MXPA97000114A - Membrane separation process - Google Patents

Abstract

This invention relates to membrane separation of a solubilized rhodium-organophosphite complex catalyst and a free organophosphite coordinating group from a homogeneous aqueous hydroformylation reaction mixture, the mixture also contains, in addition to the catalyst and the free coordinating group, an aldehyde product and an organic solvent

Description

"MEMBRANE SEPARATION PROCESS" RELATED REQUEST This application is a continuation in part of the North American Serial Number Application (ie, Attorney's License Number 17337) called MEMBRANE SEPARATION, filed on it. May 1995 BRIEF COMPENDIUM OF THE INVENTION TECHNICAL FIELD This invention relates to membrane separation of a complex organic rhodium-organophosphite catalyst catalyst and a free organophosphite coordinating group of a homogeneous non-aqueous hydroformylation reaction mixture, the mixture also contains in addition to the catalyst and the free coordinating group, a aldehyde product and an organic solvent.

BACKGROUND OF THE INVENTION The methods for producing aldehyde products by asymmetric or non-asymmetric hydroformylation of an olefin with carbon monoxide and hydrogen (which is more commonly referred to as syn gas or sin gas) in the presence of a complex rhodium-organophosphite catalyst and a free phosphite coordinating group are well known in the art as exemplified by US Pat. Nos. 4,599,206; 4,668,651; 4,717,775; 4,737,588; 4,748,261; 4,769,498; 4,774,361; 4,789,753; 4,885,401; 5,059,710; 5,113,022; 5,288,918; 5,312,996; 5,360,938 and 5,364,950. These non-asymmetric hydroformylation processes are preferably directed to produce aldehyde product mixtures of varying ratios of normal aldehyde product (straight chain) to isomer (branched chain), while these asymmetric hydroformylation processes are preferably aimed at forming products of enantiomeric aldehyde, i.e., optically active aldehydes. In addition, both types of these hydroformylation processes are carried out in a non-aqueous hydroformylation reaction medium. In these processes, the desired aldehyde product is preferably separated and recovered from the reaction product medium by distillation, and in liquid catalyst recycling operations, the residue containing the catalyst not volatilized and the coordinating group is returned to the reactor. Correspondingly, the effective separation and recovery of the desired aldhido product from its hydroformylation reaction product medium without excessive loss of the free organophosphite coordinating group and the rhodium-organophosphite complex catalyst is very important. When low molecular weight olefins are hydroformylated in non-aqueous systems, the separation of the aldehyde product even when it is a concern is usually not an overwhelming problem. However, this problem is increased and amplified when the process is directed to the hydroformylation of longer chain olefinic compounds to produce the corresponding higher molecular weight aldehydes. The higher temperatures and the more severe conditions necessary to volatilize the higher molecular weight aldehyde products during the separation of the hydroformylation reaction product medium may eventually lead to excessive loss (through chemical and thermal degradation) and even the phosphite coordinating groups, particularly through the normally prolonged reaction time periods required for a satisfactory commercial operation.

A similar problem arises when the higher boiling temperature aldehyde coordination byproducts, such as trimers and tetramers are formed during hydroformylation, and it is desired that they be separated from the hydroformylation recycling residues containing catalyst after recovery. separated from the hydroformylation aldehyde product. In this way, the discovery of a simpler, softer separation process would allow for the excellent removal of the organic solubilized rhodium-organophosphite complex catalyst and the free organophosphite coordinating group of the higher molecular weight aldehyde product containing mixtures of hydroformylation reaction, while avoiding these inherent problems with distillation separation that would clearly be highly beneficial to the art, and it is believed that this discovery is provided by the present invention which relates to the use of membrane separation. Now the use of the different membrane separation systems to separate the different solute liquids contained in them are already known. These processes comprise carrying a solution containing at least one solute in at least one solvent in intimate contact with a semi-permeable membrane, which allows the solvent and the other primary liquids pass through it, while rejecting the solute. The solution that passes through the membrane is called the permeate, and the solution (solute) that does not pass through the membrane (that is, that is rejected by) is called refining. The feed solution is typically at a higher pressure than the osmotic pressure difference between the osmotic pressure of the raffinate and that of the permeate. By way of example, U.S. Patent Nos. 5,215,667; 5,288,818; 5,298,669; all are directed to the use of a hydrophobic membrane to separate the complex catalysts of a water-soluble Group VIII noble metal ionic phosphine coordinating group from the aldehyde containing the hydroformylation reaction media comprising aqueous solutions, emulsions or suspensions of the catalysts. The present invention does not involve these aqueous systems and phosphine groups. PCT International Publication Number WO 94/19104 is directed to separate a complex catalyst of rhodium and alkylated or arylated homogeneous hydrocarbon soluble phosphine from a crude aldehyde containing a hydroformylation reaction product through a membrane separation process. The present invention is not directed to the use of these catalysts or coordinating groups of complex type of rhodium-phosphin. It has been proposed in a series of British patents to separate the transition metal complexes eg, the hydroformylation catalysts of the rhodium-trialkylphosphine complex, a solution of an organic solvent component v, gr, alcohols, aldehydes, ketones, organic acids, phosphines and amides, by a process comprising placing the solution in contact with one side of a cellulosic membrane (British Patent Number 1,243,507 corresponding to US Patent Number 3,617,553) or a silicone rubber membrane (Birtanic Patent Number 1,243,508 ) or a polyolefin membrane (British Patent Number 1,260,733) or a polyamide membrane (British Patent Number 1,266,180) at an applied pressure greater than the pressure on the opposite side of the membrane, the pressure differential being greater than the osmotic pressure of the system. Also, British Patent Number 1,312,076 proposes to use the same membranes and separation process of the four aforementioned British patents to separate the hydroforming transition metal catalyst from a secondary liquid stream of high boiling temperature byproducts of the hydroformylation process after the removal of the product from aldehyde through distillation. According to this patent, the aldehydes produced during the hydroformylation processes are continuously removed from the reactor as a stream of superior vapor product, while the liquid stream comprising the complex catalyst the aldehyde and the high boiling temperature residues are made pass under reaction pressure above the surface of a membrane, where the catalyst is retained and recycled to the reactor, while a portion of the high-boiling waste and aldehydes penetrate through the membrane and it is removed. The transition metal catalysts are preferably rhodium and beta-diketonate complexes which may contain or be free of other coordinating groups such as trialkylphosphines. The present invention does not involve this rhodium-phosphine complex type catalyst or rhodium complex catalysts free of oganophosphite coordinating groups. Similarly, British Patent Number 1,432,561 proposes a process for the hydroformylation of olefins which comprises reacting an olefin at elevated temperature and pressure with carbon monoxide and hydrogen, in the presence of a Group VIII metal catalyst complex (v. ., cobalt or rhodium) and a bifilic coordinating group of trivalent phosphorus, arsenic or antimony (e.g., the catalyst of British Patent Nos. 988,941 and 1,109,787) to provide a crude liquid hydroformylation product containing an aldehyde and / or an alcohol, separate the aldehyde and / or alcohol from the crude product and leave a liquid and optionally placing the liquid after separation of the metal compound of Group VIII and essentially free of aldehyde and alcohol, under conditions of reverse osmosis in contact with one side of a semi-permeable membrane of silica-rubber wherein the chains of the The polymer has at least partially been crosslinked by gamma radiation, whereby the liquid retained by the memebrane contains a higher concentration of the Group VIII metal compound and / or the bifyl coordinating group than the original liquid. The preferred Group VIII metal compounds are the cobalt compounds. The reference does not specifically disclose the removal of the complex rhodium-organophosphite catalysts and the free organophosphite coordinating groups of the present invention. Dutch Patent Number 8700881 proposes an improved membrane process for separating the hydroformylation catalysts from Group VIII metal (e.g., cobalt or rhodium-organophosphine complexes) and the free phosphine coordinating group of aldehyde by-product crude containing mixtures of hydroformylation comprising using silicone rubber membranes or modified derivatives thereof in combination with a. aromatic deflation such as non-polar hydrocarbons that do not contain oxygen or halogen, such as alkanes with 5 to 35 carbon atoms and aromatic compounds with 6 to 25 carbon atoms. The present invention does not involve these catalysts or groups "Coordinators of the cobalt type or rhodium-10-phosphine complex.

U.S. Patent No. 5,174,899 discloses that semi-permeable membranes of aromatic polyamides can be used to separate complex metal catalysts from organic solvents, e.g., salts Rhodium-triphenylphosphine or sulfonated or carboxylated trialkylphosphane phosphonates and ammonium salts of the hydroformylation aldehyde product mixtures. The present invention does not involve these complex rhodium-phosphine or phosphine type catalysts. US Pat. No. 5,265,734 is directed to employing crosslinked silicone composite membranes (e.g., polysiloxanes) in a substrate to concentrate and purify (ie, remove) organic solutes, such as colorants, dye intermediates. optical brighteners, antibiotics, peptides, proteins, enzymes, hormones and herbicides in organic solvents or in aqueous / organic mixtures as well as other liquid streams such as lubricating oils in concentrated organic solvents, catalysts dissolved in organic solvents, e.g., complexes metal organics useful for carrying out the catalytically improved polymerization reactions in organic media, and low molecular weight oligomers in paint residues dissolved in strong organic solvents. The reference does not specifically disclose the removal of the complex rhodium-organophosphite catalysts and the free organophosphite coordinating groups of the present invention.

EXHIBITION OF THE INVENTION It has now been discovered that certain composite membranes can be used to effectively separate the organic solubilized rhodium-organophosphite complex catalyst and the free organosphosphite coordinating group from a homogeneous non-aqueous hydroformylation reaction mixture, the mixture also containing the catalyst in addition and the free coordinating group, an aldehyde product and an organic solvent.

