MXPA97003390A - Procedure to prepare aldehi - Google Patents

Abstract

The present invention relates to a process for the preparation of aldehydes by the hydroformylation of olefinically unsaturated compounds with hydrogen and carbon monoxide, in a homogeneous phase, in the presence of a catalyst system containing complex rhodium compounds as well as aromatic phosphines, in molar excess and the separation of the catalyst system from the hydroformylation reaction mixture by means of filtration under pressure in a semipermeable membrane, of an aromatic polyamide. The process is characterized in that the hydroformylation is carried out at a pH value of 2.5 to 4.3, with the use of a molar ratio of phosphine: rhodium of at least 60 and at a rhodium concentration of at least 10 ppm by weight, with with respect to the olefinically unsaturated compound used, and it is used as aromatic phosphines especially alkylammonium and / or arylammonium salts of sulfonated or carboxylated triarylphosphines, the process according to the invention results in outstanding activity and selectivity values in the same step of hydroformylation, as well as high retention values in the membrane filtration stage

Description

PROCEDURE TO PREPARE ALDEHYDES The present invention relates to a process for preparing aldehydes by the reaction of olefimcarnen + e msaturados compounds with hydrogen and carbon monoxide, in homogeneous phase, and in the presence of a si-tite catalyst containing a complex rhodium compound, as more aromatic phosph in a molar excess; and repair of the catalyst system of the reaction product, by membrane filtration. There is an increase in the drilling of oleas effected only in a large circuit, in the presence of catalyst systems based on complex rhodium compounds containing tertiary phosphines or phosphines as ligands. Due to the fact that the ligands, as a rule, are in excess, the catalyst system consists of the complex compound rnetalorganico and free ligand in excess. In correspondence with the solubility of the catalytic systems in organic media, homogeneous hydroformylation 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 formed aldehyde, however, this is possible only in the hydroforming of lower olefins with up to about 8 carbon atoms in the molecule. During the hydroforulation of longer chain olefins or of olefinic compounds with functional groups, thermally sensitive products or products with high boiling points are formed, which no longer allow satisfactory separation by distillation of the catalyst: the thermal load of the The distillation product leads, by the formation of a heavy oil, to the considerable waste of valuable product, as well as to the decomposition of the complex compounds with loss of the catalyst. Because of this, the economic attractiveness of the process is decisively reduced. In order to solve the separation of the catalyst system, thermally, there are different procedural alternatives. A process for preparing aldehydes by reaction of olefins with hydrogen and carbon onoxide in homogeneous phase is known from FlP-fl- 0 216 375 in the presence of a catalyst system containing rod or like aromatic phosphines in molar excess.; where, as aromatic phosphors, sulfonated or carboxylated salts of tpaplfosphols are used, soluble in organic media and insoluble in water. The cations of these salts are preferably ammonium ions of the formula (NR2"H2) + and / or (NR3H) +, wherein R represents an alkyl radical of 4 to 12 carbon atoms or aplo or cycloalkyl radicals of 6 to 12 atoms of carbon. In this case, the mixture of hydroxylation with a base, for example alkaline or alkaline hydroxide solutions, is treated for the separation of the catalyst system from the reaction product. Thus, the salts of (NR2l-1) + or (NR 3"H) + the corresponding secondary or tertiary amines are liberated and, at the same time, an alkaline or lime salt is formed, soluble in water, from the < Sulfonated or carboxylated riphaphophim, Which is in the aqueous phase and must be separated in an extraction, together with the rhodium complex bound to the phosphorus, from the organic phase containing the product of hydroformy lac on. It is also known from EP-fi-0 374 615 that complex metal compounds containing phosphorus compounds (III) or their ligands, after their addition as catalysts for the hydroformylation of fine ole in homogeneous phase, they can be separated by membrane filtration of the hydro or illation products. By using polycarbonate separation membranes, selectively impermeable, it is possible to separate and recover the intact complex compounds, ie, without separation of the catalytically active metal compound. As the driving force for the separation, a pressure difference (pressure filtration) as well as a difference in concentration (dialysis) can be mentioned here. It can be mentioned as complex rhodium compounds effectively separated in EP-fi-0 174 614rn, HRhCOCPfCßHs) 313, RhClCPICßHs 333 and those compounds mentioned which contain as ligands alkyl- or aplarnon salts of sulfonated or carboxylated t -arylphosphines of the general formula: wherein X means a sulphonyl radical (S? 3 ~) or a carboxyl radical (COQ-); x1, x2 and x3 are zero or 1; each of R1 and R2, which may be the same or different, means radicals alkyl from 4 to 1? carbon atoms, radicals from 6 to 12 carbon atoms or cycloalkyl radicals from 6 to 12 carbon atoms; and R1 additionally may also represent hydrogen. In membrane separation, in two stages, from a The catalyst system containing rhodium and the salt of tn soocti lamonium of tp s (rn-sul-phononyl) -phosphine, of the crude product of the hydroformylation of dicyclopentadiene, according to EP-fl-Q 374 615, is retained 99.5% of the rhodium and 94.4% of the phosphorus compound (III); with what remains 5.6% of the The compound of phosphorus (III) in the organic hydroformylation product can be removed therefrom only by expensive means, such as complicated distillation, with large product losses. The flow in the final stationary condition of the membrane filtration, is exclusively at 5 or 10 l / rn2hour in the first or in the second stage of membrane filtration. It was, therefore, a purpose to provide a process for hydroforming olefinically more saturated compounds in a homogeneous phase, which allows high activity and selectivity indices and, at the same time, allows an improved separation of the entire catalyst system. Said purpose was met by a process for preparing aldehydes by hydroforming olefinically unsaturated compounds with hydrogen and carbon monoxide, in a homogeneous phase, in the presence of a catalyst system containing complex rod compounds, as well as aromatic phosphines. in a molar excess, and the separation of the catalyst system from the hydroforming reaction mixture by means of filtration at a pressure, in a semipermeable membrane, of an aromatic polyalpha; characterized in that the hydroforming is carried out at a pH-value of 2.5 to 4.3, using a molar ratio of phosphine: rhodium of at least 60 and with a rhodium concentration of at least 10 ppm by weight, with with respect to the unsaturated olefimcarbon compound used; and using alkyl aromatics and / or aryl ammonium salts of sulfonated or carboxylated triam-1-phosphines of the general formula I as phosphates: wherein X means a sulphonate (SO3) - or carboxylate (COO-) radical; a, b and c are the same or different and are 0 or 1; wherein at least one of the parameters a, b or c must be equal to 1; n is equal to 1, 2 or 3; R1 and R2, which may be the same or different, mean alkyl radicals of 8 to 30 atoms of Carbon or aryl or cycloalkyl of 6 to 10 carbon atoms; and R1 may also be hydrogen; and The carbon atoms in the radicals R1 and R2 must be as much as 30%. The aromatic phosphines of the general formula T are as carhoxylate or ammonium sulfonate, from 1 to 3. times the load of phosphine anion and the corresponding sum of ammonium cations appear as counter ions. They are not soluble in water or only sparingly soluble in water. In organic solvents, they have, on the contrary, good to good solubility, and are therefore suitable for use. ? f \ rather in the organic phase. In formula I, X means a carboxylate or sulfonate radical, preferably a sulfonate radical; a, b and e are the same or different and can be 0 or l; where at least one of the parameters a, b or c must be equal to l. Preferably, a, b, and c are equal to 1. R1 and R2 are the same or different and represent alkyl radicals of 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms, or aryl or cycloalkyl radicals of 6 to 10. carbon atoms, preferably phenyl or clohexyl radicals, where R1 can also be hydrogen. In this way, ammonium cations TH-NRiR2R23 + are derived from secondary or tertiary amines and contain in the radicals R1 and R2 at least 30 and a maximum tie 90, preferably from 32 to 70 and, especially, from 36 to 54. , carbon atoms. Preferably, as ammonium cations in the diasterelaronium ion, the on tricot 11 ammonium or the tp-n-octadecylammonium ion is used. For the preparation of the ammonium salts of sulfonated tp-phenyl-phosphine, the t-phenyl-phosphine according to DE 26 27 354 is then sulfonated by reaction with excess sulfur trioxide, in the form of sulfuric acid (sulfuric acid). fuming), so that the sulphonation mixture is diluted with water and then dissolved in a water-soluble organic solvent, and the water-soluble NR! R2R2 amine is added. In this way, the corresponding ammonium phases of the tp fem 1 fos j na are formed, which can be separated as an organic phase.

