DE2062352A1 - Process for the hydroforming of olefins - Google Patents

Description

Process for the hydroformylation of olefins The invention relates to a hydroformylation process using a solid heterogeneous catalyst.

The use of phosphorus-containing complexes of transition metals as homogeneous catalysts for the most diverse reactions, e.g. for carboxylation, Hydrogenation and oligomerization of olefins has already been described. the Catalysts often contain valuable metals, e.g. palladium and iridium, see above that de recovery and recycling of the catalyst is important. However, it is often a problem to achieve extensive recovery of the catalyst.

Subject of the German patent ... (patent application of the same Days according to the applicant's British patent application 61920/69) is the Preparation of a catalyst support which contains groups of the formula # Z-O-Si-O (I) #, wherein 2, is a residue obtained by removing an -OH group from an -OH group containing solid inorganic material has been formed, and Q is a group containing trivalent phosphorus. This patent describes also the manufacture of solid materials suitable for heterogeneous catalysis suitable and contain transition metal bonded to the phosphorus, and a number various catalytic applications of these materials, e.g. their use as heterogeneous catalysts for the hydroformylation of olefins.

The invention relates to the hydroformylation of olefins Alcohols, aldehydes or both by a heterogeneous process, which is characterized is that olefins with carbon monoxide and hydrogen at a temperature of 20 hydroformylated up to 250 ° C in the presence of a solid catalyst of the formula Z-O-Si-O, wherein Z is a residue obtained by removing an -OH group from an -OH group containing inorganic material has been formed, and Q is a group which contains phosphorus bound to rhodium, cobalt or iridium.

The catalysts used for the purposes of the invention can be prepared 1) by reacting a transition metal compound with a Compound containing silicon and phosphorus, e.g. (EtO) 3Si (CH2) 2PR2, into one Compound containing a transition metal bonded to phosphorus, and conversion this compound with an inorganic solid containing -OH groups, or 2) by reacting the inorganic solid with the silicon and phosphorus containing Connection and subsequent reaction of this product with the transition metal compound.

Both methods are in the German patent mentioned above described by the registrant.

As the inorganic solid material containing -OH groups, is preferred Silica used.

The catalyst preferably has the formula wherein R1 and R2 represent alkyl radicals, aryl radicals. Alkoxy radicals odor. Aryloxy radicals with up to 10 carbon atoms and R3 and R4 represent aryl or alkyl radicals with up to 10 carbon atoms.

-R¹- is an (optionally substituted) alkylene or arkylene radical with up to 24 carbon atoms, M stands for iridium, rhodium or cobalt, L is a ligand cnd m is a Zabl with such a value that the group of the formula metal is saturated are.

The radical R¹ is preferably a group of the formula (-CH2-) n, in which n is an integer from 1 to 6, or a group of the formula where p is an integer from 0 to 6.

The preferred transition metal used is rhodium.

For the purposes of the invention are olefins with 2 to 20 carbon atoms, in particular ethylene, propylene, hexene, heptene, e.g. ethylpentene, octene and nonene suitable.

The hydroformylation can be carried out at pressures from 0 to 25,000 kN / m²ga will. It is preferred to work at 1400 to 15,000 kN / m²ga.

The reaction is preferably carried out at temperatures from 200 ° C.

The olefin is preferably dispensed at a space velocity from 0.1 to 20 V / V / hour, calculated as roughness parts of liquid per space part of catalyst, fed.

Hydrogen and carbon monoxide are preferably released at a space velocity from 50 to 10,000 V / V / hour, calculated as parts of gas per part of space Catalyst, used.

It has been found that some of the catalysts are sensitive to this Oxygen is because oxygen is an elution of the metal and therefore a loss cause of the activity. It has been shown that the oxygen sensitive depending on the type of catalyst used and also on the temperature and space flow velocity depends. For example, it has been found that in the case in which the catalyst contains rhodium, which is only bonded to one phosphorus atom the oxygen can cause the rhodium to elute. It is therefore advisable don to reduce the oxygen content of the feedstock to a low level. Appropriate the oxygen content of the combined use of carbon oxide and hydrogen kept below 300 ppm. If at temperatures above 70 ° C and room flow velocities over 1 part of liquid per part of catalyst per hour or 500 parts Gas is worked per part of space catalyst per hour, the oxygen content of the use is preferably kept below 30 ppm.

