MXPA97003389A - Procedure for the preparation of aldehi - Google Patents

Abstract

The invention relates to a process for the preparation of aldehydes by hydroformylation of olefinically unsaturated compounds with hydrogen and carbon monoxide, in homogeneous phase, in the presence of a catalyst system containing a complex metal-organic compound, as well as ligands of this complex compound, in a molar excess, and separation of the catalyst system from the hydroformylation reaction mixture, by filtration under pressure in a semipermeable membrane, formed from an aromatic polyamide. This process is characterized in that the molar proportion of the ligand present in excess with respect to the aldehydes used is from 9 to 30, preferably from 10 to 25, especially from 10 to 15, so that the ligands present in excess do not contain any salt of alkyl- or of arylammonium of a sulfonated, carboxylated or phosphonated aromatic diphosphine. By restricting the molar mass ratio, high activation and selectivity values are maintained both in the hydroformylation itself and in the outstanding retention values in the membrane filtration stage for the catalysed system.

Description

PROCEDURE PflRfl Lfl PREPARATION OF ALDEHYDES The present invention relates to a process for preparing aldehydes by reacting olefinically unsaturated compounds with hydrogen and carbon monoxide, in a homogeneous phase, and in the presence of a catalyst system containing complex complexes, as well as ligands of these complex compounds, in? molar excess; and separating the catalyst system from the reaction product by filtration under pressure into a semi-aromatic membrane of an aromatic polyacid. There is an increase in the hydroforming of fine olefins made technically in a large circuit, in the presence of catalyst systems based on complex rhodium compounds containing tertiary phosphine ligands or phosphorus. Due to the fact that the ligands, generally, are in excess, the catalyst system consists of the metalorgamco complex compound and pure additional ligand. In correspondence with the solubility of these catalyst systems in organic media, hydroformylation in homogeneous phase takes place. For the separation of the reaction product and the recovery of the catalyst system homogeneously dissolved in the reaction product, the reaction product is distilled, generally from the reaction mixture. Due to the thermal properties of the fused aldehyde, however, this is possible only in the hydroformylation of lower olefins with up to about 8 carbon atoms in the molecule. During hydroformylation of longer chain defines or of olefinic compounds with functional groups, thermally sensitive products or products with high boiling points are formed, which no longer allow the separation of the catalyst by distillation: the thermal load of the product of Distillation leads, through the formation of a heavy oil, to the considerable waste of valuable product, as well as to the decomposition of complex compounds with loss of the catalyst. Due to this, the economic attractiveness of the process is reduced decisively. In order to remedy the separation of the catalyst system by thermal means, different procedures have been provided. • It is known from EP-R-0 374 fil5 that intact intact organic complexes are separated from the organic solvent, when polyakineide separation membranes are used, which are selectively semipermeable, that is, without formation of catalytically active metal compounds; and they can be recovered. As the driving force to carry out the separation, the difference in pressure (pressure filtration) as well as the difference in concentration (dialysis) can be mentioned. The process is especially suitable for the separation of complex metal-organic compounds and / or inetalcarbonyl compounds with phosphorus compounds (III) as ligands, from organic solutions, where they have found use with homogeneous catalysts. As complex rhodium compounds, which can be used for the homogeneous hydroformylation of olefins, it is mentioned in EP-fi-0 374 615, HRhC0CP (CH < sHa) 3] a, F? Cl [P (CeiHa) 333 and those compounds which contain as ligands alkylaryl or arylammonium salts or carboxylated tparylphosphmas of the general formula: Wherein X means a sulfonyl radical (S0a ~) or a carboxyl radical (C00 ~); x, x2 and x3 are zero or 1; each of Rx and R5-, which may be the same or different, means alkyl radicals of 4 to 12 carbon atoms, aryl radicals of 6 to 12 carbon atoms or cycloalkyl radicals of 6 to 12 carbon atoms. '"" "carbon, and Rl additionally may also represent hydrogen.