The formation of the catalyst system from rhodium or a rhodium compound and the fo-end compound of the formula T is carried out either in a series-forming step, the so-called preform, or, especially in a form of continuous work, in situ, during the reaction of droformilacion. The preform carried out in series with the hydroforming is preferably carried out in the reactor in which the droforrnilation is also carried out; Nevertheless, can also be carried out in a separate reaction vessel. For the preparation of the catalyst system, by pre-forming, the rhodium component (rhodium or a rhodium compound) is combined with the phosphine compound in accordance with the formula I, either in the hydroforming reactor or in a repaired reaction apparatus. For the preparation of the catalyst system by preforming, the rhodium component (rhodium or a rhodium compound) is combined with the phosphine compound in accordance with the formula I, either in the hydroforming reactor Lacion or in a separate apparatus. For olium, either rhodium or the rhodium compound is used, or else the phosphine compound according to formula I, dissolved in an organic solvent, in the case of elemental rhodium, suspended in the. They are solvent Z > , appropriate the organic solvents which are inert to the following hydroformylation conditions, such as toluene, ortho-xylene,? necta-x log, for xylene, isomeric mixtures of xi Log, 2-ethexanol, etiibenzene, rnes-Latiene, mixtures of these compounds or hydrocarbons to the fat. It is preferred to use o -lewood or toluene. The rhodium / phosphine mixture is then combined with a mixture of carbon monoxide and hydrogen and reacted under a carbon monoxide / hydrogen pressure of 0.5 to 27 MPa at temperatures of 80 to 150 ° C. for one hour, with formation of complex compounds of rod or more soluble in water and soluble in organic media, containing phosphine or ligands. They produce together with the excess phosphine dissolved in the organic solvent, the catalyst system. The solution of the catalyst system, in the case of the preparation in a separate apparatus, can be sent to the hydroforming reactor and can be transferred with the olefin which is to be droforned Lar. In the case of the preparation of the catalyst system in situ during the hydroformylation reaction, then the above-described components, rhodium or rhodium and phosphide compound, can be introduced together with the olefin into the hydroformylation reactor. Rhodium can be used as a metal or as a compound. In metallic form, it is used in the form of finely divided particles, or it can be deposited in thin layers on a carrier, such as activated carbon, calcium carbonate, aluminum silicate or aluminum clay. Mention may be made, as rhodium compounds, of those substances which are soluble or suspensible in organic solvents, or which may be soluble or suspended therein under the conditions of the reaction. Suitable are the various rhodium oxides, the hydrazide salts or the inorganic oxyacids, as well as the salts of onocarboxylic acids or aliphatic polycarboxylic acids. Examples of the salts of i-hate: rhodium nitrate, rhodium sulfate, rhodium acetate, rod 2-ethylenehexanoate, rod nalonate LO. Halogenated rhodium compounds, due to the low activity, of the resulting complexes, and due to the corrosive properties of the halogen ions, are unsuitable. Conventionally, rhodium-carbonyl compounds, such as Rh., (C0) i2 or Rhß (C0) i6 or complex salts of rod or, for example, cyclooctadiem-lrodium compounds, can be used. Rhodium oxide is preferred, and rhodium acetate as well as rhodium 2-ethexanoate is especially preferred. It is not necessary that the phosphine ligands of formula I be used in the catalyst system as individual compounds. For example, they can also be used as different sulphonation materials of fine phos and / or as sulfonate mixtures with different LOO cations. It has given good results in the formation and use of the catalyst system, that the rhodium and the aromatic phosphide of the formula T are not used in an estequiornetc ratio, in correspondence also with the chemical composition of the rhodium complex compound formed, but rather than adding the aromatic phosphine in an excess. In this way, it is essential that at least 60 rnols of phosphine be added for each mole of rhodium. A molar ratio of rhodium to aromatic phosphine of 1: (69-120) is preferred. A proportion of 1: (70-110) is especially preferred and, in particular, a ratio of 1: (80-10 (1) is used.) It has also been considered essential that the concentration of rod or hydroxide for Lacion, With respect to the unsaturated olefin compound, it is at least 10 pprn by weight, preferably at least 20 pprn by weight and, in particular, from 60 to 150 pprn by weight In the process according to the invention, it is reacted olefinically unsaturated compounds having from 2 to 30 carbon atoms, which may have one or more double bonds, and unsubstituted or substituted alkenes of from 6 to 30 carbon atoms are unsubstituted, substituted or unsubstituted dienes having from 4 to 10 volumes of Carbon, Substituted or unsubstituted cycloalkenes or Substituted or unsubstituted dichoalkenes, from 5 to 12 carbon atoms in the ring system; the esters of an unsaturated carboxylic acid, 3 to 20 carbon atoms and of an aliphatic alcohol of 1 to 18 carbon atoms, the esters of a saturated carboxylic acid of 2 to 20 carbon atoms and of an unsaturated alcohol from 2 to IR carbon atoms, the unsaturated alcohols or ethers each having 3 to 20 carbon atoms, or the araliphatic olefins of 3 to 20 carbon atoms. As substituted or unsubstituted alkenes, from 6 to 30 carbon atoms, straight-chain or branched alkenes can be mentioned, with extreme or internal positions of the double ligature. Preference is given to r-ecta chain olefins of 6 to 18 carbon atoms, such as n-hexene-L, n-heptene-1, n-octene-1, n-noneeno-1, n-decene-1, n -undecene-1, n-dodecene-L, n-octadecene-1 and the acyclic terpenes. They are appropriate 1 (1 also branched alkenes, such as dusobuti leño (2,4, 4-t pmet? Lpenteno-1), tppropileno, tetrapropileno and dirnersol (dibutiieno). Preferred examples of unsubstituted dienes of 4 to LO are carbon atoms: 1,3-butadiene, 1,5-hexadiene and 1,9-L5 decadiene. Examples of substituted or unsubstituted cycloalkenes or dicycloalkenes are 5 to 12 carbon atoms in the anion system: cyclohexene, cyclooctene, cyclohexadiene, dicyclopentadiene and cyclic terpenes, such as limonene, pinene, camphor and bisabolene. Dicyclopentadiene is preferred. Styrene is an example of araliphatic olefins of 8 to 20 carbon atoms. One can also cite co or examples of esters from a ? R Msaturated carboxylic acid, from 3 to 20 carbon atoms and from an aliphatic alcohol of L to 18 carbon atoms, the acrylic acid esters and the acid esters inetacp 1 LCO from L to 18 carbon atoms in the alcohol component . The esters of a saturated carboxylic acid, from 2 to 20 carbon atoms, and from an alcohol saturated from 2 to 18 carbon atoms, belong to the vinyol and allyl esters, from 2 to 20 carbon atoms in the carboxylic acid component. , such as, for example, vini acetate lo. As more saturated alcohols and ethers, mention may be made, for example, of the alcohol and the vinylic ether. The reaction