as explained above. For example the contact may be effected under non-hydroformylating conditions by simply mixing the aqueous alkaline or buffer εolution with the treated organic solution product of this invention such aε in a conventional washing procedure. It iε preferred to contact, e.g, wash, the treated product of this invention with the aqueous alkaline or buffer solution when employed under non-hydroformylat on conditions and preferably under nitrogen at atmospheric pressure. Non-hydroformylating contacting temperatures of from about 20 β C. to about 100 β C. and more preferably from about 25 β C. to about 65 β C. should be sufficient for most purposeε, although lower or higher temperatures may be employed if desired. Normally the washing can be completed within a matter of minutes, and the organic and aqueous phases phases of the mixture separated in any desired conventional fashion. The amount of alkaline or buffer material, when employed in the above diεcuεεed procedure, required to obtain the deεired result is not particularly critical for it obviously need only be that amount sufficient to achieve at least some improvement, and naturally more preferably the best improvement, in catalytic activity of the particular partially deactivated rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst involved. In general when employed under non-hydroformylating conditions aqueous alkaline or buffer solutions containing from about 0.1 to about 20% by weight of alkaline or buffer material and ranging from about 0.1 to about 1.5 parts by • volume ** per part of treated product of this invention should be sufficient for most purposes. Illustrative preferred aqueous alkaline solutions may include from about 0.1 to about.0.5 parts by volume of a 5 to 10 weight percent aqueouε sodium bicarbonate solution. Of course it is to be understood that when employed such aqueous alkaline or buffer εolution waεhes could be carried out more than once if desired e.g., successive washingε of the preceding obtained organic phases collected via phase separation from the aqueous phase, although it iε believed that only one such washing should be sufficient for oεt purpoεes. Further as with any εuch conventional washing procedure, the obtained separated organic phase may be further washed with water one or more times if desired to remove any small amounts of alkaline or buffer material contained in said organic phase. As described above εuch aqueous alkaline or buffer treatment procedures may be considered as being necessary for achieving any improvement in catalyst activity for the partially deactivated rhodium - tertiary non-ionic organophoεphine complex hydroformylation catalyst involved, when the organic reagent used is either (i) an alkyne or alkene compound of the above formula wherein X representε either halogen, a sulfonate or phosphoniu radical aε defined above, (ii) a methyl halide compound or (iii) a methyl sulfonate compound. Alternatively, when the organic reagent used is an alkyne or alkene compound of the above formula wherein X represents a carboxylate radical, or a propiolate compound or oxide compound as defined above, the preferred procedure may comprise merely continuously hydrofor ylating the treated organic product solution of this invention until at least a sufficient amount of the catalytic inhibitor has been eliminated in order to obtain a rhodium - tertiary non-ionic organophosphine complex hydroformylation catalyst that is more catalytically active than the partially deactivated -rhodium - tertiary non-ionic organophoεphine complex hydroformylation catalyst contained in the organic solution εtarting material. Of course it is to be understood that such continuous hydroformylation processeε, be they for reactivation and/or for confirmation of the deεired improved catalytic activity are well known in the art, as seen already herein discussed above and contained in the above mentioned cited references. Accordingly any of such conventional continuous hydroformylation processes and conditions already disclosed and discuεεed herein may be employed for εaid reactivation and/or for confirmation of the desired improved catalytic activity and εuch proceεεeε and conditionε obviously need not be further detailed again. The exact time period of continuous hydroformylation required before any improvement in catalyst activity may be observed over that of the corresponding partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst employed will of course obviously vary depending upon the compounds and procesεing conditionε involved. Thuε obviously no arbitrary time period for εuch an accomplishment can, nor eed^- e-ass ' ig ed for the elimination of the catalytic inhibitor by εuch continuouε hydroformylation. Rather it iε εufficient to understand that such may be accomplished merely by subjecting the treated organic product solution of this