In the membrane separation, in two stages, of a rhodium-containing catalyst system and the trusooctylammonium salt of tps (-sulfofen? L) -phosphine, of the crude product of the hydroformylation of dicyclopentadiene, according to EP-O- 0 374 615, 99.5% of the rhodium and 94.4% of the phosphorus compound (TIT) is retained; with which 5.5% of the phosphorus compound (III) remains in the organic hydroformylation product and can be removed therefrom only by means of costly measures, such as a complicated distillation, with large losses of product. The flow in the final stationary condition of the membrane filtration is exclusively at 5 or 10 l / rn2hour in the first or second stage of membrane filtration. It was, therefore, a purpose to provide a process for hydroforming unsaturated olefinic compounds in a homogeneous phase, which allows high activity and selectivity rates and, at the same time, makes possible an improved separation of the entire catalyst system. Said purpose was met by a process for preparing aldehydes by hydroformylation of olefinically unsaturated compounds with hydrogen and carbon monoxide, in homogeneous phase, in the presence of a catalyst system which contains a complex complex and ligands as well as ligands thereof. complex compound, in a molar excess; and separating the catalyst system from the hydroformylation reaction mixture, by means of pressure filtration in a semipermeable membrane, made of an aromatic polyamide; characterized in that the mass molar ratio in the ligand provided in molar excess, with respect to the aldehyde, is between 9 and 30, preferably between 10 and 25 and, especially, between 10 and 15; whereby the ligands do not exhibit any alkyl or anlammonium salt of aromatic diphosphonates alone, Tonated, carboxylated or phosphonated. According to the novel procedure, the complex complexes and the ligands provided in excess, of this complex do not vary, that is to say, they do not decompose or undergo other changes with which they can be recovered free of loss. By the term "metallo-organic complex compounds", according to the context of the present invention, it is meant compounds in which organic groups of carbon atoms are attached to the metal atom. As metals, there may also be mentioned sepumetals, such as boron and silicon. As organic-metal complexes, according to the invention, those compounds soluble in organic solvents can also be mentioned, in which the bond between the metal and the carbon is carried out on nitrogen, oxygen or sulfur. The metal complex of the organic-metal complexes is preferably an element of the groups IVA, VA, VTA, VIIA, VIIIA or IB of the Periodic System of the Elements, and especially manganese, iron, cobalt, nickel, palladium, platinum, r? Tenio , rhodium or iridium. The metalorgameous complex compounds contain, in addition to the metal ligands, such as CO, hydrogen, amine, phosphite, phosphate, acetate, benzonyl, acetylacetonate, dirnethyl glyoxal, pi-olef, such as 1,5-cyclooctadiene. or pi-aro atoms, such as cyclopentadienyl. As ligands, which are found in excess in the catalyst system, monodental ligands may be mentioned, in which the molar ratio of rnonoden ligand < The inorganic complex compound in the hydroformylation is at least 50, preferably from 60 to 120, and especially from 80 to 100. Particularly suitable as monodental ligands are the aromatic phosphines and especially the alkyl and / or salts thereof. or sulfonated arylalkone or carboxylated phosphine tertiary. The salt of the d sest is pointed out spatially 11 arnon i o of t p s? L phona < or from < In addition, sulfonated pyridines, quinolma, 2, 2 '-bipipdma, porfipna and pi pdil phosphma, quinine, glyoxane, sulphonated phophite and acetylacetonate substituted with alkyl have been suggested. aplo, he came out and the nandelato, as ligands that are present in excess. The reaction of the olefin with the carbon onoxide and hydrogen is carried out at a temperature of 100 to 140 ° C, preferably of 120 to 130 ° C., and a pressure of 0.5 to 27 lPa, preferably 20 to 25 nPa. The composition of the synthesis gas, ie the volume ratio of carbon monoxide and hydrogen, can be within wide limits and can be varied, for example, between 1:10 and 10: 1. In general, gaseous mixtures are used in which the volumetric ratio of carbon monoxide and hydrogen is about 1: 1 or not and far from that value. In the process according to the invention, unsaturated compounds of 2 to 30 carbon atoms are added, which may have one or more double bonds. Substituted or unsubstituted alkanes of 6 to 30 carbon atoms, substituted or unsubstituted dienes, of 4 to 10 