Therefore, an object of this invention is to provide a process for separating the organic solubilized rhodium-organophosphite complex catalyst and the free organo-phosphite coordinating group from a homogeneous non-aqueous hydroformylation reaction mixture. Other objects and advantages of this invention will become readily apparent from the following detailed description and the appended claims. Therefore, a generic aspect of this invention can be described as a process for separating an organic solubilized rhodium-organophosphite complex catalyst and a free organophosphite coordinating group from a non-aqueous hydroformylation reaction mixture, the mixture containing in addition to the catalyst and the group free coordinator, an aldehyde product and an organic solvent, comprising: (i) contacting the nonaqueous hydroformylation reaction mixture in a composite membrane in order to allow a considerable portion of the aldehyde product and the organic solvent to pass through through the membrane, while rejecting at least 90 percent by weight of the catalyst and the free coordinator group; wherein the aldehyde product has a solubility parameter relative to the membrane membrane solubility parameter composed of at least + 50 kJ / m3 units, but not more than + 500 VkJ / mJ units, and wherein the ratio of the molar volume of the organophosphite coordinating group to the aldheido product is > fifteen; and 5 (ii) recovering the aldehyde product and the organic solvent as a permeate.

DETAILED DESCRIPTION As will be apparent from the foregoing, the present invention generically encompasses separating the organic solubilized rhodium-organophosphite complex catalyst and the coordinated free organophosphite group from the homogeneous non-aqueous hydroformylation reaction mixture, or any part of it that contains, in addition to the catalyst and the free coordinating group, a product of "Aldehyde and an organic solvent." Thus, the starting materials of the homogeneous non-aqueous hydroformylation reaction mixture of this invention can be provided by any suitable known asymmetric or non-asymmetric hydroformylation process directed to produce aldehydes from olefins. In addition, as indicated above, methods for hydroformylating compounds olefins to produce aldehydes using a medium of A reaction comprising an organic solution containing a solubilized rhodium-organophosphite complex catalyst, a free organophosphite coordinating group and an organic solvent are well known in the art. Therefore, it will be evident that the specific hydroformylation process to produce these aldehydes of an olefinic compound, as well as the reaction conditions, hydroformylation process ingredients that serve only as a means to supply the material of the organic solution of the present invention are not critical features of the present invention. Therefore, it should be sufficient for the purposes of this invention to understand that any of the compounds that are present during the process of hydroformylation from which the starting materials of the organic solution of this invention are derived, as well : "* may be correspondingly present in the starting materials of the organic solution of this invention In general, these hydroformylation reactions involve the production of aldehydes by reacting an olefinic compound with carbon monoxide and hydrogen, in the presence of a dissolved rhodium-organophosphite complex catalyst and a group free organo-phosphite coordinator in a liquid medium that it also contains a solvent for the catalyst and the coordinating group. The process can be carried out in a continuous single-pass mode or more preferably in a continuous recycling mode of the liquid catalyst. The recycling process usually involves removing a portion of the liquid reaction medium containing the catalyst, the coordinating group and the aldehyde product from the hydroformylation reaction zone, either continuously or intermittently, and removing the aldehyde product from the same as appropriate, the rhodium catalyst containing the waste that is being recycled to the reaction zone. The aldehyde product can be passed for additional purification if desired and any of the reagents recovered eg the olefinic starting material and the no-gas will be recyclable in any desired way towards the hydroformylation zone. Also, the residue containing the recovered rhodium catalyst can be recycled to the hydroformylation zone in any desired conventional manner. Accordingly, the hydroformylation processing techniques of this invention can correspond to any of the known processing techniques, such as those preferably employed in conventional liquid catalyst recycling hydroformylation reactions. Therefore, the starting materials of the nonaqueous hydroformylation reaction mixture capable of being employed herein, include any organic solution derived from any corresponding hydroformylation process that contains at least a certain amount of four different major ingredients or components, i.e., the aldehyde product, a complex catalyst of the rhodium-organophosphite coordinating group, the coordinating group of free organophosphite and an organic solubilizing agent for the catalyst and the free coordinating group, the ingredients correspond to those employed and / or produced by the non-aqueous hydroformylation process from which the starting material of the hydroformylation reaction mixture can be derived not watery Of course, it will be further understood that the compositions of the non-aqueous hydroformylation reaction mixture employed herein may contain and will normally contain small amounts of additional ingredients, such as those that have been used either deliberately in the non-aqueous hydroformylation process. formed in situ during the process. Examples of these ingredients that may also be present include an unreacted olefin starting material, carbon monoxide and hydrogen gases, and in situ-formed type products, such as saturated hydrocarbons and / or isomerized olefins. unreacted which correspond to the olefin starting materials, and the condensation byproducts of high-boiling liquid aldehyde as well as other materials of inert co-solvent type or hydrocarbon additives if employed. Preferably, however, the starting materials of the hydroformylation reaction mixture of this invention are free of any deliberately added additive, whose primary purpose is to act as a deflating agent for the composite membrane employed in the specific process involved. As can be seen, the nonaqueous hydroformylation reaction mixtures employed herein contain both a complex rhodium-organophosphite catalyst and a free organophosphite coordinating group. By the term "free coordinating group" is meant an organophosphite coordinating group which is not complexed with (attached to or linked to) the rhodium atom of the complex catalyst. In addition, the term "non-aqueous" as used herein with respect to the hydroformylation process from which the starting materials of the nonaqueous hydroformylation reaction mixture of this invention can be derived, means that the hydroformylation reaction is carried out. , in the absence or essential absence of water, which is to say, that any water, if present in the hydroformylation reaction medium, is not present in an amount sufficient to cause either the hydroformylation reaction or the medium to be considered as embracing a separate aqueous or water phase or layer in addition to the phase organic Similarly, the term "non-aqueous" as used herein with respect to the starting materials of the hydroformylation reaction mixture of this invention means that the starting materials of the reaction mixture are also exempt or essentially exempt. of water, ie, of any water, if present in the starting materials of the hydroformylation reaction mixture is not present in an amount sufficient to cause the starting material of the hydroformylation reaction mixture to be considered as encompassing a separate aqueous or water phase or layer in addition to an organic phase. Among the organophosphites which can serve as the coordinating group of the rhodium-organophosphite complex catalyst and / or the free coordinating group of the starting materials of the hydroformylation reaction mixture of this invention are the mono-organophosphite, di-organo-phosphite and organo-polyphosphites which are well known in the art. Representative di-organophosphites can include those that have the formula: wherein R1 represents a divalent organic radical containing from 4 to 40 carbon atoms and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms. Representative monovalent hydrocarbon radicals represented by W in the above formula include alkyl and aryl radicals, while representative divalent organic radicals represented by R! they include divalent acyclic radicals and divalent aromatic radicals. Exemplary divalent acrylic radicals are eg, alkylene, alkylene-oxy-alkylene, alkylene-NX-alkylene, wherein X is hydrogen or a monovalent hydrocarbon radical, alkylene-S-alkylene and cycloalkylene radicals and the like . Especially preferred acrylic radicals are the divalent alkylene radicals, such as are more fully disclosed, eg, in US Pat. Nos. 3,415,906 and 4,567,302 and similar, all the exhibits of which are incorporated herein by reference thereto. Exemplary divalent aromatic radicals are e.g., arylene, bisarylene, arylene-alkylene, arylene-alkylene-arylene, arylene-oxy-arylene, arylene-NX-arylene, wherein X is hydrogen or a monovalent hydrocarbon radical, arylene-S-arylene and arylene-S-alkylene and the like. More preferably, R1 is a divalent aromatic radical as is more fully disclosed, eg, in US Patent Nos. 4,599,206 and 4,717,775 and the like, the entire disclosure of which is incorporated herein by reference thereto. Representative organopoliphosphites contain two or more tertiary (trivalent) phosphorus atoms and may include those having the formula: wherein X represents a substituted or unsubstituted m-substituted hydrocarbon radical containing from 2 to 40 atoms /, .. of carbon, wherein R1 is equal to that defined in Formula I above, wherein each radical R is independently a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms, wherein a each can have a value from 0 to 6, with the proviso that the sum of a + b is from 2 to 6 and m is equal to + b. Of course it will be understood that when a has a value of 2 or more, each radical R! It can be the same or different. Illustrative preferred organopolyphosphites may include bisphosphites, such as those of formulas III to V, which are presented below: wherein each R, R1 and X of Formulas III to V are the same as defined above for Formula II. Preferably each R, R1 and X represents a divalent hydrocarbon radical which is selected from the group consisting of alkylene, alkylene-oxy-alkylene, arylene and bisarylene, while each radical R represents a monovalent hydrocarbon radical which is selected from the group consists of alkyl and aryl radicals. These phosphites of Formulas (II) to (V) can be found described in greater detail in U.S. Patent Nos. 4,769,498; 4,885,401; 5,364,950. and 5,264,616, the total exposure of which is incorporated in the presence by reference to them. Representative mono-organophosphites may include those having the formula: wherein R ^ represents a trivalent organic radical containing from 6 to 18 carbon atoms, such as cyclic trivalent acrylic and trivalent radicals, e.g., trivalent alkylene radicals, such as those derived from 1,2, 2-trimethylolpropane and the like, or trivalent cycloalkylene radicals, such as those derived from 1,3,5-trihydroxycyclohexane and similar. These mono-organophosphites can be found described in greater detail e.g., in U.S. Patent No. 4,567,306, the total disclosure of which is incorporated herein by reference thereto. Representative of an especially preferred class of diorganophosphites are those of the formula: wherein W represents a monovalent hydrocarbon radical substituted or unsubstituted as defined above, wherein each radical Ar individually represents a subtitled or unsubstituted aryl radical, wherein each and has a value of 0 or 1, wherein Q represents a divalent bridge group that selects from the group consisting of -CRJR4-, -O-, -S-, -NR5-, SiR6R7- and -C0-, wherein each R3 and R4 independently represents a radical selected from the group consisting of hydrogen, radicals of alkyl having 1 to 12 carbon atoms, phenyl, tolyl and anisyl, wherein each R ^, R ^ and B independently represents hydrogen or a methyl radical, and n has a value of 0 or 1. These di-organophosphites described in greater detail, eg, in US Patents Nos. 4,599,206 and 4,717,775, the total disclosure of which is incorporated herein by reference thereto. Representative of the especially preferred classes of organobisphosphites are those of the following formulas VIII to X. wherein Ar, Q, R, X, n and y_ are the same as defined above and R ^ O represents a divalent hydrocarbon radical selected from the group consisting of alkylene, alkylene-oxy-alkylene and arylene radicals. See, e.g., U.S. Patent Nos. 4,769,498; 4,885,401; 5,364,950 and 5,264,616. Most preferably X represents a radical of aryl- (CH2) - (Q) n-> CH2) and divalent aryl, each having individually a value of 0 or 1; wherein n has a value of 0 or 1 and wherein Q is -CR¾4- where R ^ and 4 individually represent a hydrogen or methyl radical, more preferably, each aryl radical of the groups defined above Ar, X, R, R! R! 0 and W of the abovementioned formulas can contain from 6 to 18 carbon atoms and can be the same or different, while the preferred alkylene X radicals can contain from 2 to 18 carbon atoms and the Preferred alkylene radicals of R 10 may contain from 5 to 18 carbon atoms. In addition to Preferably, the divalent Ar radicals and the divalent aryl X radicals of the aforementioned formulas are phenylene radicals, wherein the bridging group represented by - ((¾) and - (Q) n ~ < CH2) and - is linked to the phenylene radicals in positions that are ortho to the oxygen atoms of the formulas connecting the phenylene radicals with their phosphorus atom of the formulas. It is also preferred that any substituent radical when present in these phenylene radicals be bound in the para and / or ortho position of the phenylene radicals relative to the oxygen atom which binds the given substituted phenylene radical to its phosphorus atom. In addition, if desired, any organophosphite determined in the aforementioned Formulas I to X may be an ionic phosphite, that is, it may contain one or more ionic residues which are selected from the group consisting of: SO 3 M wherein M represents inorganic cationic atoms or organic or radical, PO3M wherein M