invention to continuous hydroformylation for a sufficient period of time until there is evidenced an improvement in the catalytic activity of the process over that obtainable using the corresponding partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst of the organic εolution starting material of this invention. In general it iε preferred that εome improvement in catalyst activity should be evidenced within at least a few hours or earlier. Of course it is to be understood that any improvement in catalyεt activity should continue to get better with time until the maximum improvement possible is obtained. Again the continuous hydroformylation procedures employable are not critical and any known conventional procedure that achieves the desired result may be employed. Preferred continuous hydroformylation processes are those involving a liquid catalyst recycle process wherein one need only treat all or a part of the reaction medium or all or part of the liquid catalyst containing recycle medium according to the process of thiε invention and then continue to employ the εame hydroformylation proceεs. Further, improved regenerated hydroformylation catalytic activity may be determined by any εuitable method such as e.g., by measuring the rates of reaction of the partially deactivated rhodium complex catalyst in the organic solution εtarting material and the organic reagent treated rhodium complex product of this invention aε compared the activity of a freεh rhodium complex catalyεt employed in the same manner. This effect may be easily determined by carrying out the hydroformylation reactions and by continuouεly monitoring the rate of hydroformylation. The difference in hydroformylation rate (or difference in catalyst activity) may then be observed in a convenient laboratory time frame. Thus a particularly preferred and beneficial aspect of this invention may comprise merely stopping a rhodium organophosphine catalyzed continuous hydroformylation reaction which has been conducted in a reaction vessel (reactor) for a period of time sufficient to partially deactivate the catalyεt and treating, under non-hydroformylation conditions, the hydroformylation reactor medium with an appropriate organic reagent while said reaction medium remainε in the reactor, and thereafter merely reεtarting the same continuous hydroformylation process to obtain a desired ' hydroformylation catalyεt that is more catalytically active than the partially deactivated catalyεt contained in said untreated reaction medium. The hydroformylation reaction can be stopped by any convenient method e.g., by merely stopping the feed of the reactant gases (olefin, carbon monoxide and hydrogen) to the reaction vessel and clearing-'t e -re-cycle lines of the reaction syεtem. The appropriate organic reagent, ξ.g., propargyl acetate, may then be added to the reaction medium in the reactor in any appropriate manner and mixed therein followed by restarting the hydroformylation procesε via the readdition of the reactant gaεeε to the reactor at any deεired conventional temperature and pressure and continuing the same hydroformylation using said organic reagent treated reaction medium. Of courεe it iε not neceεsary to stop the continuous hydroformylation procesε at all if εuch iε not deεired. For example yet another preferred aεpect and benefit of this invention comprises treating all or part of the liquid catalyst containing recycle medium of a εuch a continuouε hydroformylation procesε with an appropriate organic reagent and returning the thuε treated catalyst containing recycle medium to the reaction medium in the reactor of the continuous hydroformylation process. Such may be accomplished by any εuitable method, e.g., drawing off a part of the recycle medium to an appropriate container treating εame and returning the treated medium, without any need for εtopping or εhutting down the continuous hydroformylation. Of course likewise a portion of the hydroformylation reation medium itself may be withdrawn from the reactor, and also so treated and returned to the reactor in the εame fashion, if deεired, without stopping or shutting down the continuous hydroformylation. Further in addition to being readily returnable to the reaction medium of the same hydroformylation process from whence the partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst may be derived, if desired the organic reagent treated rhodium - tertiary non-ionic organophosphine complex product of this invention may be useful as the catalytic εtarting material or as a catalytic booster for any different conventional hydroformylation process if desired. The following examples are illustrative of the present invention and are not to be regarded as limitative. It is to be understood that all parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise indicated. Rhodium concentrations were determined using conventional