carbon atoms are suitable; cycloalkenes substituted or unsubstituted or substituted or unsubstituted dicycloalkenes, from 5 to 12 carbon lathes in the ring system; the esters of a more saturated carboxylic acid, from 3 to 20 carbon atoms, and from an aliphatic alcohol of from 1 to 18 carbon atoms; the esters of saturated carboxylic acid, from 2 to 20 carbon atoms and from an unsaturated alcohol of 2 to 18 carbon atoms; unsaturated alcohols or ethers, each having 3 to 20 carbon atoms, or fat aralic olefins of 8 to 20 carbon atoms. As substituted or unsubstituted alkenes, of 6 to 30 carbon atoms, straight chain or branched alkenes can be used, with the site of the double ligation in an extreme position or in an internal position. Preferably straight chain olefms of 6 to 18 carbon atoms can be used, such as n-hexene, n-heptene-1, n-octene-1, n-noneen-1, n-decene-1, n- Ndecene-1, n-dodecene-1, n-octadecene-1 and the acyclic terpenes. Also suitable are branched alkenes, such as dusobutylene (2,4,4-rirnethyl-pentene-1), tppropylene, tetrapropylene and diolsol (di bu full). Preferred examples of unsubstituted dienes are 4 to 10 carbon atoms: 1,3-b? Tad? Ene, 1,5-hexad? Ene and 1,9-decadiene. Examples of substituted and unsubstituted cycloalkenes or dicycloalkenes are from 5 to 12 carbon atoms in the ring system: cyclohexene, cyclooctene, cyclooctadiene, dicyclopentadiene and the cyclic terpenes, such as lignin, pmeno, camphor and bisabolene. The styrene can be mentioned as an example of araliphatic olefins of 8 to 20 carbon atoms. As examples of the ester of a saturated carboxylic acid of 3 to 20 carbon atoms and of an aliphatic alcohol of 18 carbon atoms, the ester of acrylic acid and the ester of methacrylic acid of 18 carbon atoms are mentioned in the alcohol component. The vinyl ester and the allyl ester of 2 to 20 carbon atoms in the carboxylic acid component, such as, for example, vinyl acetate, belong to the esters of saturated carboxylic acid, from 2 to 20 carbon atoms. carbon, and an unsaturated alcohol of 2 to 18 carbon atoms. As the unsaturated alcohols and ethers mentioned, for example, the aralic alcohol and the vinyl ether are mentioned. The process according to the invention is optionally carried out in the presence of an organic solvent, which is inert or hydroformylation conditions and which is not harmful to the membrane in the membrane filtration step. Suitable solvents are aromatic hydrocarbons, such as toluene, ortho-xylene, net-xylene, paraxylene, the mixtures of the xylene isomers, ethylbenzene, mesitylene; mixtures of these compounds or aliphatic hydrocarbons. However, polar solvents can also be used, such as acetophenone, tetrahydrofuran, sulfinol, glycol or polyglycol. However, the hydroforming reaction can also be carried out without the addition of an organic solvent, and in that case, the hydroformylation product formed serves as the solvent. On the basis of the normally high viscosity of a reaction mixture of this type, it is generally obtained in membrane filtration only at reduced flow. The formation of the catalyst system starting from the metal compound or the ligand, is carried out either in a pre-hydroformylation step, the so-called pre-ormation, or, especially when working continuously, in situ, during the hydroformylation reaction. Both variants are described in German patent application Serial No. 196 19 527.6. The preparation of the aldehyde by reaction of the reagent q? E is in the liquid phase and in the gas phase, is carried out in conventional reactors and can proceed continuously or discontinuously. After the hydroforming is completed, the reaction mixture is generally cooled by relieving the free portions of the gas-forming ingredient., and covered with an inert gas, + al, such as, for example, nitrogen, or with a synthesis gas mixture, formed from CO and H2. F Linente, separation is effected by means of membrane filtration. However, the membrane reaction can also be carried out with the membrane also without coating. In the reaction mixture used for the membrane filtration of the hydroformylation, the concentration of the ligands used in excess of the complex organic compounds is between 2.5 and 25, preferably between 5 and 15% by weight, with respect to the mixture. of reaction used for membrane filtration. The concentration of metaorganic complex compounds in which the reaction mixture used for the membrane filtration of the hydroforming is between 2 and 400 ppm by weight, preferably between 10 and 300 ppm by weight, especially 50 to 150 ppm by weight, it refers to the reaction mixture used for membrane filtration.