represents inorganic or organic cationic atoms or radicals, NR3X 'wherein each R represents a hydrocarbon radical containing from 1 to 30 carbon atoms which is selected from the class consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl, and X 'represents inorganic or organic anionic or radical atoms, CO2 wherein M represents inorganic or organic cationic atoms or radicals, as described, e.g., in U.S. Patent Nos. 5,059,710; 5,113,022 and 5,114,473, the total exposures of which are incorporated herein by reference thereto. Therefore, if desired, these phosphite coordinating groups may contain from 1 to 3 of these ionic residues, while it is preferred that only one of this ionic residue is substituted in any given aryl residue in the phosphite coordinating group when the coordinating group contains more than one of these ionic residues. As suitable counterions, M and X ', for the anionic residues of the ionic phosphites can be mentioned hydrogen (ie, a proton), the cations of the alkali and alkaline earth metals, e.g., lithium, sodium, potassium, cesium , rubidium, calcium, barium, magnesium and strontium, the ammonium cation and the quaternary ammonium cations. Suitable anionic atoms of the radicals include, for example, sulfate, carbonate, phosphate, chloride, acetate, oxalate and the like. Of course, any of the radicals R, R ^, R ^, IO, W, X and Ar of these nonionic and ionic organophosphites of the aforementioned Formulas I to VI, can be substituted if desired with any suitable substituent containing from 1 to 30 carbon atoms which are not unduly detrimentally affects the desired result of the process or this invention. The substituents which may be in the radicals furthermore of course be the corresponding hydrocarbon radicals, such as the alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents, may include, for example, silyl radicals, such as -Si (R9) 3; amino radicals, such as - (R9> 2 phosphine radicals, such as -aryl-P (R9) 2 · 'acyl radicals, such as -C (0) R9; acyloxy radicals, such as -0C ( 0) R9; amido radicals, such as -CON (R9) 2 and -N (R9) COR9; sulfonyl radicals, such as -SO2R9; alkoxy radicals, such as -OR9; thionyl radicals, such as -SR9 phosphonyl radicals, such as -P (0) (R9) 2 as well as halogen, nitro, cyano, trifluoromethyl, hydroxy radicals and the like, wherein each R9 radical individually represents a same or different monovalent hydrocarbon radical having 1 to 18 carbon atoms (e.g., alkyl, aryl, aralkyl, alkaryl and cyclohexyl radicals) with the proviso that amino substituents, such as -N (R> 2 each R9 taken together can also represent a divalent bridge group that forms a heterocyclic radical with the nitrogen atom, and in the amido substituents, such as -C (0.} .N (R9 >; 2 and -N (R9) COR9 each R9 linked to N can also be hydrogen. Of course, it should be understood that any of the groups of substituted or unsubstituted hydrocarbon radicals that constitute a specific determined organophosphite may be the same or different. Illustrative substituents more specifically include primary, secondary and tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, butyl, secondary butyl, tertiary butyl, neo-pentyl, n-hexyl, amyl, amyl radicals. secondary, tertiary amyl, iso-octyl, decyl, octadecyl and the like; aryl radicals, such as phenyl radicals, naphthyl and the like; aralkyl radicals, such as benzyl, phenylethyl, triphenylmethyl radicals and the like; alkaryl radicals, such as tolyl, xylyl radicals and the like; alicyclic radicals, such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl radicals and the like; alkoxy radicals, such as methoxy, ethoxy, propoxy, tertiary butoxy -OCH2CH2OCH3, -O (CH2CH2) 2OCH3, -0 (CH2CH2! 3OCH3 and the like; aryloxy radicals, such as phenoxy and the like, as well as silyl radicals, such as -Si (0113) 3, -Si (00113) 3, Si (C3H7) 3 and the like; amino radicals such as -NH2-, -N (CH3) 2, -NHCH3, -H (C2H5> and the like, arylphosphine radicals, such as -CGH5 ~ P (CgHs) 2 and the like, acyl radicals, such such as -C (0) CH3, -C (0) C2H5, C (0) CgH5 and the like, carbonyloxy radicals, such as -C (0) OCH3 and the like; oxycarbonyl radicals, such as -0 (CO) CgH5 and the like, amide radicals such as -CONH2, -CON (CH3) 2i -NHC (0) CH3 and the like; sulfonyl radicals, such as -S (0) 2C2H5 and the like; sulfinyl radicals, such as -S (0) CH3 and the like, thionyl radicals, such as -SCH3- -SC2H5, -SCgH5 and the like, phosphonyl radicals, such as -P (O) (CgHs ^, -P (0) (CH3) 2, - P (O) (C2H5) 2, -P (O) (C3H7) 2, -P (O) (C4H9) 2, -P (O) (C6H13) 2, -P (0) CH3 (C6H5), - P (O) (H) (C6H5) and the like Illustrative specific examples of the coordinating groups of achiral di-organophosphite and bis-phosphite include, eg, 2-t-butyl-4-methoxyphenyl (3, 3 '-di-t-butyl-5, 51-dimethoxy-1,1' -biphenyl-2 , 2'-diyl) phosphite, which has the formula Coordinating Group A 6,6-t [3,3 '-bis (1,1-dimethylethyl) 5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diyl] bis (oxy)] bis-dibenzo [d, f] [1, 3,2] dioxaphosphepin having the formula Coordinating Group B 6, 6 '- [[3, 3 *, 5, 5' -tetrakis (1,1-dimethylpropyl) - [1,1'-biphenyl] 2,2'-diiljbis (oxy)] bis-dibenzo [d, f] [1,3,2] -dioxaphosphepin, which has the formula: Coordinating Group C 6, 6 · [[3, 3 ', 5, 5 | -tetrakis (1, 1-dimethylethyl) - [1,1'-biphenyl] | 2,2' -diiljbis (oxy)] bis-dibenzo [d, f] [1,3,2] -dioxaphosphepin, which has the formula and the like, while specific illustrative optically active bis-phosphite coordinating groups include, v.gr.,; (2R, 4R) -Di [2,2 '- (3,3', 5, 5 '-tetrakis-ter-amyl-1,1' -biphenyl)] -2, -pentyldiphosphite, having the formula Coordinating Group E (2R, 4R) -Di '[2, 2' - (3, 3 '5, 5'-tetratra-tert-butyl-1, 1'-biphenyl),] -2, -pentyl diphosphite, which has the formula Coordinating Group F (2R, 4R) -Di [2, 2 '- (3, 3' -di-amyl-5,5'-dimethoxy-1,1-biphenyl)] -, 4-pentyl diphosphite, having the formula: - - Coordinating Group G (2R, 4R) -Di [2, 2 '- (3, 3 | -di-tert-butyl-5,5'-dimethyl] -1,1-biphenyl)] -2,4-pentyl diphosphite, which has the formula Coordinating Group H (2R, R) -Di [2, 2 '- (3, 3'-di-tert-butyl-5,5'-diethylo-1, 1' biphenyl)] -2,4-pentyl diphosphite, which has the formula Coordinated Group (2R, 4R) -Di [2,2 '- (3,3'-di-tert-butyl-5,5'-diethyl-1, 1'-biphenyl)] -2, 4-pentyl diphosphite, having the formula: Coordinating Group K The concentration of the phosphite coordinating group and the hydroformylation reaction mixtures used in the process of the present invention can vary from about 0.005 percent to 15 percent by weight based on the total weight of the reaction mixture. From Preferably, the concentration of the coordinating group is between 0.001 percent and 10 percent by weight, especially preferably between about 0.05 percent and 5 percent by weight on that basis. The concentration of rhodium metal in the hydroformylation reaction mixtures used in the present invention can be as high as 2,000 parts per million by weight, based on the weight of the reaction mixture. Preferably, the rhodium concentration is between about 50 and 1,000 parts per million by weight based on the weight of the reaction mixture and most preferably, is between about 70 and 800 parts per million by weight based on the weight of the mixture of reaction. The reaction conditions of the hydroformylation processes encompassed by this invention may include any suitable type of hydroformylation conditions hitherto used to produce the optically active and non-optically active aldehydes. For example, the hydrogen pressure of total gas, carbon monoxide and the olefin starting compound of the hydroformylation process can vary from about .0703 to about 703 kilograms per absolute square centimeter. In general, however, it is preferred that the process be operated at a total gas pressure of hydrogen, carbon monoxide and the olefin starting compound of less than about 105.45 kilograms per absolute square centimeter, more preferably less than about 35.15 kilograms per absolute square centimeter. The minimum total pressure is predominantly limited by the amount of reagents necessary to obtain a desired reaction rate. More specifically, the carbon monoxide partial pressure of the hydroformylation process of this invention is preferably from about 0.703 to about 25.30 kilograms per absolute square centimeter and more preferably from about .211 to about 18.98 kilograms per centimeter. absolute square, while the hydrogen partial pressure is preferably from about 1.05 to about 33.74 kilograms per absolute square centimeter and more preferably, from about 2.11 to about 21.09 kilograms per absolute square centimeter. In general, the molar ratio of H2: CO of gaseous hydrogen to carbon monoxide can vary from about 1:10 to 100: 1 or higher; the especially preferred molar elevation of hydrogen or carbon monoxide being from about 1: 1 to about 10: 1. In addition, the hydroformylation process can be carried out at a reaction temperature of about -25 ° C to about 200 ° C. In general, the hydroformylation reaction temperature of about 50 ° C to about 120 ° C is preferred for all types of olefinic starting materials. Of course, it will be understood that when non-optically active aldehyde products are desired, achiral type olefins, a catalyst and free coordinating groups are employed and when optically active aldehyde products are desired, olefins of chiral or prochiral type, catalysts and free coordinating groups. Of course, it may also be understood that the hydroformylation reaction conditions employed will be regulated by the type of aldehyde products desired. The reactants of the olefin starting material that can be employed in the hydroformylation processes of this invention include both optically active (prochiral and chiral) and non-optically active (achiral) olefin compounds containing from 2 to 30, preferably from 4 to 20 carbon atoms. These olefin compounds can be terminally or internally unsaturated and can be straight chain, branched chain or cyclic structures as well as mixtures of olefins, such as those obtained from the oligomerization of propene, butene, isobutene, etc. (such as the so-called propylene, dimeric, trimeric or tetrameric and the like, as disclosed, e.g., in U.S. Patent Nos. 4,518,809 and 4,528,403). Furthermore, these olefin compounds can also contain one or more unsaturated ethylenic groups and, of course, mixtures of two or more different olefinic compounds which can be used as the hydroformylation starting material if desired. Also, these olefin compounds and the corresponding aldehyde products derived therefrom may contain one or more groups or substituents that do not unduly detrimentally affect the hydroformylation process or the process of this invention as described, .gr, in the North American Patents Numbers 3,527,809; 4,668,651 and similar. The illustrative achiral olefinic unsaturated compounds are alpha-olefins, internal olefins, 1,3-* -dienes, alkyl alkenoates, alkenyl alkanoates, alkenylalkyl ethers, alkenols and the like, eg, ethylene, propylene, 1- butene, 1-pentene, 1-hexene, 1-0 octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene , 1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methylpropene (isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2-heptene, cyclohexene, 5-dimers of propylene , propylene trimers, tetramers propylene, butadiene, piperylene, isoprene, 2-ethyl-1-hexene, 2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, allyl butyrate, hex-l-en-4-ol, oct-l-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, allyl propionate, methacrylate of methyl, vinylethyl ether, vinylmethyl ether, allylethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide, 4-methyl styrene, 4-isopropyl styrene, 4-tert-butyl styrene , alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene, 1,3-diisopropenylbenzene, eugenol, iso-eugenol, safrole, isosafrole, anethole, 4-allylanisole, indene, limonene, beta-pinene, dicyclopentadiene , cyclooctadiene, camphene, and linalool and the like. Preferred optically active or prochiral olefinic compounds useful in asymmetric hydroformylation include, for example, p-isobutylstyrene, 2-vinyl-6-methoxy-2-naphthylene, 3-ethenylphenyl ketone, 4-ethenylphenyl-2-thienylketone, 4-ethenyl-2. -fluorobiphenyl, 4- (1, 3-dihydro-l-oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, propenylbenzene, isobutyl-4-propenylbenzene, phenylvinyl ether and the like. Other olefinic compounds include substituted aryl ethylenes as described in the U.S. Patent Number 4,329,507, the disclosure of which is incorporated herein by reference. Illustrative prochiral and chiral definitions useful in asymmetric hydroformylation which can be used to produce mixtures of enantiomeric aldehyde and which may be encompassed by this invention, include those represented by the formula: wherein R] _, R2, R3 and R4 are the same or different (provided that R ^ is different from R2 or R3 is different from R4) and are selected from hydrogen; I rent; substituted alkyl, this substitution is selected from dialkylamino such as benzylamino and dibenzylamino, alkoxy such as methoxy and ethoxy, acyloxy such as acetoxy, halo, nitro, nitrile, thio, carbonyl, carboxamide, carboxaldehyde, carboxyl, carboxylic ester, aryl including phenyl; substituted aryl including phenyl, the substitution is selected from alkyl, amino including alkylamino and dialkylamino such as benzylamino and dibenzylamino, hydroxy, alkoxy such as methoxy and ethoxy, acyloxy, such as acetoxy, halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxylic ester , carbonyl and uncle; acyloxy such as acetoxy, alkoxy such as methoxy or ethoxy; amino including alkylamino and dialkylamino such as benzylamino and dibenzylamino; acylamino and diacylamino such as acetylbenzylamino and diacetylamino; nitro; carbonyl; nitrile; carboxyl; carboxamide, carboxaldehyde; carboxylic ester; and alkyl mercapto such as methylmercapto. It will be understood that the prochiral and chiral olefins of this definition also include molecules of the above-mentioned general formula 0 wherein the R groups are connected to form ring compounds, e.g., 3-methyl-1-cyclohexene and the like. Mixtures of the different olefinic starting materials can be used, if desired, in the hydroformylation process of the present invention. More preferably, the present invention is especially useful For the production of achiral aldehydes, by hydroformylation of alpha-olefins containing from 2 to 30, preferably from 4 to 20 carbon atoms, including isobutylene and the internal olefins containing from 4 to 20 carbon atoms. as the mixtures of the starting material of these alpha-olefins and internal olefins. Commercial alpha-olefins containing four or more carbon