Title of Invention

A PROCESS FOR THE PRODUCTION OF ALCOHOLS

Abstract The invention relates to a process for the production of alcohols having 7 to 18 C atoms by hydroformylation of the corresponding olefms with synthesis gas in the presence of an organic phase containing a cobalt catalyst at temperatures from 50 to 220°C and pressures from 100 to 400 bar, and subsequent hydrogenation of the aldehydes thus obtained, the cobalt catalyst being formed by reacting an aqueous cobalt salt solution in the presence of an organic solvent, which is only slightly miscible with water or not at all, with synthesis gas, and the organic phase containing the cobalt catalyst is obtained by extraction of the cobalt catalyst formed from the aqueous phase by means of an organic extractant which is only slightly miscible with water or not at all. The formation of the cobalt catalyst, the extraction of the cobalt catalyst formed into the organic phase and the hydroformylation of the corresponding olefms are carried out in I-stage process. The oxo alcohols produced by means of the process accordirg to the invention are used for the production of carboxylic acid esters as plasticizers for plastics.
Full Text

The present invention relates to a process for the production of alcohols having 7 to 18C atoms by hydroformylation of the corresponding olefins with a synthesis gas in the presence of an organic phase containing a cobalt catalyst at temperatures from 50 to 220°C and pressures from 100 to 400 bar and subsequent hydrogenation of the aldehydes thus obtained, the cobalt catalyst being formed by reacting an aqueous cobalt salt solution in the presence of an organic solvent, which is only slightly miscible with water or not at all, with a synthesis gas, and the organic phase containing the cobalt catalyst being obtained by extraction of the cobalt catalyst formed from the aqueous phase by means of an organic extractant which is only slightly miscible with water or not at all.
In addition the invention relates to the use of the alcohols produced for the production of carboxylic acid esters as plasticizers for plastics.
The hydroformylation of olefins with carbon monoxide and hydrogen to give aldehydes having one more C atom in the presence of transition metal catalysts such as, for example, cobalt and rhodium compounds, is known as the oxo synthesis. In general, a high proportion of straight - chain aldehydes - the intermediates in the production of the economically important plasticizer alcohols for plastics and detergent alcohols - is desired in the hydroformylation of olefins to give aldehydes.
While linear and terminal olefins (so-called a-olefins) can very readily be hydroformylated with phosphine-modified rhodium or cobalt catalysts (J. Falbe, Editor, "New Synthesis with Carbon Monoxide", Springer-Verlag, Berlin 1980, pages 55 et seq., unmodified cobalt and rhodium catalysts are preferentially employed for low-reactivity olefins, for internal olefins and for internal and branched olefins.

In the presence of modified catalysts, internal and branched olefins are hydroformylated very slowly or only partially. This precludes the possible use of modified catalysts for an economical hydroformylation of internal and branched olefins.
The hydroformylation of polymeric and isomeric olefin mixtures containing terminal and internal as well as internal and branched olefins is advantageously carried out with unmodified cobalt catalysts. As compared with rhodium catalysts, higher yields of the particularly demanded straight - chain aldehydes are obtained with cobalt catalysts, starting from the same initial olefin.
Examples of typical polymeric and isomeric olefin mixtures, which are preferably converted by cobalt-catalyzed hydroformylation to give corresponding oxo aldehydes, are the dimers, trimers and tetramers of propene, of the n-butenes (1- and 2-butene) and of isobutene.
According to the known processes, the cobalt-catalyzed hydroformylation is carried out as a multi-stage process which comprises the following four process stages: the preparation of the catalyst (precarbonylation), the catalyst extraction, the olefin hydroformylation and the removal of the catalyst from the reaction product (decobalting).
Since the development of the oxo synthesis, the individual process stages of the cobalt-catalyzed hydroformylation are continually being improved and modified.
In the first process stage, the precarbonylation, the catalyst complex (HCo(CO)4) required for the hydroformylation is prepared starting from an aqueous cobalt salt Solution by reaction with carbon monoxide and hydrogen. According to DE-OS

2,139,630, the precarbonylation is preferably carried out at temperatures from 100 to 160°C and under synthesis gas pressures from 200 to 300 bar in the presence of activated carbon, zeolites or basic ion exchangers loaded with cobalt carbonyls.
DE-OS 2,244,373 describes an improved continuous carbonylation process, in which marked shortening of the reaction time is achieved by passing the starting materials synthesis gas and aqueous cobalt salt solution in cocurrent in the presence of oxygen-containing organic solvents, which are poorly miscible with water or not at all, through a zone in which a turbulent flow is maintained. As an advantageous embodiment, use of a pressurized turbulence pipe for maintaining the turbulent flow and the addition of alcohols or aldehydes having 4 to 10 carbon atoms as the organic solvent are mentioned.
In the second process stage, the catalyst extraction, the cobalt catalyst prepared in the first process stage is extracted from the aqueous phase with an organic phase, preferably the olefin which is to be hydroformylated. According to DE-OS 2,106,252, it is expedient to employ for the catalyst extraction, in addition to the olefin, the reaction products and by-products of the hydroformylation, provided they are water-insoluble and liquid under the selected reaction conditions. The catalyst extraction is preferably carried out in countercurrent at temperatures from 20 to 100°C and under synthesis gas pressures from 100 to 400 bar. After the phase separation, the organic phase loaded with the cobalt catalyst is fed to the third process stage, the hydroformylation.
From DE-OS 2,139,630, it is known that, in the third process stage, the hydroformylation, olefins loaded with the cobalt catalyst can be hydroformylated in a high-pressure reactor with synthesis gas at temperatures between 70 and 170 °C and