The membrane filtration is carried out on a polyar- anide membrane at a pressure of 0.1 to 15, preferably 0.5 to 5, especially 1 to 2 MPa. Membrane filtration can be carried out in one or several steps, preferably in several steps, especially in two steps. However, it can be carried out with separation stages arranged in parallel or in series. The serial arrangement is preferred, wherein at each stage, the retained product is separated and the permeated solution is added to the next separation step. A series arrangement of this type allows a substantially effective reduction of the pressure of the system used, ie, the working pressure in the preceding process steps. It is considered as a particularly good result of the separation when the total amount of retention is from 8 to 90, preferably from 10 to 70, especially from 20 to 40%, with respect to the reaction mixture used, and the concentration of the separated ligands, present in the retention product of the membrane filtration, is at least three times that of the hydroformylation reaction used in the membrane filtration. In membrane filtration in two stages it is also advised that the ratio of the retention amount of the first filtration step, with respect to the retention amount of the second filtration step, be approximately 1: 1.

Another improvement of the membrane separation arrangement is obtained by using the process variants described above, by raising the overflow of the membrane with the aid of a revolution pump. The speed of the linear current on the membrane will usually be in the range of 0.1 to 10 rn / second, preferably 0.5 to 2.5 / second. The product retained in the separation step, which contains the catalyst system, can be purified and redrculated to the hydroformylation, optionally with the addition of metal and / or the complex organic compound, as well as the ligands of this complex compound to be replaced. the losses. The addition of these complementary amounts can be carried out in the two steps of membrane filtration, or to the permeation product of the first stage, before it enters the second stage of membrane filtration. In this way, a better separation result can be obtained and a more complete recirculation of the catalyst system in the hydroforming is possible, without costly losses with respect to the activity and selectivity of the catalyst system. If the process according to the invention is carried out in the presence of a solvent, then a particularly high overall efficiency can be obtained, both in the hydrophobicization step and in the membrane separation stage, when in the hydroformylation, little solvent is used to obtain a reaction as high as possible; but in the membrane stage, enough solvent is used to reduce the viscosity. In the hydroforming steps, a solvent portion of 5 to 25% by weight, preferably 7 to 13% by weight, with respect to the totality of the reaction mixture diluted with solvent is convenient; in the membrane filtration step, in contrast, it is preferred to use from 30 to 70% by weight, preferably from 40 to 60% by weight of solvent, with respect to the totality of the reaction mixture diluted with solvent. These high proportions of solvent are obtained in the reaction mixture used in the membrane filtration by distilling off the purified permeate from the separation step the organic solvent, and returning it before membrane filtration. There again it is added to the reaction mixture to be separated, from the hydroformylation. When this is obtained, a corresponding dilution is obtained which is appropriate for the obtention of higher flow conditions. The membranes used according to the invention consist of an aromatic polyamide, also called polyararnide. The polyaramide is obtained by poly condensation of aromatic dicarboxylic acids, or dicarboxylic acid derivatives and aromatic diammas, in a dipolar aprotic solvent. Examples of carboxylic acid components are terephthalic acid, 4,4'-difenecarboxylic acid, 4,4'-di-femleterdicarboxylic acid, 4,4'-diphemelsulfondicarboxylic acid or acid. 2, 6-naphthalend? Carboxyl? Co. Examples of dianin components are p-phenylenediarnine, 3,3-dirnetoxybenzydine, 3,3 '-dichlorobenzid a, 3,3'-dimethylbenzid a, 4,4'-diamino-phenylrnetane, 2,2-b? S - (4-arn? No-phenyl) propane ol, 4-b? S (4-am? Nofenox?) Benzene. Of special importance are polyarranide membranes which contain, in addition to a carboxylic acid component, different diainins with monomers. Mention may be made, for example, of polyarapps formed from terephthalic acid, p-phenylenediam a, l, 4-b? S (4-arninophenoxybenzene and 3,3'-dirnenylbenzide.) In polymers the amines may be distributed The pollenidae, however, may also have the block copolymer structure.The average molecular weight of the polyarannide can vary within wide limits, usually between 5,000 and 200,000. molar mass of 10,000 to 50,000.To prepare the membranes according to the invention, a process is used which is described in the German patent application P 38 02 030. The membranes described there consist of a copolyamide, which is formed from three different days and a dicarboxylic acid, a solution of these copolyamides in an aprotic polar solvent, of the amide type, for example N-met? i-2-? rrol? dona, is extended as liquid layer on a flat substrate. This liquid layer is kept in the falling liquid, especially water, which is miscible with the solvent in the solution, however, the polymer separates as a membrane.The dropping liquid is allowed to impinge on the membrane for so long until The solvent has been used completely by the fall liquid, in addition, it is possible that the membrane is subjected to a heating treatment, then the membrane is dried, eventually after a previous treatment with g ice ina. prepared according to the process described above, they are asymmetrically integral and are known to those skilled in the art.The membranes have a very thin active separating layer, with a thickness of 0.05 to 5 microns and a porous support structure. The thickness of the membrane consisting of an active separating layer and a support structure can be between 10 and 400 microns; preferably, it is within the range of 50 to 200 microns. The shape of the membrane can be freely selected. It can be formed as a disc and, especially as hollow fibers or capillaries; however, also all those that are appropriate for the intended use. It is crucial to obtain a stability as high as possible and, above all, a surface as wide as possible for each volumetric unit, in order to obtain a constant production satfactory. It is recommended that the membrane be pre-treated before use. In simple cases, it is submerged in the solution to be separated. However, other conditioning methods are also possible. The membrane soaked with glyce- pna for storage purposes, is then washed with water and then left for 10 minutes in hot ag- gle at 80-100 °. The ag? A is then replaced, for example by isopropanol, the membrane is left in the isopropanol and the alcohol is renewed several times. The isopropanol is then replaced in the same way by the hydroformylation reaction mixture, in which the complex organic compounds, as well as their ligands, are dissolved. In order to obtain an optimum separation condition, it is also advisable that the membrane allows to withstand a desired time under the working conditions; that is to say, that the membrane filtration is carried out under the use of the hydroformylation reaction mixture, each of the retained product and the permeate obtained, can be sent to purification and recirculated to the hydroforming reaction mixture, before of membrane filtration. By means of this conditioning called pressure, more pores of the membrane are closed, which increases the capacity of separation of the membrane. The technique and methods of conditioning the membrane are adjusted to the working conditions employed in the process according to the invention.

