Process for hydroformylation of short-chain olefins in gas phase

Abstract

The invention relates to a process for the hydroformylation of short-chain olefins, in particular C2 to C5 olefins, in a reactor, in which the catalyst system is present in heterogeneous form on a support made of a porous ceramic material, and in which synthesis gas or carbon monoxide is passed through the reactor during the process downtime.

Description

[0001] The project that gave rise to this patent application was funded by the European Union’s Horizon 2020 research and innovation programme under grant number 869896.

[0002] The invention relates to a process for the hydroformylation of short-chain olefins, in particular C2 to C5 olefins, in a reactor, wherein the catalyst system is present in heterogeneous form on a support made of a porous ceramic material and wherein synthesis gas or carbon monoxide is passed through the reactor during process downtimes.

[0003] Hydroformylation is one of the most important reactions in industrial chemistry, with a global annual production capacity of several million tons. Here, olefins (olefins) are reacted with a mixture of carbon monoxide and hydrogen (also known as synthesis gas or syngas) using a catalyst to form aldehydes, which are important and valuable intermediates for the preparation of chemical bulk products such as alcohols, esters or plasticizers.

[0004] Hydroformylation on the industrial scale is carried out exclusively under homogeneous catalysis. Soluble transition metal catalyst systems are usually based on cobalt or rhodium, which are often used together with phosphorus-containing ligands, such as phosphines or phosphites, for the hydroformylation of relatively short-chain olefins.

[0005] The known processes have various problems, among which these are particularly related to the relatively high cost of rhodium and cobalt and their compounds. Considerable expenditure on energy and process technology is required to substantially avoid catalyst losses during the hydroformylation, for example by means of catalyst recovery steps which are somewhat very expensive. Furthermore, the product purification steps are also more complex in order to ensure that as few catalyst residues as possible remain in the product.

[0006] Further problems of the known homogeneously catalyzed processes are the stability of the ligands which have to withstand the conditions of the hydroformylation, such as temperature, pressure, pH etc., and the consumption of the solvent used during the process which has to be compensated by supplementary metering.

[0007] In order to solve the above-mentioned problems in homogeneously catalyzed hydroformylation, a hydroformylation process has been developed in which the catalyst system is heterogenized, in particular by being immobilized on a support material. The terms "heterogeneous" and "immobilized" are therefore to be understood as immobilizing the catalyst by forming a thin liquid film on the surface and / or in the pores of a solid support material with the aid of an ionic liquid, and there is no reaction solution in the conventional sense in which the catalyst is homogeneously dissolved.

[0008] Hydroformylation processes in which the catalyst is present in heterogeneous form on a support material are disclosed, for example, in WO 2015 / 028284 A1, EP 3632885 A1, EP 3744707 A1, EP 3632886 A1 or EP 3736258 A1.

[0009] When carrying out hydroformylation over heterogeneous catalysts, problems may arise when downtime occurs, for example during maintenance work or due to other production technology-related reasons. In the context of the present invention, downtime is understood to be the time during which it is impossible to guide the feed mixture through the reactor and therefore it is also impossible to carry out the hydroformylation reaction. After such downtime, the reaction usually shows poor performance, i.e. lower conversion and selectivity. This may be due to the formation of high boilers and the destruction of some catalysts. In order to avoid the formation of high boilers, the product mixture is usually purged from the reaction space with nitrogen during the downtime. However, it has been found that this can lead to a decrease in reactor performance.

[0010] It was therefore an object of the present invention to provide a process for the hydroformylation of olefins which does not have the abovementioned problems and which, in particular after downtimes, can be started up more quickly and can be operated without loss of catalyst activity.

[0011] According to claim 1, this object is achieved in that the reactor is purged with synthesis gas or carbon monoxide during the downtime. Product residues are thus purged from the reaction space and the catalyst complex is protected by a high CO partial pressure.

[0012] The present invention therefore provides a process for the hydroformylation of C2 to C8 olefins using a heterogeneous catalyst system in a reaction zone, wherein

[0013] A gaseous feed mixture containing C2 to C8 olefins is conducted together with synthesis gas in at least one reactor through a support made of a porous ceramic material arranged in the at least one reactor, on which a catalyst system is present in a heterogeneous form, the catalyst system comprising a metal from Group 8 or Group 9 of the Periodic Table of Elements, at least one organic phosphorus-containing ligand, a stabilizer and optionally an ionic liquid; wherein

[0014] The carrier is monolithic, i.e. a ceramic material block, or in the form of a powder, granules or a shaped body, and the carrier consists of a carbide, nitride, silicide material or a mixture thereof, characterized in that

[0015] During the process described, downtimes occur during which no gaseous feed mixture is passed through the reactor, wherein the reactor is purged with synthesis gas or carbon monoxide during these downtimes.