atoms may contain small amounts of corresponding internal olefins and / or their saturated hydrocarbon corresponding and that these commercial olefins do not necessarily have to be purified from it before hydroformylation. As will be seen, the hydroformylation processes of this invention involve the use of a complex rhodium-organophosphite catalyst as described herein. Of course, the mixtures of these catalysts can also be used, if it is red. The amount of the complex rhodium-organophosphite catalyst present in the reaction medium of a particular hydroformylation process encompassed by this invention need only be that minimum amount necessary to provide the red determined rhodium concentration to be employed and which will supply the the basis for at least the catalytic amount of rhodium needed to catalyze the specific hydroformylation process involved, as disclosed, eg. in the aforementioned patents. In general, rhodium concentrations within the scale of about 10 parts per million of about 1000 parts per million, which is calculated as free rhodium, in the hydroformylation reaction medium should be sufficient for most processes while it is generally preferred to employ from about 10 to 500 parts per million of rhodium and more preferably of 25 to 350 parts per million of rhodium. In addition, the complex catalyst of rhodium-organophosphite coordinating group, of the free organophosphite coordinating group (i.e., the coordinating group which is not complexed with the rhodium metal) is also present in the hydroformylation reaction medium. The free organophosphite coordinating group may correspond to any of the previously defined phosphite coordinating groups discussed above as capable of being employed herein. It is preferred that the free organophosphite coordinating group be the same as the phosphite coordinating group of the rhodium-organophosphite complex catalyst employed. However, these coordinating groups do not need to be equal in any given process. The hydroformylation process of the invention may involve up to 100 moles or more of the free organophosphite coordinating group per mole of rhodium metal in the hydroformylation reaction medium. Preferably the hydroformylation process of this invention is carried out in the presence of about 1 to about 5 moles of the phosphite coordinating group, and more preferably from about 1 to about 4 moles of the phosphite coordinating group per mole of rhodium metal present in the reaction medium, these group amounts phosphite coordinator being the sum of both the amount of the coordinating phosphite group that is linked. { complex form) with the rhodium metal present as the amount of the free phosphite coordinating group (not formed in complex) present. Of course, if desired, the replacement or additional phosphite coordinating group can be supplied to the reaction medium of the hydroformylation process at any time and in any appropriate manner, e.g., to maintain a predetermined level of the free coordinating group. in the reaction medium. The hydroformylation processes encompassed by this invention are also carried out in the presence of an organic solvent for the complex rhodium-organophosphite catalyst and the free organophosphite coordinating group. Depending on the specific catalyst and the reagents employed, suitable organic solvents include, for example, alcohols, alénes, alkenes, alkynes, ethers, aldehydes, aldehyde condensation byproducts of higher boiling temperature, ketones, esters, amides, aromatic tertiary amines. and similar. Any suitable solvent that does not unduly detrimentally interfere with the proposed hydroformylation process can be employed and these solvents can include those disclosed above which are commonly employed in the process of hydroformylation of known metal catalysts. Mixtures of one or more different solvents can be used, if desired. Generally, with respect to the production of the achiral (non-optically active) aldehydes, it is preferred to employ aldehyde compounds corresponding to the desired aldehyde products to be produced and / or the liquid condensation byproducts of boiling point aldehyde. higher such as the main organic solvents as is common in the art. These aldehyde condensation byproducts can also be carried out if desired and used accordingly. Illustrative preferred solvents capable of being employed in the production of optically active aldehydes include ketones (e.g., acetone and methylethyl ketone), esters (e.g., ethyl acetate), hydrocarbons (e.g., toluene) , nitrohydrocarbons (v.gr, nitrobenzene) and ethers (e.g., tetrahydrofuran (THF) and glyme). The amount of solvent employed is not critical to the present invention and only that amount needs to be sufficient to solubilize the catalyst and the free coordinating group of the hydroformylation reaction mixture to be treated by the process of this invention. In general, the amount of the solvent can vary from about 5 weight percent to about 99 weight percent or more, based on the total weight of the starting material of the hydroformylation reaction mixture. Illustrative non-optically active aldehyde products correspondingly include, e.g., propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-methyl-1-butyraldehyde, hexanal, 2-methyl valeraldehyde, hetanal, 2-hexanal 2-methyl, octanal, 1-heptanal of 2-methyl, nonanal, 1-octanal of 2-methyl, 1-octanal of 2-ethyl, 1-hexanal of 3-propyl, decanal, adipaldehyde, 2-methylglutaraldehyde, 2- methyladipaldehyde, 3-methyladipaldehyde, 3-hydroxypropionaldehyde, 3-pentenal, 5-formylvalerate of alkyl, 2-methyl-l-nonanal, undecanal, 1-decanal of 2-methyl, dodecanal, 2-methyl-l-undecanal, tridecanal, 1-tridecanal of 2-methyl, 2-ethyl, 1-dodecanal, 3-propyl-1-undecanal, pentadecanal, 2-methyl-1-tetradecanal, hexadecanal, 2-methyl-1-pentadecanal, heptadecanal, 2-methyl- 1-hexadecanal, octadecanal, 2-methyl-1-heptadecanal, nonodecanal, 2-methyl-1-octadecanal, 2-ethyl-1-heptadecanal, 3-propyl-1-hexadecanal, eicosanal, 2-methyl-1-nonadecanal, heneicosanal, 2-methyl-l-eicosanal, tricosanal, 2-methyl-l-docosanal, tetracosanal, 2-methyl-l-tricosanal, paentacosanal, 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. Illustrative optically active aldehyde products include aldehyde compounds (enantiomeric) prepared by the asymmetric hydroformylation process of this invention such as e.g., S-2- (p-isobutylphenyl) -propionaldehyde, S-2- (6- methoxy-2-naphthyl) propionaldehyde, S-2- (3-benzoyl-phenyl) -propionaldehyde, S-2- (p-thienoylphenyl) propionaldehyde, S-2- (3-fluoro-4-phenyl) phenylpropionaldehyde, S-2- [4- (1, 3-dihydro-l-oxo-2H-isoindol-2-yl) phenyl] propionaldehyde, S-2- (2-methylacetaldehyde) -5-benzoylthiophene and the like. Hydroformylation processes may involve a liquid catalyst recycling process. These liquid catalyst recycling processes are known as disclosed, e.g., in U.S. Patent Nos. 4,668,651; 4,774,361; 5,102,505 and 5,110,990. For example, in these liquid catalyst recycling processes, it is common to continuously remove a portion of the medium from the liquid reaction product containing, e.g., the aldehyde product, the solubilized rhodium-phosphite complex catalyst, the group free phosphite coordinator and the organic solvent, as well as the byproducts produced, in situ by hydroformylation, e.g., aldehyde condensation byproducts, etc. and unreacted olefinic starting material, monoxide carbon and hydrogen (gas without) dissolved in the medium, from the hydroformylation reactor, to a distillation zone, e.g., a vaporizer / separator where the desired aldehyde product is distilled in one or more stages under reduced normal pressure or elevated, as appropriate and separated from the liquid medium. The desired distilled vaporized aldehyde product separated in this way can then be condensed and recovered in any conventional manner as discussed above. The remaining non-volatilized liquid waste containing the rhodium-phosphite complex catalyst, the solvent, the free bisphosphite coordinating group and usually a certain amount of the undistilled aldehyde product is then recycled again, with or without additional treatment as described above. desired, together with any by-products and non-volatilized gaseous reagents that could still be dissolved in the recycled liquid waste, in any desired conventional manner, to the hydroformylation reactor as disclosed, e.g., in the patents mentioned above. In addition, the reactive gases removed in this manner by this distillation of the vaporizer can also be recycled back to the reactor, if desired. Distillation and separation of the desired aldehyde product from the complex rhodium- The organophosphite containing the product solution can be carried out at any desired appropriate temperature. Generally, it is recommended that this distillation be carried out at relatively low temperatures, such as below 150 ° C, and more preferably at a temperature within the range of about 50 ° C to about 130 ° C. It is also generally recommended that this aldehyde distillation is carried out under reduced pressure, eg, a total gas pressure which is considerably lower than the total gas pressure employed during hydroformylation, when low-temperature aldehydes are involved. boiling (e.g., from 4 carbon atoms to 6 carbon atoms) or vacuum when high boiling temperature aldehydes are involved (eg, 7 carbon atoms or greater). For example, a common practice is to subject the liquid reaction product medium removed from the hydroformylation reactor to a pressure reduction in order to volatilize a considerable portion of the unreacted gases dissolved in the liquid medium which now contain a much lower concentration from the synthesis gas of what was present in the hydroformylation reaction medium to the distillation zone, e.g., the vaporizer / separator, where the desired aldehyde product is distilled. In general, they can be enough for most purposes distillation pressures ranging from vacuum pressures or lower to total gas pressure of approximately 3.52 kilograms per square centimeter gauge. In the membrane separation of this invention, an organic solvent resistant membrane compound is used which allows a considerable portion, eg, at least 60 percent of the hydroformylation aldehyde products in the organic solvent to pass. through this operation while rejecting at least 90 weight percent of the rhodium-organophosphite complex catalyst and the free organophosphite coordinating group. Membrane separation is a pressure driven process and generally the feed stream pressure (i.e., the starting material of the hydroformylation reaction mixture) can vary from as low as about 3.52 kilograms per centimeter square up to as high as about 105.45 kilograms per square centimeter. More preferably, the pressure of the feed stream of this invention is from about 7.03 kilograms per square centimeter to about 42.18 kilograms per square centimeter. The "permeate" is the current that has passed through the membrane, and in comparison with the feed stream, the permeate It is at a greatly reduced pressure. Typically, the permeate is almost at atmospheric pressure. The permeate contains a greatly reduced amount of the complex rhodium and organophosphite catalyst and the free organophosphite coordinating group dissolved in the volume of the aldehyde and the organic solvent. This permeate can be recovered in any conventional manner, v.gr, simply collected as a liquid. The "refined" current also called "concentrated" or "non-permeate" current is the current that does not pass through the membrane. The raffinate contains the volume of the rhodium-organophosphite complex catalyst and the free organophosphite coordinating group dissolved in a certain amount of the aldehyde and the organic solvent. The refining stream is typically only slightly less than the feed stream and can be recycled back to the hydroformylation reactor for reuse. The premeate stream can be re-pressured if desired to remove more of the complex catalyst and the free coordinator and sent to another membrane to undergo separation again. Furthermore, even when the satisfactory practice of this invention does not depend and is not predicted on any explanation as to exactly which membrane separation actually occurs, it is believed that the efficiency of this separation and the degree to which the feed of the starting material of the hydroformylation reaction mixture will interact with the membrane that the composite membrane employed will depend to a large extent on the relative solubility parameters of the membrane and the aldehyde product of the feed of the starting material together with the ratio of the molar volume and the organophosphite coordinating group to the aldehyde product as further defined herein. Accordingly, as can be seen here, in the present invention it is recommended to control and correlate the ratio of the solubility parameters and the ratio of the molar volume as a means to predetermine which of the membrane materials will be able to provide an appropriate effective separation between the complex rhodium and organophosphite catalyst and the free organophosphite coordinating group contained in a hydroformylation reaction mixture containing determined aldehyde. Therefore for the purposes of this invention, it should suffice simply to note that the composite membrane suitable for use in this invention can be any composite membrane capable of allowing a considerable portion of the aldehyde product and the organic solvent of the starting material of The mixture of hydroformylation reaction passing through the membrane, while rejecting at least 90 percent by weight of the complex rhodium and organo-phosphite catalyst and the free organophosphite coordinating group present in the starting material of the reaction mixture of hydroformylation, and wherein the aldehyde product has a solubility parameter relative to the membrane membrane solubility parameter composed of at least +50 VkJ / ta (preferably at least +100 VcyJ / m3) but not more than +500 (preferably not more than +400 Y + J / m3), and wherein the ratio of the molar volume of the organophosphite coordinating group to the aldehyde product is > 1.5 (preferably> 3.0). The solubility parameters of the aldehyde products, solvents and coordinator groups encompassed by this invention can be calculated from the group contribution theory as developed by (1) L. Constantinou and R. Gani, "New Group Contribution Method for Estimating Properties of Puré Compounds, "AIChE J., 40 (10), 1697 (1994) and (2) L. Constantinou, R. Gani, and JP O'Connell, "Estimation of the Acentric Factor and the Liquid Molar Volume at 298 K Through a New Group Contribution Method," Fluid Phase Equilibria, 103 (1) 11 (1995).