EJEtlPI-QS In the following, the formation of a membrane of the art is described, as can be used according to the method according to the invention.

PREPARATION OF Lfl MEMBRANE The polyaramide is obtained by condensation of: 97-99 mol% of terephthalic acid dichloride LCO, 25 mol% of p-phenylenediarin, 25 mol% of 1,4-b? s (4-aminophenoxy?) benzene, 50% molar of 3, 3 'unethylbenzide, in N-me? i ?? ideal sound as an eoliant. The terephthalic acid dichloride is added in an amount such that the polyarynnide has a Staudmger index of 200 to 300 ml / g. The amount of solvent is mixed in such a way that a solution containing about 7% by weight of polycondensate is formed. After the condensation is established, the loose amount of hydrochloric acid bound to the solvent is neutralised by the addition of 100% molar CaO. Subsequently, 5% by weight (based on the polymer solution) of water-free calcium chloride is dissolved in the reaction mixture under stirring. The solution is slightly heated, filtered and degassed. It can be used immediately for the preparation of the membrane. It is possible that the membrane is prepared free of support or on a polyester fleece as support. In the following the preparation of a free support membrane is described. The slightly hot polyarnide solution is spread with a scraper, on a glass plate, to a uniform film of about 150 microns, and immersed in a water bath of 2 ° C. After about 20 minutes the membrane is recovered from the glass plate and left for 5 minutes in hot ague at 100 ° C. After this the membrane is placed in isopropanol, in order to exchange the water that floods the pores with alcohol. The membrane is then washed with toluene, after this treatment it is ready to carry out the separation. In all operations, care must be taken that the membrane does not dry out.