[0016] The characteristic feature of the present invention is that the reactor is purged with synthesis gas and carbon monoxide during the downtime. It can be achieved that higher conversion and yield can be obtained after the downtime compared with other purge gases, so that the reactor can be put into normal operation again more quickly. The temperature when purging with synthesis gas or carbon monoxide is preferably 20 to 200° C., further preferably 22 to 175° C., more preferably 85 to 150° C. In addition, it is preferred that the reactor is kept at a maximum value of less than 10° C. below the reaction temperature during the downtime. Cooling should be avoided in this way. The pressure during the purge is relatively unimportant, but should not exceed the pressure during the hydroformylation process.

[0017] The feed mixture used can be to comprise C2 to C8 olefins, preferably C2 to C5 olefins, especially all mixtures of ethylene, propylene, 1-butene, 2-butene, 1-pentene or 2-pentene as reactants. The amount of olefins in the feed mixture should of course be high enough to be able to economically carry out hydroformylation reaction. The feed mixture that can be used in the method of the present invention also includes technical mixtures from the petrochemical industry, such as raffinate stream (raffinate I, II or III) or crude butane. According to the present invention, crude butane comprises 5 to 40 % by weight of butenes, preferably 20 to 40 % by weight of butenes (described butenes are composed of 1 to 20 % by weight of 1-butene and 80 to 99 % by weight of 2-butenes) and 60 to 95 % by weight of butanes, preferably 60 to 80 % by weight of butanes.

[0018] The method of the present invention is carried out in at least one reactor in which the hydroformylation reaction of the present invention is carried out. A carrier with a heterogeneous catalyst system is arranged in the at least one reactor. In another embodiment of the present invention, the method can also be carried out in a plurality of reactors, which can be connected in parallel or in series. Preferably, in the present case, the reactors are connected in parallel and used alternately.

[0019] The hydroformylation is preferably carried out under the following conditions: The temperature in the hydroformylation should be from 65 to 200° C., preferably from 75 to 175° C., more preferably from 85 to 150° C. The temperature can be adjusted by suitable cooling means, such as a cooling jacket. The pressure during the hydroformylation should not exceed 35 bar, preferably 30 bar, more preferably 25 bar. The molar ratio between synthesis gas and feed mixture should be from 6:1 to 1:1, preferably from 5:1 to 3:1. Optionally, the feed mixture can be diluted with an inert gas, such as an alkane present in the technical hydrocarbon stream.

[0020] The catalyst system used in the hydroformylation process of the present invention preferably comprises a transition metal from Group 8 or Group 9 of the Periodic Table of the Elements, in particular iron, ruthenium, iridium, cobalt or rhodium, further preferably cobalt and rhodium, more preferably rhodium, at least one organic phosphorus-containing ligand and a stabilizer.

[0021] The stabilizer is preferably an organic amine compound, more preferably an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit according to formula (I):

[0022]

[0023] In a particularly preferred embodiment of the present invention, the stabilizer is selected from the group consisting of compounds of the following formulae (I.1), (I.2), (I.3), (I.4), (I.5), (I.6), (I.7) and (I.8).

[0024]

[0025] wherein n is an integer from 1 to 20;

[0026]

[0027] wherein n is an integer from 1 to 12;

[0028]

[0029] wherein n is an integer from 1 to 17;

[0030]

[0031] wherein R is a C6 to C20 alkyl group.

[0032] For all film-forming components, i.e. the stabilizer in the present case, the gas solubility of the reactant should be better than the gas solubility of the product. This already allows a partial separation of the reactant olefins used and the product aldehydes formed. In principle, other film-forming substances are also conceivable for this, but care should be taken not to increase the formation of high boilers and / or to limit the supply of the reactant olefins.

[0033] The organic phosphorus-containing ligands used in the catalyst system of the present invention can be selected from the ligands known for hydroformylation. A large number of suitable ligands are known to those skilled in the art from patents and professional literature, for example monophosphite or bisphosphite ligands. The organic phosphorus-containing ligand preferably has a bisphosphite structure of the general formula (II):

[0034] R'–A–R”–A–R”'(II)

[0035] Wherein R', R" and R"' are each an organic group, and the two A's are each a bridged -OP(-O) 2 -group in which two of the three oxygen atoms -O- are each attached to a group R' and a group R'", with the proviso that R' and R'' are not identical. The organic groups R', R" and R'' preferably contain no terminal trialkoxysilane groups.