of the olefin with the carbon monoxide and the hydrogen is carried out at a temperature of from 100 to L40 ° C, preferably from 120 to 130 ° C, and under a pressure of from 0.5 to 27 MPa, preferably from 20 to 25 MPa. The synthesis gas composition, that is, the volumetric ratio of carbon onoxide and hydrogen, can be extended within certain limits and, for example, can vary between 1:10 and 10: 1. In general, gaseous mixtures are used in which the volumetric ratio of carbon monoxide and hydrogen corresponds to about 1: 1, or does not deviate much from that value. It is also of great importance that the hydroforming was carried out at a pH of 2.5 to 4.3, preferably 3.0 to 4.0, especially at 3.5. In the course of hydroformylation, the pH value can be continuously reduced by the dissociation of the ammonium salt of the sulfonated or carboxylated trifemylphosphine, to the free amine and the corresponding reduction in the form of sulphonic acid or carbonic acid. of the Ifosphine triphosphate. To maintain the pH values mentioned above, optionally free amine NRiR2R2 or a corresponding amount of metal hydroxide is added. It is preferred to carry out the process according to the invention in the presence of an organic solvent which is inert under the conditions of hydroforming, and which does not attack the membrane in the membrane filtration step. Suitable solvents are aromatic hydrocarbons, for example, toluene, ortho-xylene, meta-xylene, para-xylene, mixtures of isomeric xylenes, ethylbenzene, rnesitylene, mixtures of these compounds or aliphatic hydrocarbons. However, polar solvents can also be used, such as acetophenone, tet rahídrofuran, sulfinol, glycols, or polyalkyl alcohols. However, the process according to the invention can also be carried out without the addition of an organic solvent, in which case the starting olefinic compound and the hydroformylation product formed, work together with solvents. Based on the high viscosity obtained in a reaction mixture such as the one mentioned above, during membrane filtration, only reduced flows are obtained. D The preparation of the aldehyde by reaction of the reaction ingredients which are in the liquid phase and in the gas phase, is carried out in conventional reactors and can be carried out continuously or in a continuous manner. discont nua After the end of the drilling orrnilacion, The reaction mixture or rule is cooled, is released by expanding the free gaseous constituents and covered with an inert gas such as, for example, nitrogen or with a synthesis gas mixture, formed of CO and H2. Then the separation is effected by means of membrane filtration. However, the reaction mixture can be brought to membrane separation without cooling. In the reaction mixture used for the membrane filtration of the hydroformylation, the concentration of the ligands used in excess, of the complex compounds rnetalorgamcos 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 the complex organic compounds in which the reaction mixture used for the membrane filtration of the hydrochloride is at 2 and 400 m in weight, preferably between 10 and 300 ppm in weight, especially at 50 150 pprn on weight, refers to the reaction mixture used for membrane filtration. The membrane filtration is carried out on a polyacrylamide membrane or a pressure of 0.1 to 15, preferably 0.5 to 5, especially 1 to 2 MPa. The membrane race can be performed in one or more 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, that is to say, the working pressure in the preceding process steps. It is considered as an especially good result of separation when the total amount of retention is from 8 to 90, preferably from 10 to 70, especially from 15 to 50, most especially from 20 to 40%, with respect to the reaction mixture. used for membrane filtration, and the concentration of the aromatic phosphate separated from general formula I, present in the retention product of the membrane filtration, is at least three times that in the reaction mixture used for the membrane. membrane filtration of the hydrofor lation. In two-stage membrane filtration 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 vari before the procedure described above, by raising the overflow of the membrane with the aid of a pump to move the membrane. revolution. The speed of the linear current on the membrane will usually be on the scale from 0.1 to LO m / second, preferably from 0.5 to 2.5 rn / second. The product retained in the separation step, which contains the catalyst system, can be distilled and recirculated to the hydroformylation, optionally with the addition of metal and / or the organometallic complex compound, as well as the aromatic phosphine of the formula generates LT, pair-to replace Losses. The addition of these complementary amounts can be carried out in the two steps of membrane filtration, or to the 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 complete recirculation of the catalyst system in hydroformylation 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 hydroformylation step and on the membrane separation step, when in the step of If the solvent is used to obtain a reaction as high as possible, but in the membrane stage, a considerable amount of solvent is used to reduce the viscosity. In the drilling stages, a solvent portion of 5 to 25% by weight, of 1H, is convenient. preferably from 7 to 13% by weight, based on the total of the reaction mixture diluted with solvent; 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 permoate from the organic solvent separation step, and returning it before filtration in membrane, fill is again added to the filter. the reaction mixture to be separated, from the hydroformylation. By means of this a corresponding dilution is obtained which is appropriate for obtaining higher flow conditions. The membranes used according to the invention consist of a polyarnide ar-onatLca, also called polyararnide. The polLaramide is obtained by polycondensation of aromatic dicarboxylic acids, or derivatives of dicarboxylic acid and aromatic diarrins, in a dipolar aprotic solvent. As carboxyl-C0O acid components, there may be mentioned, for example, terephthalic acid, 4,4'-diphenylcarboxylic acid, 4,4'-di-femleterdicarboxylic acid, 4,4'-diphenyl-1-sulfonylcarboxylic acid or 2,6-naphthalend? carboxylic acid. Co-components of diam are appropriate p-feni lendiarnma, 3,3-dirnetoxLbencidina, 3,3'-didorobencidi na, 3,3'-dirne ilbencidina, 4,4'-d? Am? Nod? Fen? Limetane, 2, 2-b? S- (4-a? No-phen? 1propane or 1,4- bi s (4-arn nofenoxi Jbencono.) Polyarades membranes containing, in addition to a and carboxylic acid, different diarrins as monomers, for example, polysaccharides formed from terephthalic acid, p-femlendiamine, L, 4-b? s (4-arni ofenoxybenzene and 3,3'-dimethylbenzidine). In the polymers the amines can be randomly distributed.The polyarnides, however, can also possess the structure of block copolymers.The average molecular weight of the polyarnide can vary within wide limits. it finds between 5,000 and 200,000 Pol ararnides with a molar mass of 10,000 to 50,000 is preferred 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 copolyaride, What is formed from three different diarrhemes and one dicarboxylic acid.