atomic absorption spectroscopy (AAS). Moreover, the sodium salt of 3-(diphenylphosphino) benzene εulfonic acid may be repreεented has having the formula EXAMPLES 1 to 15 This example illustrateε increasing the amount of rhodium capable of being extracted into an aqueouε εolution of a sodium salt of 3-(diphenylphoεphino) benzene sulfonic acid (TPPMS-Na) from an organic solution of a partially deactivated rhodium - triphenylphosphine complex hydroformylation catalyst composition that had been employed in a non-aqueous hydroformylation procesε directed to producing butyraldehyde by hydroformylating propylene and whoεe catalytic activity activity had declined from 100% active to about 85 percent of fresh catalyst. Each experiment was conducted in essentially the s ' ame manner, the treatments being carried out in standard laboratory glassware and under an inert nitrogen atmosphere. The procedure .employed conεiεted of adding variouε amounts of the chemical reagents reported in the table below to individual 25 gram samples of said rhodium - triphenylphosphine complex catalyst composition consisting essentially of about 12 weight percent triphenylphosphine (TPP) ligand and * about 272 ppm rhodium, calculated as rhodium metal, the remainder being esεentially butyraldehyde product (about 75-80 weight percent) and - hydroformylation by-products. About 25 grams of dioctylphthalate (DOP) waε alεo added to each treated catalyst εolution mixture to facilitate stripping of the butyraldehyde and other lights, and to allow for a more consistent continuous single paεε reactor operation. Each εolution mixture waε then warmed to about 60°C for about 4 hourε and eεεentially all of the butyraldehye lights waε nitrogen εtripped from the εolution. Each solution was then added to a single pass glass reactor and employed in a continuous single pass hydroformylation procesε directed to hydroformylating propylene (at about 100 β C. uεing a gaseous mixture of about 100 psig. hydrogen, about 18 psig. carbon monoxide and about 23 psig. propylene) for from about 16 to about 28 hours. The catalyst solutions were then discharged from the glaεε reactor and the extractability of rhodium therefrom into an aqueous solution containing 10 weight percent of said TPPMS-Na ligand determined by the following procedure. In each example a 10 gram sample of each said discharged organic catalyst solution was mixed with 15 gram samples of said aqueous solution at room temperature for about 3 hourε. The phases were allowed to separate and each was recovered and the amount of rhodium remaining in the organic phase measured and compared with that amount of rhodium in the 10 gram sample employed for said extraction. The results of each experiment aε compared to the rhodium extractability from a fresh catalyst solution and the initial partially deactivated catalyst solution are given in the following Table 1. TABLE 1 Rhodium Ex. Reagent/ (ppm) No . Reagent Rhodium a Before 1 None (Fresh 272 Catalyst) None (Spent 272 Catalyst) d 3 Allyl Chloride 4.98 214 4 Propargyl Benzene 10.04 200 Sulfonate 5 Propargyl Chloride 10.13 225 6 Furfuryl Acetate 10.75 222 7 Allyl Methacrylate 10.00 203 8 Benzyl Acetate 9.92 224 9 Cyclohexene Oxide 10.04 211 10 Cyclopentene Oxide 10.00 202 11 Diketene 10.08 203 12 Propargyl Triphenyl- 9.89 209 phosphonium Bromide 13 Allyl Trifluoroacetate 9.82 255 14 Ethyl Propiolate 10.0 212 15 Propargyl Alcohol 10.0 222 a. Reagent to Rhodium Molar Ratio. b. Amount of rhodium, parts per million, before extraction in organic solution starting material. c. Amount of- rhodium, parts per million, after extraction remaining in the separated organic phase. Initial partially deactivated untreated catalyst solution starting material. e. Rhodium recovery extraction efficiency. SUBSTITUTESHEET EXAMPLES 16 to 25 Thiε example illuεtrateε increaεing the amount of rhodium capable of being extracted into an aqueous solution of a sodium salt of 3-(diphenylphosphino) benzene εulfonic acid (TPPMS-Na) from an organic εolution of a partially deactivated rhodium - triphenylphosphine complex hydroformylation catalyst composition that had been employed in a non-aqueous hydroformylation process directed to producing butyraldehyde by hydroformylating propylene and whose catalytic activity activity had declined from 100% active to about 35 percent of fresh catalyεt. Each experiment was conducted in esεentially the εame manner, the treatmentε being carried out in εtandard laboratory glaεsware and under an inert nitrogen atmosphere. The procedure employed consisted of adding various amounts of the chemical reagents reported in the table below to individual 25 gram samples of said rhodium - triphenylphosphine complex catalyst composition consisting esεentially of about 12 weight percent triphenylphoεphine (TPP) ligand and about 750 ppm rhodium, calculated aε rhodium metal, the remainder being