EXAMPLES 2 - 6 AND COMPARATIVE EXAMPLES 1. 7 AND 8 The hydroformylation of dicyclopentadiene is obtained (DCP) through the use of r-hate catalyst systems and different ammonium salts of triphenyl phosphine toll-fonate (TPPTS): a) Preparation of the disteranlamonium salt of TPPTS 253 g of a solution of Na-TPPTS are introduced, under nitrogen, into a shake flask, and heated to 65 ° C. Then a solution of 250.3 g of distetramine in 595 g of toluene is introduced. Within 60 minutes, 90 rnl of 20% sulfuric acid is added with stirring, until a pH value of 2.6 is obtained, and it is allowed to continue reacting for 2.5 hours. For a better phase separation, ß adds 170 g of isopropanol. After 15 minutes, 1037.5 g of an organic phase containing the distearylarnionium salt of TPPT ?, is separated with 0.33 moles of TPPTS per mole of amine. The organic phase contains 126 molsols of phosphorus III) / kg. Other salts of TPPTS are prepared analogously in the stage described above (examples 2 to 7 and the example cornpara-t i vo i). The commercial products called Jeffamines, used in example 3, as well as in comparative examples 7 and R, are from Texaco Chemical Corporation and have the following structure: Jeffarn M 600: (molar mass = 600 g / rnol) CHaOCH siCHaO - (CHICHO ) n - CHa - CH - NHS Jeffainin D 2000: (molar mass = 2, 000 g / rnol) HaN - CH - CH2 * - 0 - CH ^ CH * "HS III and CH3 CH3 Jeffamip T 3000: (molar mass - 3,000 g / mol) [0- CHa -CH ^ Ha /! / CHa CHa-CHa - C [-OCHaCt-KhnNHa \! \ CH3 \ CHa B) Hydroxylation dlSCPrv nua dfi diciclopentadieno u- ligand salt Je tiies earilamoniQ -Je TPPTS.

A stirring autoclave of 2.15 liters is washed with nitrogen. In a glass flask with an installation for the addition of nitrogen, 212.8 g of the ligand solution of a) is added, as well as 0.29 rhodium mrnols in the form of a salt of 2-ethylhexanoate disil ( 60 ppm by weight of Rh, proportion of P / Rh: 100) and 500 g of toluene, under nitrogen, to the autoclave. Then, with stirring and under addition of synthesis gas, a pressure of 27 MPa is established. After reaching a reaction temperature of 130 ° C, it is allowed to stand for two hours. Then, within one hour, 500 g of dicyclopentadiene is pumped into the autoclave.

When cooling with an air current, the temperature is maintained at 130 ° C. At the end of the addition of dicyclopentadiene, let it continue to react for 3 more hours. Finally, the autoclave is cooled to room temperature and opened. The contents of the autoclave are added with residual pressure in a 2-liter, three-necked flask, with a dip tube and extracted. The production of dicyclopentadiene is calculated from the increase in e-so. The hydroformylation of dicyclopentadiene is carried out analogously, by using the ammonium salts of TPPTS according to examples 3 and 6 and comparative examples 1, 7 and 8. The results obtained are shown in table i. c) Membrane filtration in a single stage The respective reaction product above, from step b), is added to a membrane filter installation. A membrane of polyarnide from Hoechst AG (UF-PA (PET 100)) is used as the membrane. Then continue the membrane for 10 minutes at 80 ° C in ag? a. The membrane is then used by means of a rotary pump, with a current of more than 200 l / hour, and at a pressure of 1 MPa. After a recovery temperature of 40 ° C, the quantity given in table 1 of the hydroformylation product is passed through the membrane, as a product of 00 perrneacion. In the permeation product, the content of part of catalyst is calculated, from which the recirculation value is obtained, with r-speci fi c to the reaction mixture used in the hydrolynination, which is given in Table 1 It can be obtained from Table 1 that with only the maintenance of a molar proportion [molar mass (ligand): molar mass (aldehyde) 1 = 9 - 30, in addition to hydroformylation, outstanding selectivity can be obtained, as well as recovery values outstanding in membrane separation.