A solution of these copolymers licked in an aprotic polar solvent, of the amide type, for example N-rnetyl-2-pyrroiidone, is spread as a liquid layer on a piano substrate. This liquid layer is maintained in the falling liquid, especially water, which is insiscible with the solvent of the solution, however, the polymer is separated as a membrane. It is said that the dropping liquid affects so much time on the membrane until the solvent has been used completely by the falling liquid. In addition, it is possible that the membrane is subjected to a heating treatment, then the membrane is dried, possibly after a previous treatment with gilceri a. The membranes prepared according to the method described above 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 may 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 with 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 as high a stability as possible and, above all, a surface as wide as possible for each volumetric unit, in order to obtain a satisfactory constant production. 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 glycerin for storage purposes is then washed with water and then a for 10 minutes in hot water at 80-100 °. Then water is replaced, for example, by isopropanol, the membrane is left in isopropanol and the alcohol is renewed several times. Then the isopropanol is replaced in the same way by the hydroformylation reaction mixture, in which the complex metalorgam compounds, as well as their ligands, are released. In order to obtain an optimum separation condition, it is also advisable that the membrane be able to withstand a desired time under working conditions; that is, membrane filtration is effected under the use of the hydroformylation reaction mixture, each of the product retained and the permeate obtained, can be sent for purification and recirculated to the hydroformylation reaction mixture, before the 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. The process according to the invention is characterized by the combination of different special hydroformylation conditions, as well as by the use of aromatic phosphine ligands, with particular ammonium cations. If it is 77 it maintains the values previously given or the scales of values previously given for the concentration of rod LO, with respect to the olefin used, the proportion of rhodium and the pH value, and the phosphine ligand is used according to the General formula I, then both the selectivity and the activity value indicated in the hydroformylation step are thus obtained as well as the retention values indicated for the membrane filtration that is carried out below. In a single stage membrane filtration, 95 to 98% of the rhodium is retained, as well as at least 90% of the ligand. In a two-stage operation, 99 to 99.5% rhodium is recovered and at least 97%, in many cases up to more than 98%, of the Ligand. The important thing here is to put an end to the dissemination of the values mentioned for the parameters, as well as the selection of the correct phosphine ligand. If only one of the parameters or the ligand deviates from the limits given for the values, or from the general formula T, then, either in the hydroformylation or in the membrane filtration, or in both steps, negative values are observed. If ammonium salts are used, for example, from tertiary amines, which have a high number of carbon atoms in the radicals R * and R2, then, based on the higher ester requirements of the amine, rates of outstanding retention for Ligand and amine; Due to the high molecular weight of the amine, which leads to the use of necessary P: Rh ratios, the good results of hydroforming, of at least 60 for the existence of a large extreme amount of ligand in the reactor. In this way, the corresponding volume of the reactor is reduced for the usual reactants, especially the olefin. This is an effect that results in a lower volume of product in the stage of hydroformylation and, with this, high procedural costs, which do not constitute an economic attraction for the process. If, on the other hand, an amine is used to decrease the carbon lattice count, for example, tpisooctyia ina, then it obtains in the hydrophobic ratio outstanding selectivities which mean retention regimes during membrane filtration which are substantially lower. . If the scale of given pH values is not maintained, then a damage in the hydro-reaction reaction is obtained, in the form of reduced selectivity. In case the process according to the invention is carried out in the presence of a solvent, then it is essential that a reaction mixture with a solvent concentration of 30 to 70% by weight is introduced to the membrane filtration. If less solvent is used, then the flow is reduced, so that to obtain richer productions, correspondingly larger membrane surfaces must be used. If the same solvent concentration is used from 30 to 70% by weight, but in the hydroformylation stage, then the reaction is reduced as well as the productivity of the process. Therefore, it is advantageous if only one solvent concentration of 5 to 25% by weight is maintained in the reaction mixture.