[0036] In a preferred embodiment, R', R" and R'"' in the compounds of formula (VI) are preferably selected from substituted or unsubstituted 1,1'-biphenyl, 1,1'-binaphthyl and o-phenyl, in particular substituted or unsubstituted 1,1'-biphenyl, with the proviso that R' and R'"' are not identical. More preferably, the substituted 1,1'-biphenyl has an alkyl and / or alkoxy group, in particular a C1-C4 alkyl group, more preferably a tert-butyl group and / or a methyl group, and / or preferably a C1-C5 alkoxy group, more preferably a methoxy group, in the 3,3' and / or 5,5' position of the 1,1'-biphenyl base structure.

[0037] According to the present invention, the above-mentioned catalyst system is present in a heterogeneous form on a support formed of a porous ceramic material. In the context of the present invention, the expression "present in a heterogeneous form on a support" is understood to mean that the catalyst system is fixed on the inner and / or outer surface of the support by forming a thin solid or liquid film with the aid of a stabilizer. The film can also be solid at room temperature and liquid under reaction conditions.

[0038] The inner surface of the solid support material includes in particular the inner surfaces of the pores. The concept of immobilization includes both the case where the catalyst system and / or the catalytically active substance is present in dissolved form in a solid or liquid film and the case where a stabilizer acts as an adhesion promoter or the catalyst system is adsorbed on the surface but is not chemically or covalently bonded to the surface.

[0039] According to the invention, therefore, there is no reaction solution in the conventional sense in which the catalyst is homogeneously dissolved; instead, the catalyst system is dispersedly distributed on the surface and / or in the pores of the support.

[0040] The porous support material is preferably selected from nitride ceramics, carbide ceramics, silicide ceramics and mixtures thereof, such as carbonitride materials.

[0041] The nitride ceramic is preferably selected from silicon nitride, boron nitride, aluminum nitride and mixtures thereof. The carbide ceramic is preferably selected from silicon carbide, boron carbide, tungsten carbide or mixtures thereof. Mixtures of carbide and nitride ceramics (so-called carbonitrides) are also conceivable. The silicide ceramic is preferably molybdenum silicide. The support to which the catalyst system is applied according to the invention preferably consists of a carbide ceramic, more preferably silicon carbide.

[0042] In the present invention, the support may be present as a monolith, ie a block of ceramic material, or in the form of a powder, granules or a shaped body.

[0043] If the carrier is monolithic, it consists of a block (three-dimensional object) of porous ceramic material. The block can be in a single piece or can consist of a plurality of, i.e. at least two, individual parts which can be connected together to form the block and / or can be connected to each other in a fixed or detachable manner.

[0044] The support made of porous ceramic material is preferably a three-dimensionally extending component, which in its cross section can in principle be of any geometric shape, for example round, angular, square, etc. In a preferred embodiment, the three-dimensionally extending component that can be used as a support has a longitudinal direction (direction of the longest extension) in the main flow direction (direction in which the feed mixture and synthesis gas flow from the inlet to the outlet of the reactor).

[0045] The carrier monolithic block made of porous ceramic material thus formed has at least one continuous channel in the main flow direction. However, the one or more channels may also be configured so that they are not completely continuous, but terminate at one end opposite to the reactor inlet or the channel is closed toward the end. The carrier monolithic block may also have at least two or more channels. The diameter of the channel may be 0.25 to 50 mm, preferably 1 to 30 mm, further preferably 1.5 to 20 mm, more preferably 2 to 16 mm. If there are multiple channels, the diameters of the channels may be the same or different from each other. Relative to the diameter or one of the diameters of the entire carrier, the selection of the diameter of the channel should especially make the mechanical stability unaffected.

[0046] In addition, the support monolith made of ceramic material is porous, i.e. has pores. In particular, the catalyst system of the invention is also present in the liquid or solid film in these pores. The pore size is preferably from 0.9 nm to 30 μm, preferably from 10 nm to 25 μm, more preferably from 70 nm to 20 μm. The pore size can be determined according to DIN 66133 (edition: 1993-06) by nitrogen adsorption or mercury porosimetry.