E3EI1PLQ 9 It is washed thoroughly with nitrogen, a 5 liter agitation autoclave, with a dip tube for the gas inlet and the product outlet, as well as a gas exhaust valve. To the autoclave is added 872 g of a toluene salt solution of TPPTS distearylamine with a phosphorus content (III) of 138 mmol / g, as well as 120 rng of rhodium in the form of Rh 2-ethexanoate, of a sample with a protection of neither ogen. The catalyst is then preformed for 2 hours at 27 MPa and 125 ° C. Then, in the course of 1 hour, 1500 g of propylene, from a sample, is pumped through the immersion tube (80 ppm Rh, with respect to propylene, molar ratio P: Rh = 100). The heat of the reaction is extracted by means of a chiller in the reactor. He will react one more hour and cool down. The autoclave is uncapped, emptied into a three-necked flask with agitator device and recovered (3,028 kg). The reaction is carried out in 95%, and the n / i ratio is 63/37. The reaction product is then introduced into a membrane working facility and filtered in 2 stages. The membrane pressure is 1.5 MPa. A membrane UF-PA5 (PET 100) from Hoechst AG is used. The recirculation values and flow conditions given in Table 2 are obtained. The retention product of the first and second stages is then returned and is again introduced into the autoclave to react with propylene. The very low loss of Rh and phosphorus III) is correspondingly compensated by the addition of rhodium 2-ethexanoate or of a solution of the salt of onesteapla onium of TPPTS. The complement is added to the permeation product of the first stage. The catalyst is re-circulated a total of 10 times, without substantially the reaction (90-95%), the selectivity (ratio n / i 63/37) or the recirculation value (see table 2). In the values given in table 2 for the flow rate, the first value represents the initial value in the respective membrane filtration stage, while the second value characterizes the addition for weight equalization. Table 2 indicates that in the use again the flow rate due to a concentration that increases, leads again to a thick oil; however, it stabilizes at a low level, ie, also the thick oil is permeated and, thus, a separation of the catalyst * and thick oil ingredients is possible. Table 2 also indicates that according to the process of the invention, the metal complex and the excess ligands of the product are distinguished in the first place; and then the thick oil is separated and can be recirculated.

"* ~" TABLE 1 Ex. Amine in salt Molar mass- Provide- Hi.droform? .lation No. of ammonium of Mi of the mo mo. Reac - Selectivi- TPPGS salt of the master Ml / tion, - nity, di l - nium of TPP MITTCD- (%) dehyde / mo- (g / rnol) dial) * monoenal. - 1 (C) tnisooct il- 1563.5 8.1 99.9 99/1 to ina 2 Diesteapl- 2068.47 10.8 99.4 97/3 arnma 3 Jeffarnin M600 2302.47 12.0 98.8 4 Triacel Illamma 2573.43 13.4 98.7 96/4 tp -n-octade- 2825.91 14.7 98.5 91/9 cilamine Tp docosi lamina 3330.87 17.3 99.7 90/10 7 (O 3effarnme D2000 (5502.47 33.8 98.1 69/31 8 (C) D ffan e T300 9502.47 49.4 98. 63/37 * M (TCD-dial) = 192.26 g / mol CUñPRQ 1 (continuation? E. Qty i Flow Rate Retention (%) of the added perme nd number (l / rn = h) Rh Ligand (P) Amine (N) (additive). - 1 (C) 15 64 89.3 69.8 16.5 2 66 61 97.5 96.1 78.3 3 3 9 99.7 98.7 63.9 4 22 44 95.0 90.0 73.3 53 49 93.0 87.0 88.7 6 48.8 29 96.5 94.7 81.9 7 (C) 29 22 99.5 89.4 93.9 8 (C) 56 31 99.7 97.7 91.4 CUñPRQ 2 SEPARATION IN MEMBRflNfl AND RECIRCULFlTION OF AN Rh CATALYZER SYSTEM WITH ITS DIESTEARILAMONIO SALT OF TPPTS LIKE LINKING. IN PROPYLENE HYDROFORMILATION Hi drofor-m11ation Time Tempera- RecirAntity of per- Retention Rectum flow rate ° C calamitous (% of (% of the (l / rn2 / h) action - addition adícion) la. E- 2a. Rh P (total) the e-2a. E-- lid - lid. 2 125 0 87 86 95.96 89.3 103-10 136-51 2 125 1 85 94 99.23 92.7 97-16 115-40 2 125 2 85 96 99.71 99.3 97- 1 7 82.29 2 125 3 88 93 98.85 99.2 82-15 75-24 2 125 4 84 94 99.30 99.4 76-17 68-28 2. 3 125 5 82 90 99.57 98.9 72-17 56-15 2. 5 1.27 6 83 95 98.61 99.0 67-13 66-10 2 128 7 84 93 99.52 97.2 67-12 89-30 126 8 83 9 99.09 96.7 -10 74-16 128 9 83 94 99.07 97.6 -1.0 76-22 125 .10 81 93 98.80 98.2 -1.2 62-21.