EXAMPLES 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 THE MEMBRANE The polyamide is obtained by condensation of: 97-99 mol% of terephthalic acid dichloride, 25 mol% of p-phenylenediamine, 25 mol% of 1,4-b? S (4-arnmofenox?) Benzene, 50 % rnolar of 3, 3 'di rnet 11 bencí di na, in N-rnet j ipirr-oli dona as solvent. The terephthalic acid dichloride is added in an amount such that the polyarynnide has a Staudinger index of 200 to 300 rnl / g. The amount of solvent is mixed in such a manner that a solution containing about 7% by weight of condensed poly is formed.

After the condensation is established, Liza is removed. The loose amount of hydrochloric acid bound to the solvent by the addition of 100% molar CaO, is then dissolved in the reaction mixture, with stirring, 5% by weight (with respect to the polymer solution) of water-free calcium chloride. The solution is slightly heated, filtered and degassed. It can be used inrned lately for the preparation of the membrane. It is possible that the membrane is prepared free of support or on a polyester fleece as a support. In the following the preparation of a free support membrane is described. The slightly hot pol ararnide solution is spread with a scraper, on a glass plate, to a uniform film of about 150 microns, and immersed in a 2 ° C water bath. After about 20 minutes the membrane is recovered from the glass plate and left for 5 minutes in hot water at 100 ° C. After this the membrane is placed in isopropanol, in order to exchange the water that floods the pores with alcohol, then the membrane is washed with toluene, after this treatment is ready to carry out the repair. In all operations, care must be taken that the membrane does not dry out.

EXAMPLES 1 - 7 AND COMPARATIVE EXAMPLE 1 The hydroformylation of di ci cl opent adiene (DCP) is obtained by the use of rhodium-containing catalyst systand different ammonium salts of the phonyl phosphine phthalate (TPPTS): a) Preparation of the lardon salt of TPPTS 253 g of a Na-ÍPPTS solution are introduced, under nitrogen, into a shake flask, and heated to 65 ° C. Then a solution of 250.3 g of disteplarnin in 595 g of toluene is introduced. Within 60 minutes, 90 ml of 20% sulfuric acid is added with stirring until a pH value of 2.6 is obtained, and the reaction is continued for 2.5 hours. For better phase separation, 170 g of isopropanol is added. After 15 minutes, 1037.5 g of an organic phase containing the ammonium diesterap 1 salt of ÍPPTS is separated off with 0.33 rnoles of TPPTS per mol of amine. In a manner analogous to the previous step described above, other ammonium salts are obtained from IPPTS (examples 2 to 7 and comparative example 1). b) Discontinuous dicrillopentadi orrnilacion no.