The molar ratio of hydrogen to carbon dioxide in the material can be 10: 1 up to 1:10 am. A ratio of 2: 1 is preferred, which reduces alcohol formation favors, and a ratio of 1: 1, which favors the formation of aldehydes The olefin can be introduced in a solvent.

Any inert organic compounds are suitable as solvents, e.g. saturated or aromatic hydrocarbons or alcohols. Normal paraft'ine, e.g. n-xexene, n-heptane and n-octane are also suitable.

Example 1 I. Production of silicon dioxide, trivalent phosphorus Contains all attempts for the production of catalysts bound with silicon dioxide were degassed under oxygen-free nitrogen using dry, degassed solvent carried out. As silicon was used in all cases the product "U40" from J.Crosfield is used, which is washed with dilute acid, extracted in a Soxhlet extraction apparatus with distilled water and then Had been dried at 180 ° C for 4 hours.

a) Preparation of (C2H5O) 3SiCH2CH2P (C6H5) 2 (P) triethoxyvinylsilane (69.6 g, 0.36 mol) was added dropwise to diphenylphosphine (80.4 g, 0.42 mol) added stirring to diphenylphosphine (80.4 g, 0.42 mol) The mixture was added then irradiated with a high intensity ultraviolet lamp for 70 hours. That The reaction product was distilled and the 0.1 mm Hg passing over at 155 to 165 ° C Fraction collected (127 g, yield 85%).

Silicon dioxide (quality "U40", manufacturer J. Crosfield) was also included diluted acid and then washed with distilled water in a Soxhlet apparatus and dried at 180 ° C for 4 hours.

b) Reaction with silica 60 g of the silica were with 60 g of the compound (P) in 500 ml of xylene which were heated under reflux for 8 hours treated under nitrogen. The ethanol was removed from the reaction mixture by azeotropic distillation severed. The silicon dioxide was then 6 hours under nitrogen in washed with toluene in a Soxlet apparatus and dried under reduced pressure Phosphorus content 1.0% by weight II. Preparation of the rhodium-containing catalyst 10 g of the product which had been prepared in the manner described under 1. (b) and 1% by weight of phosphorus were mixed with 2.1 g of Rh (CO) 2 (acac) (acac being the Acetylacetone anion is treated in 50 ml of toluene at 50 ° C. for 15 minutes. The product was washed with toluene and pentane and dried under reduced pressure. A yellow Product was obtained.

Rhodium content 2.2% by weight III. Hydroformylation of hexene-1 into one 100: i1 hexene-1, 200 ml of n-heptane and 0.2 g of the catalyst were used in 1 l shaking autoclaves given, the production of which has been described in Part II. The mixture was Maintained for 3 hours at 000C under a CC / H2 pressure (1: 1) of 4100 kN / m² (ga). the Bomb was pressed hourly again to 4100 kN / m2 (ga) on J ') ar autoclave was used Over the weekend of cooling leave 100% by weight of molar activity of V7 aldehydes 30% by weight ratio of normal compounds to branched compounds: 1.95 (70% of the olefin was isomerized to olefin with an internal double bond.) The result shows that the rhodium-containing catalysts after the aforementioned second method (in which an inorganic solid containing -OH groups, with a compound containing silicon and phosphorus to form a carrier is reacted, which is then reacted with a transition metal compound) produced are active hydroformylation catalysts.

Example 2 I. Catalyst preparation a) The compound (C2H5O) 3SiCH2CH2P (C6H5) 2 (£ A) was made from triethoxyvinylsilane and diphenylphosphine to the one described in Example 1 Way.

b) A solution of 17.4 g of compound (A) in 10 ml of benzene was added to 3.8 g of cyclooctadiene rhodium (I) chloride (#RhCl (C8H12) # 2) in 100 ml of benzene. The light orange solution turned light red in color. The resolution was under for 16 hours Nitrogen stirred at room temperature. The benzene was then removed under reduced pressure evaporated, whereby a red viscous material was obtained. The complex was dissolved in pentane; and then precipitated from solution by cooling. The above solution was decanted and the remaining viscous material 14 hours at 60 ° C and 10-4 mm @ to obtain Compound (B).

A solution of 6.03 g of compound (B) in 60 ml of benzene was taken under Nitrogen was added to a suspension of 50 g of silicon dioxide in 150 ml of benzene. The reaction mixture was refluxed for 2 hours and the ethanol formed separated by azeotropic distillation with a Dean & Stark apparatus. To after decanting the above liquid, the resulting red residue became washed three times with 50 ml of benzene each time, dried and submerged with benzene for 10 hours Nitrogen extracted in a Soxhlet extraction apparatus. The catalyst was then dried under reduced pressure.