These methods have been explained as including the heat of vaporization and the molar volume contributions for the [> P-] derived from the triphenylphosphine data. [Daubret, T.E., Danner, R.P., Sibul, H.M. and Stebbins, C.C., "DIPPR (R) Data Collection of Puré Compound Propoerties", Project 801, Sponsor Relay, July 1995, Design Institute for Physical Property Data, AIChE, New York, NY. ] Extrapolated values of 91.44 kj / mol and 0.1353 cubic meter / mol were used to derive the group contribution increments for [> P-] of -14.5 kJ / mol (for the heat of vaporization) and 0.0124 cubic meter / mol (for the molar volume of the liquid). The membrane solubility parameter of the composite membranes encompassed by this invention can be easily obtained and literature sources and / or can be determined by methods well known in the art. The specific solubility parameters illustrated from the different polymer membranes are given in Table 1.

Table 1 Solubility Parameters of Illustrative Polymer Membranes * Polymer Solubility Parameter VkJ / m3 Teflon 400 Polydimethylsiloxane 471 Polyethylene 510 Polyisobutylene 523 Polybutadiene 555 Polystyrene 587 Polymethyl methacrylate 613 Polyvinyl chloride 626 Cellulose diacetate 704 787 Polyvinylidene Chloride Polyacrylonitrile 994 * Almost 25 ° C: From J. M. Prausnitz, Molecular Thermodynamics of Fluid-Phase Equilibria, Prentice-Hall, NJ, page 298.

VkJ / m3 represents the square root of kilo-joules per cubic meter. The illustrative solubility parameters and the molar volumes of the various specific aldehydes, organic solvents and organophosphorus coordinating groups are given in Table 2.