An autoclave of agathate, 2.15 liters, is washed with nitrogen. In a glass flask with installation for the addition of nitrogen, 212.0 g of the ligand solution of a) is added, as well as 0.29 rnmoles of rhodium in the form of a salt of free 2-ethexanoate di (60 pprn in weight of Rh, proportion of P / Rh: 100) and 500 g of toluene, ba or nitrogen, to the autoclave. Then, with stirring and with the 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. After the end of one hour, 500 g of dicyclopentadiene is pumped into the autoclave. When cooling with an air current, the temperature is maintained at 130 ° C. After completing 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 three neck flask, of 2 liters, with immersion tube and extracted. The reaction of dicyclopentadiene is calculated from the weight increase. , which is given in Table 1. The droforrnilation of dicyclopentadiene is carried out in an analogous manner, by using the ammonium salts of TPPTS according to examples 2 to 7 and comparative examples 1. The results obtained are gathered in table L. 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 polyaramide from Hoechst AG (UF ~ Pfl (PET 100)) is used as the membrane. The membrane is then tended for 10 minutes at 80 ° C in water. The membrane is then used by means of a rotary pump, with a current of more than 200 1 / hour, and at a pressure of 1 MPa. After a recovery temperature of 40 ° C, the amount given in table L of the hydroforming product is passed through the membrane, as permeation product. In the permeation product, the content of catalyst parts is calculated, from which the recirculation value is obtained, with respect to the reaction mixture used in hydroformylation, which is given in Table L.

EXAMPLES B AND 9, COMPARATIVE EXAMPLE 2 Continuous hydroformylation of dicyclopentadiene (examples 8 and 9: use of the disteteaplateinium salt of TPPTS as a ligand in the rhodium catalyst system, comparative example 2: use of salt of et i ldiestoap lamon or of TPPTS as a ligand in the rhodium catalyst system). The hydroforming process is continuously carried out in a 17 liter pressure tube, under the reaction conditions given in table 2. With the use of the salt of methyl iodiesteap larnome of TPPTS (comparative example 2), the influence of a P / Rh ratio of less than 15. This indicates that a rhodium loss of 15% is experienced during the course of the hydrophobicization. When changing to a higher P / Rh ratio, there is no longer any loss of Rh in the droforrm lation (example 8). The product, which is obtained with example 9, is cooled after hydroforming at 40 ° C in an intermediate exchange system, covered with nitrogen, and then subjected to membrane filtration in order to obtain high retention. of ligand and Rh complex compound, the membrane filtration is carried out in two stages. The membrane installation consists of normal plate modules from the Dow firm (type DOS 30-4.5). The membrane surface of the first stage consists of 1.4 rn2 and that of the second stage, 0.2 rn2. The filtration takes place at an installation temperature of 40 ° C. Inside the module, the reaction mixture to be filtered is conducted in each case Length of the membrane surface. The current or flow is thus 0.5 to 2.5 in / second. The reaction mixture of hydroformy Lation, before the first filtration cap, is dissolved with toluene in such a way that the toluene portion reaches 50-55% by weight, then the reaction mixture is concentrated at 50%, with respect to the total amount used. The perrneado obtained in the first stage of filtration is passed after supplementing or supplementing the small amounts of rhodium and DSfl / TPPTS, which are indicated as losses of Rh or P (ITI) in table 2, to the second stage of filtration. The product retained in both stages is purified and sent directly back to the reaction of the Droforrní Lacion. The reaction product of the Lation drill, the cyclodecanodial resin, as well as the thick oil formed, permeate the membrane in addition to the toluene, under the prevailing working pressure of about 1 MPa in the first and second stages and they are added as per the additional treatment. The toluene is then removed by distillation from the permeate and recirculated to the hydrophobing reaction mixture, before membrane filtration, where the reaction mixture of hydroxyation is diluted to 50% by weight. . For both stages of filtration of Example 9, the results of the flow rate are indicated in Table 3. Due to the continuous research time of more than 12 weeks, there was no decrease in activity. Most of the loss of P (TII) is accompanied by formation of phosphate oxide.

THE INFLUENCE OF A PRESSURE CONDITIONING OF THE POLYARAMIDE MEMBRANE ON THE PURIFICATION INSTALLATION A non-hardened UF-Pfi 5 (PET 100) membrane is constructed in a work cell and then used with the hydrophobic reaction mixture of the einpLo 9. The permeate and the retention product obtained under the filtration conditions in membrane, according to example 9 see Table 2), they are again purified after membrane filtration and the hydroforming reaction mixture is returned before membrane filtration. The retention value for phosphorus (HT) is analyzed in dependence on time (see Table 3): PICTURE. 3 Duration of pressure conditions (hours 6 16 32 34 37 Retention of PflII) (% of the amount used) 65 71 > 90 > 90 > 90 EXAMPLES 10-13 Continuous flow of dicyclopentadiene with variation in rhodium concentration, with respect to DCP The hydroformylation is carried out continuously under the reaction conditions given in table 4. fl then membrane filtration is carried out analogously to example 9. The results obtained are summarized in table 4. It should be noted that activity and selectivity are increased with the increase in rhodium concentration and, likewise, the result of membrane filtration is improved.

EXAMPLES J -17 Membrane filtration of a continuous hydroproduction reaction mixture of DCP, with the use of TPPTS distepaplate salt as a ligand, in the Rh catalyst system. In Examples 14-17, the dependence between the toluene concentration in the reaction mixture used for membrane filtration and the flow rate, as well as the retention rates is investigated. For the membrane filtration, a reaction mixture obtained by continuous hydroformylation is used under the conditions given in example 8, as well as with a phosphorus: rhodium ratio of 76. Membrane filtration is carried out in a single step , at an installation temperature of 40 ° C, ba or a pressure of 1 MPa and with an excess current of 200 1 / h on the membrane. The flow rates obtained as well as the retention values are summarized in Table 5. It should be clarified that an increasing portion of toluene in which the reaction mixture used for membrane filtration has a favorable effect on the flow rate as well as on the the retention rate.

CUfiPRQ 1 Discontinuous hydroformy of dicyclopentadiene as well as filtration in a single phase, in a single stage, of the hydrofluoride reaction mixture, with the use of different ammonium salts of TPPTS as co-liquids.