[0047] In a preferred embodiment, the carrier monolith has at least partially continuous pores extending from the surface to the channel and / or from one channel to one or more adjacent channels. A plurality of pores may also be connected to each other, thus forming a single continuous pore as a whole.

[0048] According to the invention, the carrier can also be in the form of a powder, a granular material or a shaped body, such as a pellet, a ring, a ball, etc. The average particle size (d50) of the carrier can be from 0.1 mm to 7 mm, preferably from 0.3 to 6 mm, more preferably from 0.5 mm to 5 mm. The average particle size can be determined by imaging methods, in particular by the methods mentioned in the standards ISO 13322-1 (version: 2004-12-01) and ISO 13322-2 (version: 2006-11-01). The carrier in the form of a powder, a granular material or a shaped body can be produced according to methods known to those skilled in the art. This can be achieved by mechanically crushing a monolithic block made of a carbide, nitride, silicide material or a mixture thereof using, for example, a jaw crusher and adjusting the particle size of the resulting crushed granular material by screening.

[0049] In contrast to the support monolith, the particles of the powder, granules or shaped bodies made of ceramic material are porous, i.e. have pores. In particular, the catalyst system of the invention is also present in a solid or liquid film in these pores. The pore diameter is preferably from 0.9 nm to 30 μm, preferably from 10 nm to 25 μm, more preferably from 70 nm to 20 μm. The pore diameter can be determined according to DIN 66133 (edition: 1993-06) by nitrogen adsorption or mercury porosimetry.

[0050] Whether it is a monolith, powder, granules or a shaped body, the carrier is made as follows:

[0051] For the provided support in the form of powder, granules or pellets made of ceramic material, a so-called coating can also be applied, which is made of the same or different ceramic material, preferably silicon oxide, based on the ceramic material of the support. The coating itself can be porous or non-porous, and the coating is preferably non-porous. The particle size of the coating is preferably 5nm to 3μm, preferably 7nm to 700nm. The coating is used to introduce or generate the required pore size and / or increase the surface area of ​​the support. The coating can be applied in particular by immersion (dip coating) in a coating solution containing a ceramic material (optionally also as a precursor) containing the coating. The amount of coating present on the support is ≤20% by weight, preferably ≤15% by weight, and more preferably ≤10% by weight based on the total amount of the support. However, in a preferred embodiment of the present invention, the support has no coating.

[0052] The catalyst system is applied to a support with or without a coating. For this purpose, a catalyst solution is first prepared by mixing (especially at room temperature and ambient pressure), wherein the catalyst solution comprises at least one organic phosphorus-containing ligand, at least one metal precursor (e.g. chloride, oxide, carboxylate of the respective metal), at least one stabilizer and at least one solvent. When preparing the catalyst system, ionic liquids can optionally be used, but it is also possible to prepare the catalyst solution without the use of ionic liquids. The catalyst solution should be prepared in particular in an inert environment, for example in a glove box. In this case, an "inert environment" refers to an atmosphere that is as free of water and oxygen as possible.

[0053] The solvent can be selected from all solvent classes (protic, aprotic, polar or nonpolar). The prerequisite for the solvent is the solubility of the catalyst system (ligand, metal precursor, stabilizer and optional ionic liquid) and preferably also the solubility of the high boilers formed in the hydroformylation. In the immobilization step, the solubility can be increased by heating.

[0054] The solvent is preferably aprotic, polar, such as acetonitrile and ethyl acetate, or aprotic, nonpolar, such as THF and diethyl ether. Chlorinated hydrocarbons, such as dichloromethane, or aldehydes can also be used as solvents.

[0055] The catalyst solution thus produced is then brought into contact with the support, optionally including the coating, for example by immersion (dip coating) or by filling a pressure vessel, for example directly in the reactor (in situ impregnation). If the catalyst solution is applied outside the reactor, the support must of course be installed in the reactor again after the solvent has been separated off. Preferably, the catalyst solution is applied directly to the support with the coating in the reactor, since this avoids potentially time-consuming installation and removal steps and possible contamination of the catalyst.

[0056] The catalyst solution can be charged into the reactor through the normal inlet or outlet, for example by a pump. Liquid distributors or nozzles within the reactor, and optionally pressure drop internals or metering rate regulators, ensure uniform distribution of the catalyst liquid.