Rhodium treated 0.54% by weight chlorine content 0.3% by weight phosphorus content 0.6 % By weight II. Hydroformylation 20 ml of the catalyst based on that described under (I.) Way had been prepared were placed in an experimental apparatus and subjected to hydrogenation of olefins used in steam cracked gasoline, the 100 ppm added mercaptan sulfur (as n-butyl mercaptan) and 100 ppm added thiophenesulfur (as thiohen).

After a test duration of 71 hours, the supply of liquid the feed and hydrogen aborted and the reactor cooling down Leave room temperature under a hydrogen pressure of kN / m² (ga). About the catalyst degassed benzene was passed to add any remaining steam-cracked gasoline eutfornen. The reactor was flushed with CO / H2 (1: 1). The temperature was then to 80 ° C. and the pressure to 4100 kN / m² (ga), whereupon a 33% by weight of hexene-1 containing solution in n-heptane (degassed before use) with a room flow velocity of 3 parts of liquid per part of catalyst per hour over the catalyst @@ - directs wurdo. The following results were obtained: running time, hours 2-4 11-13 Temperature, ° C 80 140 Pressure, kN / m² (ga) 4100 4100 Room flow velocity, V gas / V / hour 1200 1600 Conversion to aldehydes,% by weight 5 47 ratio of normal compounds to branched compounds 2.2 2.6 Example 3 In this and in the following No precautions have been taken to attempt the experiments described in the examples to prevent the entry of air during the filling of the catalytic converter or to free the CO / H2 of oxygen.

a) A cobalt complex on silicon dioxide as a carrier (cobalt content 1.6 wt%) was made from # Co2 (CO) 6 ((EtO) 3SiCH2 CH2P (C6H5) 2) 2 # and silica.

Preparation of Co2 (CO) 6 ((EtO) 3SiCH2CH2PO) 2) 0.8 g freshly sublimated Co2 (CO) 8 was added to a flask containing 20 ml of degassed pentane, whereupon 1.9 g (EtO) 3SiCH2CH2PO2 were added under nitrogen. The reaction mixture was stirred for 2 to 3 hours at 0 ° C and then 66 hours in an ice box, whereby a viscous one was removed under reduced pressure, leaving a viscous brown one Material was obtained.

2.6 g of the complex # Co2 (CO) 6 ((EtO) 3SiCH2CH2P (C6H5) 2) 2 # were in 175 ml of dry, degassed benzene under nitrogen in a 250 ml three-necked flask solved. After addition of 10 g of silica was the reaction mixture Heated under reflux with stirring for 4 hours. The ethanol was made by azo-tropic distillation lotion separated from the reaction mixture using a Dean & Stark apparatus. Get the oac Silica containing bound cobalt was extracted in a Soxhlet extraction apparatus Extracted with benzene under nitrogen for 24 hours and then under reduced pressure dried.

Cobalt content 1.6% by weight b) Into a 500 ml agitator autoclave stainless steel was 0.368 g of the catalyst along with 84 g of hexene-1 and 200 ml of n-heptane are given. The reaction mixture was then 4 hours at one temperature of 180 ° C and a CO / H2 pressure (1: 1) of 6900 kN / m² (ga) g. The reaction vessel was cooled to room temperature.

Conversion: 55.4% by weight selectivity to aldehydes: 18% by weight ratio from normal aldehyde to branched aldehyde: 1.2 selectivity to olefins with internal Double bond: 82% by weight The product contained show that the elution of cobalt from the silicon dioxide is insignificant during the reaction, and that cobalt-containing, which are prepared by the first process mentioned above, for hydroformylation active sinf.

Example 4 Catalyst preparation a) The compound (C2H5O) 3SiCH2CH2P (C6H5) 2 (A) was made from triethoxyvinylsilane and diphenylphosphine to that in Example 1 Way made.

b) A solution of 3.67 g of compound (B) is prepared benzene was added to a suspension of 20 g in 50 ml of benzene. The reaction mixture was heated under reflux for 2 hours under nitrogen and the ethanol formed in the process by azeotropic distillation with a Dean & Stark apparatus from the reaction mixture severed. The benzene was decanted from the silica and the resulting dark red Washed silica three times with 30 ml of benzene each time. The silica was then transferred under nitrogen in a Soxhlet extractor and 10 hours with Benzene extracted (after this time the eluent was colorless). The silicon dioxide was dried under reduced pressure.