Ex. Hydrophoration amine Membrane filtration No. salt of master- Reac- Selecti- Canti- Flow Retention (% used) child of the di vi. Flow rate Rh Ligan- Amina TPPTS (%). - aldehyde periné ^, or (1 / do (P) () / rnonoenal do (% rn2 / h) .. of use) CL Tr-? sooct il- 99.9 99/1 15 64 89.3 69. 8 16.5 ami a. 1 Met i di se 99.6 92/8 11 71 91.9 95.0 76.4 boarní na. 2 Diesteapl- 99.4 97/3 66 61 97.5 96. L 78.3 tni na 3 Metiidies- 99.4 95/5 10 77 97.1 94.3 tearilar í na 4 fpcetiiami 98.7 96/4 22 44 95.0 90.0 73.3 na.

Tp-n-octa- 98, 9L / 9 53 9 93.0 87.0 88.7 deci l mine 6 Tpeicosi 1 - 99.0 95/5 22 59 98.9 95. 9 88.3 even na. 7 Tpdocosi 1- 99.7 90/10 48..8 29 96.5 94. 7 81.9 a i n.

CURPRQ 2 Continuous hydrophobic DCP FC2 Ex. 8 Ex. 9 Arn i na MDSfl * D A D? Fl Concentration of Rh with respect to DCP (pprn by weight) 157 100 100 Pressure (MPa) 27 27 27 Proportion P (III) / Rh (mol / mol) 15 85 100 Tempera ura ° C 135 135 130 Load: volume of DCP / (volume 0.07 0.07 0.03 ** of reactor) (.hour (1 h) Toluene concentration respec42 4 < 15 to the DCP in the hydro fo 1 ation (%) Reaction (%) 100 100 100 Proportion dial / tnonoenal 89/11 89/11 91/9 Lost of Rh (% used) 15 0.8 Loss of P (IT1) (% of used) ** The paging charge conforms to the membrane installation provided and reduces its power. TABLE 4 Ex.9 Ex.10 Ex.ll E.12 Ami na DSO D A DSA DSA Rh concentration relative to DCP (pprn by weight) 100 60 45 20 Pressure (MPa) 27 27 27 27 Proportion P (III) / Rh (rnol / 100 100 100 100 mol) Temperature ° C 130 130 130 130 Load: Volume of DCP / (vo- 0.03 ** 0.0.1 ** 0.0 ** 0.03 * * reactor lumen) «-hour (Ih) Toluene concentration < 15 < 15 < 15 < 15 r-es? Ecto to DCP in the hydrofiniation (%) Reaction (%) 100 100 100 100 Provided on di / rnonoenai 91/9 60/40 40/60 27/73 Filter pressure in 1 1 1 1 membrane (MPa) Rh loss (% used) 0.8 1.4 1.7 Loss of P (HT) (% of 3.5 4.2 5.0 used) rga of passage: First stage (l / rn2 / h) 6 6.5 7.1 7.6 Second stage (l / m2 / h) 30 33 37 41 ** The step load is adjusted to the membrane installation provided and reduces its power.

CUñPRQ 5

Claims (25)