Table 2 Solubility Parameters and Molar Volumes for Components and Hydroformylation Reaction Membranes Parameter of Molar Volume Solubility in meter-Vkmol Substance Aldehydes propionaldehyde 617. .8 0.0747 butyraldehyde 603. .3 0.0911 valeraldehyde 593, .0 0.1075 3-pentenal 594,, 2 0.1016 adipaldehyde 659, .6 0.1178 naproxen aldehyde 759. .5 0.1947 Acetone solvents 632. .7 0.0748 benzene 587..1 0., 0911 MEK 615. .9 0. .0912 ethyl acetate 620. .0 0. .997 Butiraldehyde 639., at 0.2235 Trimer Valeraldehido 622. .5 0. .2735 Trimer Coordinating Groups triethylphosphite 396. .7 0. .1723 tributylphosphine 430. .9 0. .2506 triphenylphosphine 623., 5 0..253 triphenylphosphite 625. 6 0.2554 Coordinating Group K * 665. .6 0. .7724 Coordinating Group D * 677.8 0.7166 Coordinating Group A * 682.9 0.5127 * The structural formulas and the names of the coordinating groups are provided herein in the foregoing. The illustrative solubility parameters of the different membranes minus the solubility parameters of different aldehydes are shown in Table 4. The illustrative molar volumes of the different coordinating groups divided by the molar volumes of the different aldehydes are shown in Table 4.

Table 3 Parameters of Membrane Solubility Less the Aldehyde Solubility Parameter All Values are in units of VkJ / m3, which is the square root of kiloJoules per cubic meter Membrane- Membrane- Membrane- Propional- Butiral- Valeraldehyde dehyde dehyde Membrane Solubility Parameter Teflon 400 -218 -203 -193 Polydimethyl siloxane 471 -147 -132 -122 Polyethylene 510 -108 -93 -83 Polyisobutylene 523 -95 -80 -70 Polybutadiene 555 -63 -48 -38 Polystyrene 587 -31 -16 -6 Polymethyl methacrylate 613 Chloride Polivin 626 8 23 33 Diacetate cellulose 704 86 101 111 Polyvinylidene Chloride 787 169 184 194 Poliacriloni-trilo 994 376 391 401 Table 3 (continued) Membrane Membrane 3-pentenal adipaldehyde Naproxen Teflon -194 -260 -360 Polydimethylsiloxane -123-189-289 Polyethylene -84 -150 -250 Polyisobutylene -71 -137 -237 Polybutadiene -39 -105 -205 Polystyrene -7 -73 -173 Polymethyl methacrylate 19 -47-147 Polyvinyl Chloride 32 -34 -134 Cellulose Diacetate 110 44 -56 Polyvinylidene chloride 193 127 27 Polyacrylonitrile 400 334 234 Table 4 Molar Volume of the Coordinating Group Divided among the Molar Volume of Adehyide Coordination Group - Coordination Group - Coordination Group / Producer / builder / varaldehyde tyraldehyde leraldehyde Coordinating Group triethylphosphite 2.31 1. .89 1. .60 tributylphosphine 3.35 2. .75 2. .33 triphenylphosphine 3.15 2. .58 2, .19 triphenyl phosphite 3.42 2. .80 2. .38 Coordinating Group K 10.34 8. .48 7. .19 Coordinating Group D 9.59 7., 87 6., 67 Coordinating Group A 6.86 5., 63 4. .77 Table 4 (continued) Coordination Group - Coordinating Group - Coordinating Group / 3- nador / adiponador / Aldehi- pentenal aldehido do de Naproxen Coordinating Group Triethylphosphite 1.70 1.46 0, .88 tributylphosphite 2.47 2.13 1, .29 triphenylphosphite 2.32 2.00 1. .21 triphenylphosphite 2.51 2.17 1., 31 Coordinating Group K 7.60 6.56 3. .97 Coordinating Group D 7.05 6.08 3. .68 Coordinating Group A 5.05 4.35 2. .63 Structures of Coordinating Groups K, D and A are as defined above.

Illustrative examples of these membranes can be employed in the practice of this invention include, e.g., cellulose acetate (CA), cellulose triacetate, CA-triacetate mixtures, mixed cellulose esters, cellulose nitrate, regenerated cellulose, gelatin, aromatic polyamide, polyimide, polybenzimidazole, polybenzimidazolone, polyacrylonitrile (PAN), copolymer of PAN- polyvinyl chloride, PAN-methylallyl sulphonate copolymer, polaryl ether sulfones, polydimethylphenylene oxide, polycarbonate, polyester, polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polyelectrolyte complexes, polymethyl methacrylate, polydimethylsiloxane and the like (as given to know, e.g., in "Membranes" by I. Cabasso in the Encyclopedia of Polymer Science and Technology, John Wiley and Sons, New York, 1987). In addition, the composite membrane of this invention includes any suitable effective membrane as defined herein supported on a porous support. These support materials help to provide the structural design of the composite membrane as opposed to the actual desired separation of the process of this invention, which is provided by the specific membrane employed, these support-type materials are well known in the art and include eg, porous supports made of non-woven and woven cellulosic materials, polyethylene, polypropylene, nylon, polyacrylonitrile, homo- and co- -polymers of vinyl chloride, polystyrene, polyesters such as polyethylene terephthalate, polyvinylidene fluoride, polytetrafluoroethylene, polydimethylsiloxane, glass fibers, porous carbon, graphite, inorganic supports based on alumina and / or silica, and those inorganic supports coated with oxides of zirconium and the like. Polyethylene and polypropylene can be the preferred support materials. In addition, the composite membranes employed in this invention can be formed in any desired shape or configuration, eg, a hollow fiber or a tubular membrane or can be used as planar sheets. More preferably, these composite membranes can be used in the form of membrane modules (e.g., spiral wound modules). Accordingly, the support material (substrate layer) of the composite membrane is not too critical and can be any porous polymer support that provides a composite membrane suitable for use in the invention, which is insoluble and stable in the organic solvent and the aldehyde product of the starting materials of the hydroformylation reaction mixture of this invention. In addition, these composite membranes suitable for use in this invention can be prepared by any known method commonly employed heretofore in the art. By way of example, as disclosed in US Pat. No. 5,265,734, a composite membrane can be derived by subjecting a polymer of the substrate eg, a polymer that is selected from polymers and ethylenically unsaturated nitrile homopolymers to a sequence of treatments. stepwise comprising (1) insolubilizing the polymer by crosslinking, (2) coating e.g., with a silicone polymer membrane layer and (3) crosslinking the silicone polymer. These composite membranes can also be characterized by at least one of the following features (a), (b), (c) and (d), namely: (a) The specific porous support polymer employed; (b) Prior to step (2), the crosslinked insolubilized obtained in step (1) can be treated if desired with a pore protector in the absence of curing agents and catalysts therefor; (c) The membrane, e.g., the coating layer The silicone may comprise at least one member selected from the group consisting of silanol-terminated polydimethylsiloxane, other polysiloxanes terminated with silanol, other polysiloxanes terminated with hydroxy, siloxanes containing alkyl groups, silicones containing aryl groups and silicones containing both alkyl and aryl groups; (d) Preferably, the composite membrane is swollen to a degree of no more than about 10 percent when immersed in the solvents. The optional pore protector that may be present in these composite membranes can be any appropriate polymer and can be selected from the class of polymers that can serve as the membrane, e.g., it can be a silicone polymer having at least , a member selected from the group copying polysiloxanes terminated with silanol, other polysiloxanes terminated with silanol, other polysiloxanes terminated with hydroxy, silicones containing alkyl groups, silicones containing aryl groups and silicones containing both alkyl groups and of aril. The substrate layer can be self-supporting or the substrate layer can be held in other porous material. The insolubilization step may comprise at least step (i) of the following steps (i) and (ii) / namely: (i) treatment with at least one base selected from organic and inorganic bases; (ii) subsequent to step (i), subjecting the substrate to heat treatment, preferably at a temperature within a range of about 110 ° C to 130 ° C. In U.S. Patent No. 5,265,734, the substrate is preferably treated with a pore guard (in the absence of a curing agent) and then coated with the membrane, eg, the silicone layer which is then crosslinked. The pore protector (which may be, for example, a hydroxy-terminated polysiloxane) is said to serve the dual purposes of: (1) preventing pores from collapsing when the support dries during curing of the subsequently applied membrane , e.g., the silicone layer and (2) prevent the passage of the subsequently applied membrane, eg, the silicone layer, deep into the pores and, therefore, also prevent an undue reduction of the flow of the finished membrane. The treatment with the pore protector can be carried out, for example, by immersing the substrate of the membrane in a dilute solution of the pore protector and an inert solvent of low boiling temperature (e.g., an alcohol). low boiling temperature having 1 to 4 carbon atoms, such as methanol, ethanol, propanol or butanol). The final membrane silicone layer and the intermediate pore protective silicone layer can have any appropriate total thickness e.g., a total thickness within the range of 500 to 5,000 angstrom units and more preferably, within the scale of 1, 000 to 2,000 angstrom units should be appropriate for most purposes. Especially preferred composite membranes capable of being employed in this invention, are those derived from polydimethylsiloxane membranes, such as those composite polydimethylsiloxane membranes encompassed by US Pat. No. 5,265,734, the entire disclosure of which is incorporated herein by reference to the same More particularly, the membrane separation process of this invention only comprises contacting the starting materials of the liquid hydroformylation reaction mixture with the membrane of the composite membrane in any conventional manner, using any suitable equipment and technique, the preferred result is the rejection of at least 90 percent by weight of the rhodium-organophosphite complex catalyst and the free organophosphite coordinating group, while allowing that a considerable amount of the aldehyde product and the organic solvent pass through the membrane as a permeate. Generally, by allowing only the starting material of the liquid hydroformylation reaction mixture to pass through the surface of the membrane of the composite membrane at a predetermined pressure and flow rate, it must be sufficient to achieve the desired result. As mentioned above, the contact of the starting material of the hydroformylation reaction mixture and the membrane should be carried out at a pressure ranging from about 3.52 kilograms per square centimeter to about 105.40 kilograms per square centimeter. For example, nanofiltration is usually carried out at a pressure of about 5.24 kilograms per square centimeter at 42.18 kilograms per square centimeter; Ultrafiltration, in general, is carried out at a pressure of approximately 1.76 kilograms per square centimeter at 14.06 kilograms per square centimeter; while reverse osmosis, in general, is carried out at a pressure of approximately 17.58 kilograms per centimeter calculated at 70.30 kilograms per square centimeter. Preferably, the contact of the starting materials of the hydroformylation reaction mixture and the membranes in this The invention is generally carried out at a pressure of about 7.03 kilograms per square centimeter at 42.18 kilograms per square centimeter. Generally, the flow rate of the starting materials of the hydroformylation reaction mixture through the membrane in this invention can be from about 814 liter per square centimeter · hour, to about 325.6 liters per square centimeter · hour, with the preferred commercial type flow rates being from approximately 1.22 liters per square centimeter-hour to 50. B8 liters per square centimeter-hour. As a practical matter, however, any appropriate flow regime that succeeds in helping the desired end result can be used, of course. The temperature at which the contact of the starting material of the hydroformylation reaction mixture with the membrane is effected is also not too critical. Broadly, the contact can be carried out at any appropriate temperature eg, from about -20 ° C to about 120 ° C. As a practical matter, the temperature employed is preferably from about 0 ° C to about 60 ° C. Accordingly, it is considered that the membrane separation of the process of this invention may allow possibly eliminating the need for conventional separation by distillation and / or vaporization of the desired aldehyde product from the rhodium-organophosphite complex catalysts contained in the hydroformylation reaction product mixtures of the conventional liquid catalyst recycle hydroformylations. Alternatively, the membrane separation process of this invention can also serve as a means to treat all or any part of any obtained conventional liquid catalyst residue hydroformylation recycle stream, after first conventionally separating the desired aldehyde product from the complex rhodium-organophosphite catalyst contained in the mixtures of the hydroformylation reaction product by distillation and / or vaporization, in order to remove the aldehyde trimers and tetramers from the catalyst recycle streams. This method can serve to help control the concentration of those in situ type by-products of trimer and aldehyde tetramer in the hydroformylation reactor and, therefore, avoid any detrimental accumulation thereof in the reactor. Of course it should be understood that even when the use of the invention is necessary to achieve the best results and desired efficiency depend on the experience of a person in the use of the present invention, only a certain measure of experimentation must be necessary to ensure those conditions that are optimal for a given situation and, therefore, must be within the knowledge of an expert in the art and can be easily obtained by following the especially preferred aspects of this invention as explained herein and / or by simple routine experiments. The optically active aldehyde products and the derivatives of these products have a wide utility scale which is well known and documented in the art eg, they can be especially useful as pharmaceutical compounds, taste flavoring substances, fragrances, agricultural and the like . Exemplary therapeutic applications include, for example, non-steroidal anti-inflammatory drugs, ACE inhibitors, beta-blockers, analgesics, bronchodilators, spamolytics, anti-histimines, antibiotics, counter-tumor agents and the like. Finally, the non-optically active aldehyde products of the hydroformylation process of this invention have a wide utility scale which is well known and documented in the prior art, e.g., they are especially useful as starting materials for the production of alcohols and acids. The following examples are illustrative of the present invention and should not be considered as limiting. It will be understood that all parts, percentages and proportions to which reference is made herein and in the appended claims, are by weight unless otherwise indicated.