eεεentially butyraldehyde product (about 75-80 weight percent) and hydroformylation by-productε. Each εolution mixture was then warmed to temperature for the stated period of time given in the table below, and the extractability of rhodium therefrom into an aqueouε solution containing 5 weight percent cf said TPPMS-Na ligand determined by the following procedure. In each example a 50 gram sample of each organic εolution of said rhodium - TPP complex catalyεt composition (a 200 gram sample was used in Example 19 and a 20 gram sample was used in Example 20) was mixed with 10 gram samples (25 gram samples in Example 16, 17 and 19 and a 12 gram sample in Example' 20) of said aqueous εolution at 50°C. for thirty minutes. The phases were allowed to separate and each was recovered. Each extraction procedure was then repeated on each obtained organic phaεe and then εequentially repeated for a third time on the εecond obtained organic phase ( the same sequential extraction procedure being carried out a total of five times in Example 19). The amount of rhodium remaining in the final obtained organic phase of each example was then measured and compared with that amount of rhodium in the initial sample of the organic solution starting material. The resultε of each experiment aε compared to rhodium extractable from the initial partially deactivated catalyεt εolution are given in the following TABLE 2. TABLE 2 Reagent Rhodium Rhodium Rhodium Ex. Amount Time Temp, (ppm) (ppm) X ____ Reagent (Grams) (Hours) CO Before 3 After 0 Recovery 0 16 (Spent None 0 0 750 482 36 Catalyst d ) 17 Allyl Chloride 18 Allyl Chloride 19 Allyl Chloride 20 Benzyl Bromide 21 Allyl Chloride 22 Allyl Acetate 23 Allyl Bromide 24 Allyl Butyrate 25 Allyl Iodide a. Amount of rhodium, parts per million, before extraction in organic solution starting material. b. Amount of rhodium, parts per million after extraction remaining in final obtained separated organic phase. c. Rhodium recovery extraction efficiency. d. Initial partially deactivated untreated catalyst solution starting material. :_5ϊ I s o ua3T! UTESHEET EXAMPLES 26 TO 30 Each of the following Exampleε 26 to 30 employed a sample of a catalyεt solution derived from a continuous non-aqueous hydroformylation procesε directed to producing butyraldehyde from propylene using a rhodium - TPP complex catalyst, which had been operated for a sufficient period of time to cause intrinsic deactivation of the catalyεt to about 42% of a freεh catalyεt. The partially deactivated catalyεt εolutionε employed contained about 450 pmm rhodium, calculated aε rhodium metal, about 12 wt.% triphenylphoεphine (TPP) and about 14 wt.% butyraldehyde, the remainder being hydroformylation by-productε, e.g., aldehyde condenεation by productε. Each untreated catalyεt solution (20 gram sampleε) waε charged to * a continuouεly operating εingle paεε hydroformylation reactor. A mixture of carbon monoxide, hydrogen, propylene and nitrogen waε fed to the reacting system. The reactor was heated to 100°C. and a steady state mixture of reactant gaεeε (i.e., syn gas and propylene) was obtained in the syεtem (carbon monoxide about 18 psig; hydrogen about 95 psig; propylene about 23 psig) . Total reaction pressure was about 160 psig. The butyraldehyde production rates, in gram moles per liter per hour, were determined: " by monitoring the flow rate and composition of off-gases from the reactor. Once stable production rate had been achieved (note Table 3 below) the reacting gases were valved off to the reactor and the prescribed amount of organic reagent of Table 4 below added to each solution contained in the reactor and in the absence of said reactant gaεeε. The contentε of the reactor were then held at temperature under 160 psig. nitrogen for the period of time given in Table 4 below. (In Example 27, 100 equivalents of the organic reagent based on the total rhodium content waε added to the catalyst solution every hour for 5 hours.) The reacting gases i.e., εyn gas and propylene, were then re-introduced to the reactor establiεhing the previously achieved reaction conditions. Upon re-introduction of the gases each reaction waε continued until a stable aldehyde production rate was re-achieved, within 5 to 16 hours. Each reaction solution was then removed from the reactor and the extractability of rhodium therefrom into an aqueous solution containing 5 weight percent of the sodium salt of 3-(diphenylphosphino) benzene sulfonic acid (TPPMS-Na) ligand determined by the following procedure. In each example a 15 gram εample of each organic εolution of 'εaid organic reagent treated rhodium - TPP complex catalyst composition was mixed with 7.5 gram samples of said aqueous solution at 50 β C. for thirty minutes. The phases were allowed to separate and each was recovered. The εame extraction procedure was repeated on each obtained organic phase and then εequentially