Rhodium content 0.7% by weight Phosphorus content 0.7% by weight c) In a 500 1.5 ml stainless steel stirred autoclaves received 1.411 g of the catalyst given together with 84 g of hexene-1 and 200 ml of n-heptane. The reaction mixture was then held for 4 hours at 140 ° C. and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga). The reaction vessel was cooled to room temperature.

Conversion: 55.4% by weight selectivity to aldehydes: 18% by weight ratio from normal aldehyde to branched aldehyde: 1.2 selectivity to olefins with internal Double bond: 82 wt .-% These results show that rhodium-containing catalysts, according to the aforementioned orsten process (in which the metal compound first with a compound containing silicon and phosphorus and then with an -OH group containing inorganic solid is reacted) are produced, active for are the hydroformylation.

Example 5 a) A rhodium complex on silicon dioxide as a carrier (rhodium content 0.9% by weight) became from the complex #RhCl (CO) ((EtO) 3SiCH2CH2P (C6H5) 2) 2 # and silica. The complex was made as follows: Preparation of the complex RhCl (CO) ((EtO) 3SiCH2CH2P (C6H5) 2) 2 A solution of 2.487 g (6.4 mmol) Rhodium dicarbonyl chloride in 100 ml of benzene was made up in a flask whereupon a solution of 9.599 g (25.5 nmol) (2-diphenyl phosphinethyl) triethoxysilane ((EtO) 3SiCH2CH2PO2 in 50 ml of benzene was added under nitrogen at room temperature Carbon oxide evolved and the red solution turned yellow. The reaction mixture was stirred for 15 minutes while nitrogen was passed through and k @ a @ over After left standing. The benzene was evaporated to a small volume and that Product precipitated with pentane.

The yellow crystals obtained were filtered off, washed with pentane and sucked dry.

Analysis Calculated Found Rh 11.19 11.11 C 53.56 53.68 53.89 H 6.36 6.57 6.39 P 6.74 7.12 7.13 Cl 3.86 3.55 3.71 # (CO) = 1966 cm-1 A solution of 5.5 g of the complex in 175 ml of toluene was placed under nitrogen in a 250 ml three-necked flask given.

After adding 20 g of silica, the reaction mixture became 4 hours heated to reflux with stirring. The ethanol was made by axcotropic distillation separated from the reaction mixture using a Dean & Stark apparatus.

An orange-red product was formed. The rhodium-containing Silica under nitrogen in a Soxhlet apparatus with toluene for 24 hours extracted and dried under reduced pressure.

Rhodium content 0.9% by weight phosphorus content 0.6% by weight b) In a 500 ml stainless steel autoclave was placed 1.119 g of the catalyst given together with (; 4 g of hexene 1 and 200 ml of n-heptane. The reaction mixture was then 4 hours at a temperature of 14000 and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga). The reaction vessel was cooled to room temperature.

Conversion 100% by weight selectivity to aldehydes 56% by weight ratio from normal aldehyde to branched aldehyde 0.7 selectivity to olefins with internal Double bond 44% by weight c) That produced in the experiment described above under (b) The catalyst was washed with acetone and dried under reduced pressure. The catalyst w was kept in contact with air for 22 days. The reaction mixture was then held for 4 hours at 140 ° C and a (1: 1) of 4130 kN / m² (ga). That The reaction mixture was cooled to room temperature.

Conversion 100% by weight selectivity to aldehydes 76% by weight ratio from normal aldehyde to branched aldehyde 0.6 selectivity to olefins with internal Double bond 24 wt .-% These results show that the rhodium-containing catalysts are resistant to air and moisture, as they are essentially their activity keep. The selectivity to aldehydes increases, while the ratio of normal Aldehyde drops easily to branched aldehyde.

Example 6 a) A rhodium complex on silicon dioxide as a carrier (rhodium content 1.2% by weight) was prepared from the complex #RhH (CO) ((EtO) 3SiCH2CH2P (C6H5) 2) 3 #.

Preparation of the complex (RhH (CO) ((EtO) 3SiCH2CH2PO2) 3) 5 g (RhCl (CO) ((EtO) 3SiCH2CH2PO2) 2) and 8.3 g of (EtO) 3SiCH2CH PO2 were added in 150 ml of ethanol which was heated to reflux.

solved. 2 g of sodium borohydride in 40 ml of ethanol were slowly added to the solution while the solution was refluxed under nitrogen. A precipitation was formed slowly. After 2 to 3 hours the solid was filtered off and washed with ethanol. The solid then became from benzene / pentane and benzene / ethanol umknstallisiert, whereby an orange-yellow solid was obtained.