Claims (16)

NOVELTY OF THE INVENTION REIVIN ICATIONS

1. - Process for preparing aldehydes by hydrotornylation of olefinically saturated compounds, with hydrogen and carbon monoxide in a homogeneous phase, in the presence of a catalyst system which contains a complex organic compound, as well as ligands of this complex compound, in a molar excess, and the separation of the catalyst system from the hydroformylation reaction mixture, by filtration under pressure in a semipermeable membrane, formed of an aromatic polyarnide; said process characterized in that the proportion of molar mass of the ligand present in excess, with respect to the aldehyde prepared is between 9 and 30, preferably between 10 and 25, especially between 10 and 15; so that the ligands present in excess do not contain any alkyl- or aplarnon salt or phosphonated, phosphonated, phosphonated, buffered aromatase diphosphines.

2. Method according to claim 1, further characterized in that the metal of the metalorganic complex compound is an element of the groups IVA, VA, VIA, VTIA, VIIIA or IB of the Periodic System of the Elements and, especially, it is manganese, iron, cobalt, nickel, palladium, platinum, ruthenium, rhodium or iridium.

3. Method according to claim 2, further characterized in that the ligand present in excess is a rnonodental ligand, and the molar ratio of rnonodental ligand to complex organic compound in hydroformylation is at least 50, preferably between 60 and 120 and, especially, between 80 and 100.

4. Method according to one or more of claims 1 to 3, further characterized in that the ligand present in excess is selected from sulphonated pyridines, quina, 2, 2. '-b? p? pd? na, porphyrin and pipdylphosphine, quinine, glyoxyrn, sulphonated phosphite, as well as acetyl-carbonate, alkyl- and apl-substituted salicylates or mandelics.

5. Process according to one or more of claims 1 to 4, further characterized in that the reaction of the olefin with carbon monoxide and hydrogen is carried out at a temperature of 100 to 140 ° C, preferably 120 to 100 ° C. 130 ° C, and under a pressure of 0.5 to 27 MP, preferably 20 to 25 MPa.

6. Method according to one or more of claims 1 to 5, further characterized in that olefinically unsaturated compounds of 2 to 30 carbon atoms are used for the hydroforming, which have more or less double bonds.

7. Method according to one or more of claims 1 to 6, further characterized in that it is carried out in the presence of an organic solvent.

8. Method of compliance with one or more of claims 1 to 7, further characterized in that in the hydroformylation reaction mixture, used for membrane filtration, the concentration of ligands present in excess, of the complex compounds, it is between 2.5 and 25, preferably between 5 and 15% by weight, with respect to the reaction mixture used for membrane filtration.

9. Method according to one or more of claims 1 to 8, further characterized in that the concentration of the organometallic complex compound in the hydroformylation reaction mixture used for membrane filtration is between 2 and 400 pprn by weight, preferably between 10 and 300 ppm by weight, especially between 50 and 150 ppm by weight, with respect to the reaction mixture used for membrane filtration.

10. Method according to one or more of claims 9, characterized in that the membrane filtration is carried out in a polyarynnary embryo, under a pressure of 0.1 to 15, preferably of 0.5 to 5, especially of 1 to 2 NPa, and is carried out in one or several stages, preferably in two stages.

11. Method according to claim 1 or more of claims 1 to 10, further characterized in that the membrane filtration is carried out with separation steps arranged in series.

12. Method according to one or more of claims 1 to 11, further characterized in that the total amount of separation product of the membrane filtration is from 8 to 90%, preferably from 10 to 70%, and especially from 20 to 40%, with respect to the hydrofornylation reaction mixture used; and the concentration of the ligand separated from the complex compound in the retention product is at least three times higher than in the hydroformylation reaction mixture used for membrane filtration. 13.- Procedure according to claim 12 or claims of claim 12, further characterized in that in the two-stage membrane filtration, the proportion of the amount of retention product of the first stage of retention with respect to the The amount of retention product of the second stage is approximately 1: 1. 14. Process according to claim 1 or claim 13, further characterized in that the retention product containing the catalyst system, the steps of membrane filtration separation is recirculated to hydroformylation, event? Ally under complementary addition of metal and / or of the metallo-organic complex compound, as well as of the ligands of this complex compound. 15. Method according to claim 14, further characterized in that in the implementation in two stages of the membrane filtration the complementary addition of the metal and / or complex metal-organic compound and the ligand of said complex compound to the product is effected. of permeation of the first filtration stage, before passing it to the second filtration stage. 16. Process according to claim 1 or claim 15, further characterized in that the distillate solvent product is separated from the purified permeate from the separation steps of the membrane filtration, recirculated before membrane filtration. and the hydrotormylation reaction mixture is added before membrane filtration.