repeated for a third time on the εecond obtained organic phaεe. The amount of rhodium remaining in the final obtained organic phase of each example as well as in each aqueouε phase was measured and compared with that amount of rhodium in the initial εample of the organic solution εtarting material. The resultε of each experiment as compared to rhodium extractable from a sample of the initial partially deactivated catalyst solution by the same procedure are given in the following TABLE 5. TABLE 3 a) Butyraldehyde production in gram, moles per l l iitteerr p ■ noerr h "hrourr TABLE 4 30 Spent Catalyst b None a) Reagent to rhodium mole ratio. b) Initial partially deactivated untreated catalyst solution starting material. SUBSTITUTESHEET TABLE 5 Rh (ppm) Rh (ppm) Rh (ppm) Rh Ex. Rh (ppm) 1st Aqueous 2nd Aqueous 3rd Aqueous Rh (ppm) Percent 5 0 h 0 Ph " e f a) Amount of rhodium, parts per million, before extraction in organic solution starting material. b) Amount of rhodium, parts per million, in first extracted aqueous phase. c) Amount of rhodium, parts per million, in second extracted aqueous phase. d) Amount of rhodium, parts per million, the third extracted aqueous phase. e) Amount of rhodium, parts per million, after three extractions remaining in final obtained separated organic phase. f) Rhodium recovery extraction efficiency. SUBSTITUTE SH SET EXAMPLES 31 TO 32 Two 50 gram εampleε of a concentrated catalyεt εolution derived from a continuouε non-aqueouε hydroformylation proceεε directed to producing butraldehyde from propylene using a rhodium - TPP complex catalyεt, which had been operated for a εufficient period of time to cauεe serve intrinsic deactivation of the catalyst to about 42% of a freεh catalyst, and containing about 11,898 ppm rhodium, calculated aε rhodium metal and a minor amount of triphenylphosphine (TPP), the remainder consiεting essentially of triphenylphosphine oxide and high boiling hydroformylation by-products, e.g., aldehyde pentamers were obtained via the procedure described in USP 4,297,239. Each experiment was conducted in essentially the same manner, the treatments being carried out in standard laboratory glasεware and under an inert nitrogen atmosphere. About o.7 grams of allyl chloride was added to and mixed with one said 50 grams sample solutions and the solution warmed to about 80 β C. for 48 hours (Examples 31). The other 50 gram sample solution waε left untreated (Example 32). The extractability of rhodium from εaid 50 gram εa ples was determined by mixing them with 25 -86- gram samples of an aqueous solution of 10 percent by weight of the sodium salt of 3-(diphenylρhosphino)- benzene sulfonic acid (TPPMS-Na) ligand at 50 β C. for about thirty minutes. The phases were allowed to separate and each was recovered. The same extraction procedure was repeated on each obtained organic phaεe and then εe uentially repeated for a third time on the εecond obtained organic phaεe. The amount of rhodium remaining in the final obtained organic phase of each example was then measured and compared with the amount of rhodium in the initial εample of the organic solution starting material. The resultε of each experiment are given in the following TABLE 6. TABLE 6 Ex. Organic Rh (ppm) Rh (ppm) Rh (%) No. Reagent Before- After- Recovery- 31 Allyl Chloride 11,898 2,763 77 32 None 11.898 5,723 52 a) Amount of rhodium, parts per million, before extraction, in the organic solution εtarting material. b) Amount of rhodium, partε per million, after extraction remaining .in final obtained separated organic phase. c) Rhodium recovery extraction efficiency. Variouε modifications and variations of this invention will be obvious to a worker skilled in the art and it iε to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.

Claims: WHAT IS CLAIMED IS 1. A procesε for increaεing the amount of rhodium capable of being extracted into an aqueouε εolution containing an ionic organophosphine ligand, which rhodium is present in an organic solution containing a partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst, said procesε compriεing mixing under non-hydroformyl tion conditionε, said organic solution with an organic reagent selected from the group consiεting of (a) alkyne compoundε having the formula R-C=C-CH,-X, (b) alkene compounds having the formula (R 1 ) (R^)C=C(R 3 )-CH 2 -X, (c) diketene, (d) methyl halides, (e) methyl sulfonateε, (f) propiolate compoundε having the formula H HCC≤≤CC--CCl(0)OR 14, and (g) oxide compoundε having the formula wherein X repreεentε a radical selected from the group conεisting of halogen atomε, a hydroxyl radical, a carboxylate radical of the formula a -OC(0)R , a εulfonate radical of the formula o -OSO- and a phoεphonium radical of the formula [-P + (R 8 ) 3 3 [Y-l; wherein R 8 in the above formulae for X, each individually represent a monovalent hydrocarbon radical having from 1 to 18 carbon