Example 1 A crude hydroformylation reaction mixture was processed through a membrane to remove the rhodium and the coordinating group. This reaction mixture was obtained by hydroformylating a solubilized organic solution of 6-methoxy-2-vinylnaphthalene (approximately 395 grams), Coordinating Group K [(2R, 4R) -Di [2,2 '- (3, 3'-di -ter-butyl-5, 5'-dimethoxy-1, 1-biphenyl) -2,4-pentyldiphosphite] (approximately 6 grams), Rh (CO) 12 (approximately 0.9 grams) and acetone (approximately 1500 milliliters) under pressure of approximately 17.58 kilograms per square centimeter with 1: 1 of H2 / CO. This hydroformylation reaction mixture was found to contain 2- (6-methoxy-2-naphthyl) -radionaldehyde, (naproxen aldehyde, about 30 percent) dissolved in acetone (about 70 weight percent). The mixture of The crude reaction also contained rhodium (approximately 263 parts per million) and approximately 0.2 weight percent of Coordinating Group K (approximately 50 percent complexed and 50 percent free). Three composite membranes were placed in parallel and used as follows: Three 5.08 cm circles were cut from a 20.32 cm by 27.94 cm sheet of MPF-50 (Lot number 0021192, code 5107) a membrane composed of polydimethylsiloxane obtained from Membrane Products Kiryat Weizmann Ltd. and which is believed to be at the center of the scope of US Pat. No. 5,265,734. These circles were placed in three Osmónicas membrane holders. The crude hydroformylation mixture (feed) was placed in a 2L Hoke cylinder under a nitrogen atmosphere. The feed was pumped at 35.15 kilograms per square centimeter at a flow rate of approximately 380 milliliters per minute. The feed flowed through a 60 micron filter and then divided into three streams that were sent to the membranes. The flow meters were used to ensure that the flow was equally divided in the membrane holders. The perneados were combined and collected under a nitrogen atmosphere. The refined ones flowed to a back pressure regulator and then were returned to the cylinder Hoke. The product solubility parameter of 2- (6-methoxy-2-naphthyl) ropionaldehyde is 760 VcJ / m3, while the solubility parameter for the polydimethylsiloxane membrane is 471 / m3, the difference between the solubilities being -289 J 7m3. "The molar volume for the 2- (6-methoxy-2-naphthyl) propionaldehyde product is 0.1947 cubic meter / kmol and the molar volume for Coordinating Group K is 0.7724 cubic meter / kmol, the ratio of the coordinating group to the aldehyde being 3.97 Approximately 1500 grams of the crude hydroformylation reaction mixture were infiltrated and the rhodium content of the resulting permeate was about 69.4 parts per million This high amount of rhodium in the permeate indicated a rejection of only about 74 weight percent of the catalyst and the coordinating group It was subsequently determined that the cells of the membrane, more specifically the O-rings that retain the compounds of the membrane in place, were not installed properly, and that this allowed the liquid reaction mixture to run around the membrane instead of through the membrane, it is believed that this was the cause of the apparent low rejection of the catalyst and the coordinating group.

Example 2 The hydroformylation reaction and membrane separation procedures of Example 1 were repeated. The same three installed composite membranes were employed, this time being careful to ensure that the membrane compounds were properly placed in the o-rings of the membrane holders. The three composite membranes were placed in parallel and used in Example 1. Three 5.08 cm circles were cut from a 20.32 cm by 27.94 cm sheet of the MPF-50 polydimethylsiloxane composite membrane obtained from Membrane Products iryat Weizmann Ltd. These Circulóos were placed in three Osmonics bracelet holders. The crude hydroformylation mixture (feed) was placed in a 2L Hoke cylinder under a nitrogen atmosphere. The feed was pumped at 35.15 kilograms per square centimeter at a flow rate of approximately 380 milliliters per minute. The feed flowed through a 60 micron filter and then divided into three streams that were sent to the membranes. Flow meters were used to ensure that the flow was equally divided in the membrane holders. The permeate was converted and collected under a nitrogen atmosphere. The refining flowed to a back pressure regulator and then returned to the Hoke cylinder. The solubility parameter of the 2- (6-methoxy-2-naphthyl) propionaldehyde product is 760 and TcJ / m3, while the solubility parameter for the polydimethylsiloxane membrane is 471 VkJ / m3, the difference between the solubilities being of -289 (VkJ / m '.) The molar volume for the 2- (6-methoxy-2-naphthyl) propionaldehyde product is 0.1947 cubic meter per kmol and the molar volume for Coordinating Group K [2R, 4R) - Say [2,2'-. { 3, 3'-di-tert-butyl-5, 5'-dimethoxy-1, 1-biphenyl)] 2,4-pentyldiphosphite] is 0.7724 cubic meter per kmol, the ratio of the coordinating group being to the aldehyde of 3.97. . The membrane separation feed was a 4 liter batch of the crude hydroformylation reaction mixture containing 2- (6-methoxy-2-naph il) -propionaldehyde (approximately 30 weight percent) in acetone (approximately 70% by weight). cent in weight). The mixture also contained rhodium (approximately 389 parts per million) and Coordinating Group K. Approximately 3325 grams of this feed solution was infiltrated through the composite membranes and the resulting solution of the permeate had a rhodium content of about 36.3 parts per million. Samples of the feed solution and permeate were purchased at the same time and the feed was found to have approximately 389 parts per million rhodium, while the permeate was found to have approximately 21.6 parts per million rhodium, which is a rejection of approximately 94.5 percent by weight of the catalyst and the coordinator group. The system was emptied, cleaned with acetone and the residue was discarded. 3325 grams of the permeate solution containing 36.3 parts per million of rhodium were again placed in the Hoke cylinder and approximately 1439 grams of this solution was again infiltrated through the composite membranes. This second solution of the resulting permeate contained about 5.6 parts per million of rhodium. Samples of the feed and permeate were purchased at the same time and feed was found to have 51.1 parts per million of rhodium, while the permeate was found to have 3.8 parts per million of rhodium, which is a rejection of approximately 92.6 per cent. weight percent of the catalyst and the coordinator group. The 1439 grams of the solution containing 5.6 parts per million of rhodium was placed back into the Hoke cylinder and passed through the composite membranes for the third time again. Approximately 935 grams of this solution was infiltrated through the membranes and the resulting perneate had about 1.2 parts per million rhodium. Samples of the feed and permeate were purchased at the same time and the feed was found to contain 18.2 parts per million of rhodium, while the permeate was found to have 1.3 parts per million of rhodium which is a rejection of 92.9 percent in weight of the catalyst and the coordinator group.