[0057] After the catalyst system has been applied, the solvent is separated off. In this process, the residual catalyst solution is first discharged through the reactor outlet. The solvent residues remaining in the reactor are then evaporated by adjusting the pressure or increasing the temperature. In another embodiment, the pressure can also be adjusted while increasing the temperature at the same time. The temperature can be between 20 and 150° C., depending on the solvent. The pressure can be adjusted to a high vacuum (10 -3 Up to 10 -7 mbar), depending on the solvent, but overpressures of a few mbar to several bar are also conceivable, depending on the solvent and temperature.

[0058] The stabilizer and the ionic liquid, if present, remain in heterogeneous form on the support together with the catalyst composed of a transition metal, in particular cobalt or rhodium, and an organic phosphorus-containing ligand.

[0059] The catalyst system can be applied to the carrier directly in the reactor (in situ) or outside the reactor. If the catalyst system is applied outside the reactor, the carrier must always be transported under the exclusion of air, which is achieved, for example, by nitrogen countercurrent. In a preferred embodiment of the present invention, the catalyst system is directly in the reactor, i.e., applied in situ. After separating the solvent, the reactor can be used immediately and the feed mixture can be loaded. The advantage of doing so is that time-consuming installation and disassembly steps are not required, which can cause longer shutdowns of the reactor. In addition, there is no longer any restriction on the size of the carrier because there is a suitable space with an inert environment of a specific size. The size of the carrier can be freely selected according to the reactor design.

[0060] After the catalyst system has been applied to the support and the solvent has been separated off, the plant, in particular the reactor, can be started up, ie put into operation, by a two-stage or more stage start-up procedure. Suitable start-up procedures are described, for example, in EP 3632887.

[0061] Preferably, a gaseous output comprising at least a portion of the product aldehyde formed and at least a portion of the unreacted olefin is continuously withdrawn from the reaction zone in which the hydroformylation according to the invention is carried out. The gaseous output can be subjected to one or more material separation steps, wherein the gaseous output is separated into at least one phase rich in unreacted olefin and at least one phase rich in product aldehyde.

[0062] The material separation can be carried out by using known material separation methods, such as condensation, distillation, centrifugation, nanofiltration or a combination of multiple thereof, preferably condensation or distillation.

[0063] In the case of a multi-stage separation of materials, the phase rich in product aldehydes formed in the first separation of materials can be sent to a second separation of materials, in particular a downstream aldehyde separation, wherein the product aldehydes are separated from other materials present in this phase (usually alkanes and reactant olefins). The phase rich in unreacted olefins can be recycled to the hydroformylation step or, in the case of a multi-stage configuration, to one of the hydroformylation steps for further hydroformylation of the olefins contained therein to product aldehydes.

[0064] In the material separation, in addition to the above phases, a purge gas stream having a composition at least similar to or identical to that of the phase rich in unreacted olefins can also be taken out. The purge gas stream can also be conveyed to a second material separation or aldehyde separation to separate the product aldehyde contained therein and to output impurities (e.g. nitrogen in the synthesis gas) or inert substances (e.g. alkanes in the feed mixture) from the system. Impurities or inert substances can usually be taken out as volatile substances in the second material separation, for example at the top of the tower.

[0065] Another subject of the present invention is also an apparatus for carrying out the process, which apparatus comprises in particular a reactor for carrying out the hydroformylation step according to the invention. Furthermore, the apparatus may comprise a substance separation unit for separating the gaseous output from the hydroformylation step into at least one phase rich in unreacted olefins and at least one phase rich in product aldehydes, wherein the substance separation unit is arranged downstream of the hydroformylation according to the invention. Downstream of the first substance separation there may be a second substance separation unit, in particular an aldehyde separation unit, for separating off the product aldehydes.

[0066] Even without further elaboration, it is believed that one skilled in the art can utilize the above description to its fullest extent.Therefore, the preferred embodiments and examples should be interpreted as descriptive disclosures only and not limiting disclosures in any way.

[0067] The present invention will be described in more detail below with the aid of examples. Alternative embodiments of the present invention can be obtained by analogous methods. Example:

[0068] Experiment 1-4: Purging with different gases during system downtime

[0069] The starting material used as a support is SiC pellets (SIKAT SarL SIC-3). The SiC pellets are placed in a 20 cm long, 1 inch (about 2.54 cm) diameter circular reactor casing, where glass beads of similar size are placed above and below the pellets. Then, a solution containing Rh(acac)(CO) is added to the SiC pellets. 2 A catalyst solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (stabilizer) and dichloromethane (solvent) was prepared. For this purpose, the catalyst solution was introduced into the reactor under a slight overpressure after purging the reactor with nitrogen. After the solvent was removed from the reactor by drainage and evaporation, the catalyst system present in heterogeneous form on the support granules was used for hydroformylation.