atomε εelected from the group conεiεting of alkyl, aryl, aralkyl, alkaryl and cycloalkyl radicals and wherein Y representε an acid anion; and wherein each R, R , R , R , R , R , R , R 7, and 14 radical individually repreεentε hydrogen or a monovalent hydrocarbon radical having from 1 to 18 carbon atoms selected from the group consiεting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl radicalε; with the following proviεoε: a that R in the above carboxylate formula can alεo be hydrogen; that R 2 and R3 the above formula for the alkene compoundε can alεo be bonded together to form a five or six membered heterocyclic ring or monocyclic hydrocarbon ring along with the C=C group shown in said formula; and wherein any two of said R , R , R and R groups in the above formula for the oxides can be bonded together to form- a five or six membered monocyclic hydrocarbon ring along with the C-C group shown in said formula; to obtain an organic εolution of an organic reagent treated solubilized rhodium - tertiary non-ionic organophosphine complex product that contains more rhodium correspondingly capable of being extracted into an aqueouε solution containing an ionic organophosphine ligand than contained in the organic solution starting material of this process. 2. A process as defined in claim l, wherein the organic reagent is an alkyne compound having the above defined formula and wherein X representε a radical selected from the group consiεting of halogen, a hydroxyl radical, and a carboxylate radical having the above formula. 3. A proceεs as defined in claim 2, wherein R representε hydrogen. 4. A process as defined in claim 3, wherein X represents a carboxylate radical. 5. A procesε aε defined in claim 3, wherein X repreεentε a halogen atom. 6. A proceεε aε defined in claim 3, wherein X repreεentε a hydroxy radical. 7. A process as defined in claim 3, wherein the organic reagent is selected from the group consiεting of propargyl acetate, propargyl cyanoacetate, propargyl propionate and propargyl chloride, and propargyl alcohol. 8. A proceεε a defined in claim 2, wherein said partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst is a hydroformylation catalyst derived from a procesε involving the hydroformylation of an alpha olefin. 9. A process as defined in claim 8, wherein the tertiary non-ionic organophosphine is triphenylphosphine. 10. A process as defined in claim 1, wherein the organic reagent is an alkene compound having the above formula and wherein X represents a radical selected from the group consiεting of halogen, a carboxylate radical having the above formula, and a sulfonate radical having the above formula. 11. A procesε aε defined in claim 10, wherein R 1, R and 3 each repreεent hydrogen. 12. A process aε defined in claim 11, wherein X representε a halogen atom. 13. A procesε aε defined in claim 11, wherein X representε a carboxylate radical. 14. A proceεε as defined in claim 10, wherein said partially deactivated rhodium - tertiary non-ionic organophosphine complex catalyst is a hydroformylation catalyst derived from a procesε involving the hydroformylation of an alpha olefin. 15. A proceεε aε defined in claim 14, wherein the tertiary non-ionic organophoεphine iε triphenylphoεphine. 16. A procesε aε defined in claim 8, wherein the organic reagent is selected from the group consiεting of propargyl acetate, propargyl chloride, propargyl cyanoacetate, and propargyl propionate, and propargyl alcohol. 17. A procesε as defined in claim 10, wherein the organic reagent is selected from the group consiεting of allyl acetate, allyl propionate, allyl butyrate, allyl methacrylate, furfuryl acetate, allyl trifluroacetate, benzyl acetate, allyl chloride, allyl bromide, allyl iodide, allyl benzene sulfonate, allyl cyanoacetate, allyl triphenylphosphonium bromide and benzyl bromide. 18. A process as defined in claim 14, wherein the organic reagent is an alkene halide. 19. A process as defined in claim 1, wherein the organic reagent is a propiolate compound. 20. A proceεε as defined in claim 19, wherein R representε a phenyl radical or an alkyl radical. 21. A proceεε aε defined in claim 20 wherein the organic reagent iε ethyl propiolate. 22. A procesε as defined in claim 1, wherein the organic reagent is a methyl halide. 23. A process as defined in claim 1, wherein the organic reagent is a methyl sulfonate 24. A process as defined in claim 1, wherein the organic reagent is an oxide compound. 25. A process as defined in claim 1, wherein the organic reagent is diketene.

Inventors: BILLIG ERNST, BRYANT DAVID ROBERT, MILLER DAVID JAMES, SHAW BERNARD LESLIE, BILLIG, ERNST, BRYANT, DAVID, ROBERT, MILLER, DAVID, JAMES, SHAW, BERNARD, LESLIE
Applicants: UNION CARBIDE CHEM PLASTIC, UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC.
Application year: 1989
Main classification: B01J31
IPC codes: B01J31, B01J38, C07B61, C07C45, C07C47