Example 3 Using the same installation, equipment and composite membranes as described in Example 2, the organic solubilized solutions of the 5 carbon and 6 carbon atoms aldehydes were passed through the membranes to separate the catalyst and coordinator groups of the solutions. (a) A mixture of 90 weight percent butyraldehyde, 10 weight percent butyric aldehyde trimer with 27 parts per million rhodium and 0.14 weight percent of Coordinating Group D, 6, 6 '- [[3, 3 ', 5, 5' -tetrakis (1,1-dimethylethyl) - [1,1'-biphenyl] -2, 2'-diyl] bis (oxy)] bis-dibenzo [d, f] [1, 3 , 2] -dioxafosfepin] was passed through the composite membranes of MPF-50. He butyraldehyde had a solubility parameter of 603 A / kJ / m3, while the polydimethylsiloxane membrane had a solubility parameter of 471 the difference between the solubilities being -132 VkJ ~ / m3. The molar volume of butyraldehyde is 0.0911 cubic meter per kmol and the molar volume of Coordinating Group D is 0.7166 square meter per kmol, the ratio of the coordinating group to the aldehyde being 7.87. The permeate solution was collected at a rate of 2.44 liters per square centimeter of membrane per day and contained less than 0.8 parts per million rhodium (greater than 97 percent rejection) and 0.0056 percent by weight of Coordinating Group D (a rejection). of 96 percent). (b) A mixture of 90 weight percent valeraldehyde, 10 weight percent butyric acid trimer with 60 parts per million rhodium and 0.27 weight percent of Coordinating Group D 6, 6 '- [[3, 3 ', 5, 5' -tetrakis (1,1-dimethylethyl) - [1, 1-biphenyl] -2,2'-diyl] bis (oxy)] bis-dibenzo [d, f] [1, 3, 2] -dioxaphosfepin] was passed through the membranes composed of PF-50. Valearaldehyde has a solubility parameter of 593 VkJ / m3, while the polydimethylsiloxane membrane has a solubility parameter of 471 the difference between the solubilities being -122 Vkj "/ m The molar volume of valeraldehyde is 0. 108 cubic meter per kmol and the molar volume for Coordinating Group D is 0.7166 cubic meters per kmol, the ratio of the Coordinating Group in aldehyde being 6.67. The permeate solution was collected at a rate of 2.85 liters per square centimeter of membrane per day and contained less than 0.9 part per million of rhodium (greater than 98.5 percent rejection) and 0.0081 percent by weight of Coordinating Group D (a rejection). of 97 percent). (c) The same experiment carried out in test (b) above was repeated with another membrane composed of polydimethylsiloxane, ie MPF-60, obtained from Membrane Products Kiryat Weizmann Ltd. and a 90 weight percent blend of valeraldehyde, 10 weight percent of the valeraldehyde trimer with 500 parts per million of rhodium and 1.25 weight percent of the Coordinating Group D. The permeate was collected at a rate of .204 liter per square centimeter in membrane per day and contained 4.2 parts per million rhodium (one rerchazo of 99.15 percent) and no detectable quantities of the Coordinating Group D (rejection of almost 100 percent).

Example 4 In this example, a composite membrane MPS-50 of spirally wrapped polydimethylsiloxane was used obtained from embrane Products Kiryat Weizmann, Ltd. This membrane module contained 7.64 cubic centimeters of membrane, and therefore represents a small commercial unit. A crude hydroformylation reaction mixture similar to the crude reaction product produced in Example 1 above was processed through a membrane to remove the rhodium and the coordinating group. The crude reaction mixture to which acetone was added contained 2- (6-methoxy-2-naphthyl) propionaldehyde (12 weight percent) dissolved in acetone (88 weight percent) and also rhodium (90 parts per million) and Coordinating Group K [2R, 4R) -Di [2,2 '- (3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl)] 2,4-pentyldiphosphite]. The solubility parameter of 2- (6-methoxy-2-naphthyl) propionaldehyde is 760 (VkJ / m3, while the solubility parameter for the polydimethylsiloxane membrane is 471 the difference between the solubilities being -289 'kJ / m3 The molar volume of 2- (6-methoxy-2-naphthyl) propionaldehyde is 0.1947 cubic meters per kmol and the molar volume for Coordinating Group K is 0.7724 cubic meter per kmol, with the ratio of molar volume of the aldehyde to the Coordinating Group being 3.97 and 7.570 liters of the feed of the mixture of The crude hydroformylation reaction was added to a Hoke vessel (and associated pipe), which was used as the feed tank. The solution was pumped at a rate of 3,785 liters per minute through a 10 micron filter and associated valves and flow meters to the composite membrane MPS-50. The volume of the aldehyde solution flowed through the MPS-50 membrane module, which is contained in a pressure hull, and the refining flowed to a back pressure regulator that graduated to 28.12 kilograms per square centimeter gauge. The refining then flowed through the heat exchanger, for temperature control and back to the feed tank. The permeate flowed back into the feed tank. The sampling of the valves allowed the samples to be acquired for analysis. When the temperature of the module is graded at 22 ° C, the rejection of the rhodium catalyst was found to be 92.8 percent, at a permeate flow rate of approximately 15.87 liters per square centimeter of membrane per day. When the temperature of the module was graduated at 18 ° C, the rejection of the rhodium catalyst was measured as being 93.6 percent at the same flow rate of the permeate.

Example 5 A crude hydroformylation reaction mixture similar to the crude reaction product produced in Example 1 above was processed through a membrane to remove the rhodium and the coordinating group. The crude reaction product contained 2- (6-methoxy-2-naphthyl) propionaldehyde (25 weight percent) dissolved in acetone (75 weight percent) and also contained rhodium (300 parts per million) and Coordinating Group K [2R, 4R) -Di [2,2'- (3, 3'-di-tert-butyl-5,5'-dimethoxy-1, 1-biphenyl)] -2,4-pentyldiphosphite]. A similar membrane apparatus was used as noted in Example 1, except that only one composite membrane module was used and that it is similar in design to the design of the Osmonics cell used in Example 1. The solubility parameter of 2- (6-methoxy-2-naphthyl) propionaldehyde, is 760 VkJ /, while the solubility parameter for the polydimethylsiloxane membrane is 471 VkTIvc? , with the difference between the solubilities being -289 VkJ / m ^. The molar volume of 2- (6-methoxy-2-naphthyl) propionaldehyde is 0.1947 cubic meter per kmol and the molar volume for Coordinating Group K is 0.7724 cubic meter per kmol, with the ratio of the molar volume of the aldehyde to the Group Coordinator K, being 3.97.

The crude reaction product was divided into three batches. One did not touch. The acetone was purified from the other two batches and added to a methylethyl ketone, and to the other ethyl acetate was added. Therefore, three identical batches of rhodium-complex catalyst from Coordinating Group K were prepared in the aldehyde produced, 2- (6-methoxy-2-naphthyl) propionaldehyde, with the exception that three different solvents were used. Then a series of membrane separations were carried out one after the other using three different solubilized aldehyde product solutions. After each test the system was emptied and cleaned to prepare for the next test. The first test used the solution of the solubilized aldehyde product based on ethyl acetate and yielded 87 weight percent rejection of the rhodium catalyst. The second test used the solution of the solubilized aldehyde product based on acetone and yielded 98 weight percent rejection of the rhodium catalyst. The third test employed the solution of the solubilized aldehyde product based on methylethyl ketone and yielded 98.3 weight percent of the rejection of the rhodium catalyst. The fourth test was a re-test of the solution of the solubilized aldehyde product based on ethyl acetate and yielded 97.8 weight percent rejection of the rhodium catalyst. The fifth test was a re-assay of the solution of the solubilized aldehyde product based on acetone and yielded 99.4 weight percent rejection of the rhodium catalyst. The sixth test was a re-assay of the solution of the solubilized aldehyde product based on methylethyl ketone and yielded 98 weight percent of the rejection of the rhodium catalyst.

Example 6 The mixture of the solubilized aldehyde product based on acetone of Example 5 was passed through the polydimethylsiloxane membrane supported on a polyamidimide support obtainable from GKSS-Forschungszentrum Geesthacht GmbH (Germany) under the designation Torlon, using a composite membrane installation similar to that described in Example 5. A rejection of 94.7 weight percent of the rhodium catalyst was obtained from feeding the mixture of the aldehyde product. Even though the invention has been illustrated by certain of the previous examples, they should not be interpreted as being limited by them; but rather, the invention covers the generic area that has been disclosed hereinabove. Various modifications and variations of this invention will be apparent to a researcher skilled in the art and it should be understood that these modifications and variations should be included within the provisions of this application and the spirit and scope of the appended claims.

Claims (11)

CLAIMS:

1. A process for separating a complex organic rhodium-organophosphite dissolved catalyst and a free organophosphite coordinating group from a non-aqueous hydroformylation reaction mixture, the mixture contains, in addition to the catalyst and the free coordinating group, an aldehyde product and a solvent organic, which includes: (i) contacting the non-aqueous hydroformylation reaction mixture with a composite membrane in order to allow a considerable portion of the aldehyde product and the organic solvent to pass through the membrane, while rejecting at least 90 percent by weight of the catalyst and the free coordinating group; wherein the aldehyde product has a solubility parameter in relation to the solubility parameter of the composite membrane of at least +50 units, and wherein the ratio of the molar volume and the organophosphite coordinating group to the aldehyde product it's from > 1.5; and (ii) recovering the aldehyde product and the organic solvent as a permeate.

2. A process according to claim 1, wherein the aldehyde product is a optically active aldehyde.

3. A process according to claim 1, wherein the aldehyde product is a non-optically active aldehyde.

4. A process according to claim 1, wherein the aldehyde product has a solubility parameter in relation to the membrane membrane solubility parameter composed of at least + 100 VkJ / m3 units but no more of + 400? / kJ / m3 units.

5. A process according to claim 4, wherein the ratio of the molar volume of the organophosphite coordinating group to the aldehyde product is > 3.0.

6. A process according to claim 2, wherein the organophosphite is an organobisphosphite.

7. A process according to claim 3, wherein the organophosphite is an organobisphosphite.

8. A process according to claim 2, wherein the membrane of the composite membrane is a polydimethylsiloxane polymer.

9. A process according to claim 3, wherein the membrane of the membrane compound is a polydimethylsiloxane polymer.

10. A process according to claim 5, wherein the organophosphite is an organobisphosphite, wherein the membrane of the composite membrane is a polydimethylsiloxane polymer and wherein the aldehyde product is an optically active aldehyde.

11. A process according to claim 5, wherein the organophosphite is an organobisphosphite, wherein the membrane of the composite membrane is a polydimethylsiloxane polymer and wherein the aldehyde product is an optically inactive aldehyde.