1. NQVEPflP PE Lfl INVENTION REINFORCEMPTIONS 1. - Process for preparing aldehydes by hydroformylation of olefinic compounds unsaturated with hydrogen and carbon monoxide in a homogeneous phase, in the presence of a catalyst system consisting of a complex rhodium compound, as well as of aromatic phosphides in an excess rnolar, and separation of the catalyst system from the hydroformylation reaction mixture, by pressure filtration, in a semipermeable membrane, formed from an aromatic polyamide; The said process is characterized in that Hydrofornylation is carried out at a pH value of 2.5 to 4.3, with the use of a rnolar ratio of fos i na: rhodium of at least 60, and at a rhodium concentration of at least LO ppm by weight, with respect to the olefinically saturated compound employed; and aromatic phosphine is used as alkyl-and / or aplarnome salts of sulfonated or carboxylated tpaplfosf, of the gene formula r-al I: wherein X means a sulphonate (S0.3 ~) or carboxylate (C00-) radical; a, b and c are the same or different and are ce r-o or 1; where at least one of the pairs a, b or c must be equal to l; n is 1, 2 or 3; Ra and R 12 are different or different and 5 represent alkyl radicals of 8 to 30 carbon atoms or aplo or cycloalkyl radicals of 6 to 10 carbon atoms; and R can also be hydrogen; and The sum of the carbon atoms in the radicals R1- and R ^ must be at least 30.? . - Process according to claim L, characterized further because X ori the general formula I represents a sulphonate radical. 3. Procedure according to claim 1 0 2, further characterized because R3- and RH in the general formula 1 are the same or different and represent the alkyl radical of 12 12 to 22 carbon atoms or a phenol or cycloalkyl radical. 4. Method according to one or more of claims 1 to 3, further characterized in that a, b and c are 1 .. 5.- Procedure according to one or more of the claims 1 to 4, further characterized because the cations ammonium GHNR ^ R ^ R12] "in the general formula I have in total at least 30 and a maximum of 90 carbon atoms, preferably from 32 to 70 and, especially, from 36 to 54 carbon atoms in the radicals R and R3. ') P1 6.- Process according to claim 5, further characterized in that ammonium cation p-INR: lR: r 2l + is used in general fopnuLa 1, distearylarnonio ion, fn cetllamónio ion or 7.- Process according to one or more of Claims L to 6, further characterized in that the molar ratio of rhodium to aromatic phosphine of the general formula T is 1. (60-120) ), preferably 1: (70-110), especially L: (80-100) 8.- Procedure according to one or more of the claims L to 7, further characterized in that the concentration of Rh in the droforpu lation, with respect to the olefinically unsaturated compound, is at least 20 pp by weight, preferably 60 to 150 ppm by weight. 9. Process according to one or more of claims 1 to 8, further characterized in that the catalyst system is prepared in an exchange step of the process, or is formed in situ during the process. 10. Method according to claim 9, further characterized in that for the preparation of the catalyst system in an exchange step, each of the rhodium component and the di-phosphine of the formula I are dissolved or suspended in an organic solvent; they are combined and reacted at a pressure of carbon monoxide / hydrogen of 15 to 25 MPa, at a temperature of 80 to 150 ° C, for at least one hour. 11. Method according to one or more of claims 1 to 10, further characterized by the fact that substituted or unsubstituted alkenes of 2 to 30 carbon atoms are used as olefinic compounds + e unsaturated; substituted or unsubstituted dienes of 10 carbon atoms; substituted or unsubstituted cycloal uenes or substituted or unsubstituted dicycloalkyl, of 5 to 12 carbon atoms in the ring system; esters of an unsaturated carboxylic acid of 3 to 20 carbon atoms and of an aliphatic alcohol of 1 to 18 carbon atoms; esters of a saturated carboxylic acid of 2 to 20 carbon atoms and of an unsaturated alcohol of 2 to 18 carbon atoms; alcohols or saturated ethers, each with 3 to 20 carbon atoms, or araliphatic olefins of 8 to 20 carbon atoms. 12. Process according to claim 11, further characterized in that dicyclopentadiene is used as an olefinically unsaturated compound. 13. Method according to one or more of claims 1 to 12, further characterized in that the hydroforming is carried out at a temperature of 100 to 140 ° C, preferably of 120 to 130 ° C, and under a pressure of 0.5. at 27 MPa, preferably 20 to 25 MPa. 14. Proeedirnient or according to one or more of claims 1 to 13, further characterized in that the hydroforming is carried out at a pH value of 3.0 to 4.0, especially 3.5. 15. Pr-ocedim ent or according to one or more of claims 1 to 14, further characterized by working in the presence of an organic solvent. 16. Method according to claim 15, further characterized in that the concentration of the solvent in the reaction of hydroforming is from 5 to 25% by weight, preferably from 7 to 13% by weight, with respect to the mixture. of total reaction of hydroformylation; and in the metric filtration, it is from 30 to 70% by weight, preferably from 40 to 60% by weight, with respect to the total of the reaction mixture used in the membrane filtration. 17. Process according to one or more of claims 1 to 16, further characterized in that in the hydrofornylation reaction mixture used in the membrane filtration, the concentration of the aromatic phosphine present in excess, of the General formula I is in 2.5 and 25% by weight, preferably 5 to 15% by weight, with respect to the total of the reaction mixture used in the membrane reaction. 18. Process according to one or more of claims 1 to 17, further characterized in that the concentration of the complex rhodium compound in the hydroformylation reaction mixture, used in the filtration in the morning, is between 2 and 400 ppm. by weight, preferably between 10 and 300 pprn by weight, especially between 50 and 150 ppm by weight, with respect to the totality of the reaction mixture used in membrane filtration. 19. Method according to one or more of claims L to 18, further characterized in that the membrane filtration is carried out under a pressure of 0.1 to 15, preferably of 0.5 to 5 and, especially, of 1 to 2 MPa; and is carried out in one or several steps, preferably in two stages. 20. Method according to one or more of claims 1 to 19, further characterized in that the membrane filtration is carried out with a step of separation willingly. 21. Method according to one or more of claims 1 to 20, further characterized in that the total amount of product separated in the membrane filtration is between 8 and 90%, preferably between 10 and 70, especially between 15 and 50 and, very especially between 20 and 40%, with r-specil to the reaction mixture used in membrane filtration, and the concentration of the aromatic phosphine of the separate general formula T, present in the retained product, is by less than three times the amount in the hydroformylation reaction mixture used for membrane filtration. 22. Method according to one or more of claims 21, further characterized in that in membrane filtration in two stages the proportion of the amount of product retained from the first filtration step with respect to the amount of product retained in the second stage is about 1: 1. 23. - Process according to one or more of Claims L to 22, further characterized in that the retention product containing catalyst system, from the stage of separation of the membrane filtration, is recirculated back to the hydroforpution, possibly with complementary addition of rhodium and / or complex rhodium compounds, as well as aromatic foefine of general formula T. 24.- Method according to claim 23, further characterized in that during the implementation of membrane filtration , in two stages, the complementary addition of rhodium and / or complex compounds of rodi or, as well as the aromatic phosphine of formula T, to the permeate product of the first filtration stage is carried out before its transfer to the second stage of filtration. 25. Method according to one or more of claims 1 to 24, further characterized in that the solvent is removed by distillation, from the collected permeate of the separation steps of the membrane filtration, before the membrane filtration is recovered. and added to the hydroformylation reaction mixture, before membrane filtration. RF SUMMARY OF THE INVENTION The present invention relates to a process for the preparation of aldehydes by the hydroformylation of olefinically saturated compounds with hydrogen and carbon monoxide, in homogeneous phase, in the presence of a catalyst system containing complex rhodium compounds as well as aromatic phosphines, in molar excess; and The separation of the catalyst system from the hydroformylation reaction mixture by means of pressure filtration in a semipermeable membrane, of an aromatic polyarnide. The process is characterized in that the hydroforlation is carried out at a pH value of 2.5 to 4.3, with the use of a rnolar ratio of phosphine: rhodium of at least 60 and at a rhodium concentration of at least 10 ppm by weight , with r-specific to the saturated olefin compound employed; and especially aromatic phosphines of alkylaryl and / or of sulfonated or carboxylated naphthylphosphines are used; the process according to the invention results in outstanding activity and selectivity values in the actual drilling step, as well as high retention values in the membrane filtration step. CR / cgt * P9P / 460