The infrared spectrum showed absorptions at 1970 cm-1 and 1900 cm 1 attributable to the Co and Rh-H stretching frequencies.

In a 250 ml three-necked flask, 4.5 g of complex in 175 ml of toluene solved under N2. After the addition of 20 g of silicon dioxide, the reaction mixture was 4 Heated under reflux with stirring for hours. The ethanol was made by azeotropic distillation separated from the reaction content with a Dean & Stark apparatus. A dark red one Product was formed. The obtained rhodium-containing silica was in a Soxhlet extraction apparatus extracted with toluene under nitrogen for 24 hours and then dried under reduced pressure.

Rhodium content 1.2% by weight, phosphorus content 1.15 b) in a 500 ml autoclave stainless steel gave 0.888 g of the catalyst along with 84 g of hexene-1 and added 200 ml of n-heptane. The reaction mixture was then 4 hours at a Temperature of 140 ° C and kept under a CO / H2 pressure (1: 1) of 4130 kN / m2 (ga). The reaction vessel was then cooled to room temperature, sales 100% by weight selectivity to aldehydes, 50% by weight ratio of norinal aldehydes to branched aldehyde 1.3 selectivity to olefins with internal double bond 50 % By weight c) The catalyst prepared according to Example 6 (b) was washed with acetoin and dried under reduced pressure. He was then in contact with for 10 days kept under air.

In a 500 ml stainless steel autoclave, 0.822 g this catalyst is added together with 77.7 g of 1-hexene and 200 ml of n-heptane. That The reaction vessel was then heated for 4 hours at 140 ° C. and under a CO / H2 pressure f1: 1 of 4130 kN / m² (ga). The reaction vessel was then cooled to room temperature.

Conversion 100% by weight selectivity to aldehydes 59% by weight ratio from normal aldehyde to branched aldehyde 0.7 selectivity to olefins with internal Double bond 41% by weight The product contained less than 1 ppm rhodium.

These results show that the rhodium-containing catalysts against Air and moisture are stable because they essentially retain their activity. The selectivity to aldehydes increases somewhat, while the ratio of normal Aldehyde drops to branched aldehyde.

Example 7 a) A rhodium complex on silicon dioxide as a carrier (rhodium content 1.2% by weight) was prepared from the complex # Rh.SBu. (CO) ((EtO) 3SiCH2CH2P (C6H5) 2) 2 #.

Preparation of the complex (RhSBun (CO) ((EtO) 3SiCH2CH2PO2) 2) in a Flasks were 0.899 g of (Rh (CO) 2SBu ") 2 (made from (Rh (CO) 2Cl) 2 and nBuSH) and 50 ml of degassed pentene were added, whereupon 4 g of (EtO) 3SiCH2CH2PO2 were added under nitrogen became. Carbon oxide was developed here.

The reaction mixture was stirred at room temperature for 2 hours. Try, the reaction product to precipitate with methanol @ u @ were unsuccessful. The reaction mixture was therefore evaporated to dryness and the product was gelcisted again in pentane. The solution was cooled to -78 ° C, with a low. melting solid precipitated became. The.

Solution was left to warm to room temperature.

and discard the top pentane layer. The red obtained: viscous In this way, the liquid was precipitated three times from pentane and then under dried under reduced pressure.

The infrared spectrum showed a single CO beam frequency at about 1950 cm (the starting material shows five CO stretching frequencies, two of which Main bands are around 2000 1 and 20501).

2.5 g of the complex (RhSBu (CO) ((EtO) 3SiCH2CH2PO2) 2) dissolved in 170 ml of benzene under nitrogen. After adding 10 g of silicon dioxide was the reaction mixture is heated under reflux with stirring for 4 hours. The ethanol was by azeotropic distillation with a Dean & Stark apparatus from the reaction mixture severed. The obtained rhodium-containing silica was in a Soxhlet extraction apparatus Extracted with benzene for 24 hours and then dried under reduced pressure.

Rhodium content 1.2% by weight b) In a 500 ml stainless steel autoclave Steel were 0.873 g of the catalyst together Illit 84 g of hexene-1 and 200 ml of n-heptane given. J) ac reaction mixture was 4 hours.

kept at 140 ° C and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga). The reaction vessel was brought to room temperature chilled.