[0070] The feed mixture used was a hydrocarbon stream having the following composition:

[0071] Amount (weight %) Butene 13 Butane 87

[0072] For the hydroformylation, the feed mixture was introduced into the reactor together with synthesis gas (molar ratio synthesis gas:feed mixture=3.5:1) at a gas volume flow rate of 390 ml / min. The hydroformylation was carried out at a temperature of 120-130° C. and a pressure of 17 bar.

[0073] During the experiments, the reactant flow was interrupted several times for extended periods of time (downtime) and various strategies for maintaining the activity of the catalyst system were investigated.

[0074] Experiment 1: During the first downtime 1, the reactor, which continued to be heated to 120°C, was purged with a nitrogen stream at a pressure of 1.2 bar.

[0075] Experiment 2: During the second downtime 2, the reactor, which continued to be heated to 120°C, was purged with a nitrogen stream at a pressure of 17 bar.

[0076] Experiment 3: During the third shutdown time 3, the reactor, which continued to be heated to 120°C, was purged with synthesis gas at a pressure of 17 bar.

[0077] Experiment 4: During the fourth downtime 4, the reactor, which continued to be heated to 120°C, was purged with synthesis gas at a pressure of 1.2 bar.

[0078] The conversion and yield were determined before and after each experimental date. The results are shown in Table 1 below:

[0079] Table 1: Results of the above experiments

[0080]

[0081] It is shown that when purging with synthesis gas, the yield and conversion reach similar high values ​​again after the downtime. When purging with nitrogen, the yield and conversion are significantly lower than before the downtime.

Claims

1. A process for the hydroformylation of C2 to C8 olefins using a heterogeneous catalyst system in a reaction zone, wherein A gaseous feed mixture containing C2 to C8 olefins is conducted together with synthesis gas in at least one reactor through a support made of a porous ceramic material arranged in the at least one reactor, on which a catalyst system is present in a heterogeneous form, the catalyst system comprising a metal of Group 8 or Group 9 of the Periodic Table of Elements, at least one organic phosphorus-containing ligand and a stabilizer; wherein The carrier is monolithic, i.e. a ceramic material block, or in the form of a powder, granules or a shaped body, and the carrier consists of a carbide, nitride, silicide material or a mixture thereof, characterized in that During the process described, downtimes occur during which no gaseous feed mixture is passed through the reactor, wherein the reactor is purged with synthesis gas or carbon monoxide during these downtimes.

2. The method according to claim 1, wherein no coating is applied to the carrier, but a carrier without a coating is used.

3. The process according to claim 1 or 2, wherein the organic phosphorus-containing ligand of the hydroformylation catalyst system preferably has the general formula (II): R'–A–R”–A–R”'(II) wherein R', R" and R'" are each an organic group, provided that R' and R'" are not the same, and the two A's are each a bridging -OP(-O)2- group, in which two of the three oxygen atoms -O- are each connected to the group R' and the group R'".

4. The method according to any one of claims 1 to 3, wherein the stabilizer is an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit according to formula (I):

5. The method according to any one of claims 1 to 4, wherein the nitride ceramic is selected from silicon nitride, boron nitride, aluminum nitride and mixtures thereof; the carbide ceramic is selected from silicon carbide, boron carbide, tungsten carbide or mixtures thereof; and the silicide ceramic is molybdenum silicide. The method according to claim 5 , wherein the support is composed of carbide ceramic. The method according to claim 6 , wherein the support consists of silicon carbide.

8. The process according to any one of claims 1 to 7, wherein the hydroformylation is carried out at a temperature of 65 to 200°C, preferably 75 to 175°C, more preferably 85 to 150°C.

9. The process according to any one of claims 1 to 8, wherein the pressure in the hydroformylation is not more than 35 bar, preferably not more than 30 bar, more preferably not more than 25 bar.

10. The process according to any one of claims 1 to 9, wherein the catalyst system does not comprise an ionic liquid.

11. The process according to any one of claims 1 to 10, wherein C4 olefins are used in the hydroformylation process.

12. The process according to any one of claims 1 to 11, wherein the metal of Group 8 or Group 9 of the Periodic Table of the Elements used is rhodium.

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