Conversion 100% by weight selectivity to aldehydes 67% by weight ratio from normal aldehyde to branched aldehyde 0.6 selectivity to olefins with internal Double bond 44% by weight The product contained less than 2 ppm rhodium.

c) The catalyst prepared according to Example 7 (b) was treated with acetone washed and dried under reduced pressure. He was then in touch for 9 days held in the air.

In a 500 ml stainless steel autoclave was placed 0.437 g of the prepared catalyst together with 42 g of hexene-1 and 100 ml of n-heptane. The reaction mixture was then 4 hours at 14,000 and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga). The reaction vessel was cooled to room temperature.

Conversion 100% by weight selectivity to aldehydes 63% by weight ratio from normal aldehyde to branched aldehyde 0.8 selectivity to olefins with internal Double bond 27 wt .-% This result shows that rhodium-containing catalysts, in which the rhodium is bonded to sulfur, are active for hydroformylation. It also shows then the.

Catalysts resistant to stainless steel were example 8 In a 500 ml stainless steel autoclave, 1.25 g of the Serving silica, 84 g of hexene-1 and 200 ml of n-heptane. The mixture was then 4 hours at 140 ° C and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga) held. The reaction vessel was cooled to room temperature. The product contained less than 2 wt. Aldehydes, although 44 wt.% Of hexene-1 is noted with internal double bonds had been isomerized. When repeating the Reaction in the absence of silica did not find hydroformylation or isomerization Fed up.

This result shows that the silica itself has little activity for hydroformylation, but essential activity for isomerization Has. It also shows that the autoclave itself is neither suitable for hydroformylation nor was catalytically active for isomerization.

Example 8 above is included for comparison purposes only.

Example 9 A rhodium complex on silicon dioxide as a carrier (rhodium content 1.2 wt%) was made up of #RhH (CO) ((EtO) 3SiCH2 CH2P (C6H5) 2) 3 # and silica prepared in the manner described in Example 6 (a).

In a 500 ml stainless steel autoclave, 0.888 g of the catalyst are added together with 84 g of hexene-1 and 200 ml of n-heptane. The reaction mixture was 4 hours at 80 to 83 ° C and under a CO / H2 pressure (1: 1) of 4130 kN / m² (ga) held. The reaction mixture was then cooled to room temperature.

Conversion 32% by weight selectivity to aldehydes 84% by weight of olefins internal double bond 16% by weight ratio of normal aldehyde to branched aldehyde 2.32 The rhodium content of the product was less than 1 ppm.

Example 10 A complex on silicon dioxide as a carrier (rhodium content 1.2% by weight) was made from #RhH (CO ()) EtO) 3SiCH2CH2 @ (C6H5) 2) 3 and silicon dioxide on the prepared in the manner described in Example G (a).

In a 500 ml stainless steel autoclave, 0.888 g of des Catalyst given together with 84 g of hexene-1 and 200 ml of n-heptane. The reaction mixture was then 4 hours at 100 to 101 ° C and a CO / H2 pressure (1: 1) of 4130 kN / m² (ga) held. The reaction vessel was.

then cooled to room temperature.

Conversion 67% by weight selectivity to aldehydes G4% by weight selectivity to olefins with an internal double bond 36% by weight ratio of normal aldehyde to branched aldehyde 2.75 The rhodium content of the product was below 1 ppm.

Claims (3)

Claims 1. Process for the hydroformylation of olefins to alcohols, aldehydes or both by hydroformylation of olefins with carbon dioxide and hydrogen at a temperature of 20 to 250 ° C, characterized in that a solid catalyst is used, which contains units of the formula Z-O-Si-O, where Z is a radical, the solid obtained by removing an -OH group from an -OH group inorganic material has been formed, and Q is a group attached to rhodium, Contains cobalt or iridium bound phosphorus. 2. The method according to claim 1, characterized in that as -OH groups inorganic solid material containing silicon dioxide is used. 3. The method according to claim 1 and 2, characterized in that a catalyst is used, the units of the formula contains, where R1 and R2 represent alkyl radicals, aryl radicals, alkoxy radicals or aryloxy radicals with up to 10 carbon atoms and R3 and R4 represent aryl radicals or alkyl radicals with up to 10 carbon atoms, -R1- an (optionally substituted) alkylene or arylene radical with up to 24 carbon atoms, M is a metal from the group consisting of rhodium, iridium and cobalt, L is a ligand and m is a number with a value such that the free valences of the metal are saturated.