at pressures from 100 to 400 bar to give the corresponding aldehydes. Some of the aldehydes formed can be hydrogenated to the alcohol under the hydroformylation conditions, in particular at high temperatures.
The reactor product which, in addition to the valuable products aldehyde and alcohol, additionally contains by-products, residual olefin which is not hydroformylated, and cobalt catalyst, is let down to 1 to 15 bar and then fed to the catalyst reprocessing stage.
In the fourth process stage, the decobalting, the organic phase of the reactor product is freed of the cobalt carbonyl complexes in the presence of complex-free process water by treatment with oxygen or air. According to WO 93/24438, the decobalting is carried out at temperatures from 60 to 100°C and pressures from 1 to 20 bar. In this way, the cobalt catalyst is oxidatively destroyed and the resulting cobalt salts are back-extracted into the aqueous phase. The resulting aqueous cobalt salt solution from the decobalting is recycled into the first process stage, the precarbonylation.
A further embodiment is described in WO 93/24437 and EP-OS 0,183,546. In this case, gas scrubbing with synthesis gas or nitrogen is carried out before the oxidative destruction of the cobalt catalyst.
After the gas phase has been separated off, the reaction products in the remaining organic phase are converted to the corresponding alcohols in further processing stages, such as hydrogenation and distillation.
The known multi-stage production processes for oxo aldehydes in the presence of cobalt catalysts have a number of industrial disadvantages. Thus, two process stages expensive in engineering terms - precarbonylation and catalyst extraction - are

required for preparing the cobalt catalyst needed for the hydroformylation. Due to the mass transfer processes occurring in the two process stages, namely gas/liquid mass transfer in the precarbonylation and liquid/liquid mass transfer in the catalyst extraction, two mutually separate pressure-resistant equipment items such as, for example, stirred vessels or packed columns, are necessary. The actual hydroformylation subsequently takes place again in a separate pressure reactor. The removal of the cobalt catalyst is tied to a further plant section.
The known multi-stage hydroformylation processes consequently presuppose very high investment in addition to a large process engineering effort.
The present invention is therefore based on the object of developing a novel hydroformylation process for olefins with subsequent hydrogenation of the aldehydes obtained, which is easier to carry out in process engineering terms and is more economical.
It has now been found, surprisingly, that the formation of the cobalt catalyst, the extraction of the cobalt catalyst formed into the organic phase and the hydroformylation of the corresponding olefins can be carried out in a 1- stage process.
Thus, the first three process steps of the conventional processes, namely the precarbonylation, the catalyst extraction and the hydroformylation, are carried out in a 1-stage process, preferably in one reactor.
The expensive separation of the equipment for the process stages is thus eliminated. This is of particular economic interest, since the reduction of the process stages means considerable lowering of the investment costs. In the process according to the invention, the precarbonylation, extraction and hydroformylation proceed side by side

and partially in situ. Moreover, the 1-stage process according to the invention is preferably carried out continuously, the cobalt salt solution arising after the decobalting preferably being circulated.
The present invention relates therefore to a process for the production of alcohols having 7 to 18 C atoms by hydroIformylation of the corresponding olefins with synthesis gas in the presence of an organic phase containing a cobalt catalyst at temperatures from 50 to 220°C and pressures from 100 to 400 bar and subsequent hydrogenation of the aldehydes thus obtained, the cobalt catalyst being formed by reacting an aqueous cobalt salt solution in the presence of an organic solvent, which is only slightly miscible with water or not at all, with synthesis gas, and the organic phase containing the cobalt catalyst being obtained by extraction of the cobalt catalyst formed from the aqueous phase by means of an organic extractant which is only slightly miscible with water or not at all, which comprises carrying out the formation of the cobalt catalyst, the extraction of the cobalt catalyst formed into the organic phase and the hydroformylation of the corresponding olefins in a 1-stage process.
Preferably, the formation of the cobalt catalyst, the extraction of the cobalt catalyst into the organic phase and the hydroformylation of the corresponding olefins are carried out in one single reactor.
In addition, the present invention relates to the use of the alcohols produced according to the invention for the production of carboxylic acid esters as plasticizers for plastics.
The process according to the invention is preferably carried out continuously.
The preferred cobalt salts used are water-soluble cobalt salts such as, for example, formates and acetates. Cobalt acetate, which is preferably employed as an aqueous

solution with a cobalt content of from 0.2 to 2 % by weight, particularly preferably from 0.5 to 1.5 % by weight, calculated as metal, has proved particularly suitable.
The organic solvent can be the olefin to be hydroformylated and/or an aldehyde and/or an alcohol, the aldehyde and the alcohol preferably being the reaction products formed during the hydroformylation.
Thus, the organic solvent which is only slightly miscible with water or not at all is preferably an olefin and/or an aldehyde and/or an alcohol, particularly preferably the reaction product from the 1-stage process.
The extractant required for the extraction of the cobalt catalyst from the aqueous phase can be any organic solvent which is only poorly miscible with water or not at all, provided that it has sufficient solubility for the cobalt catalyst. However, a mixture of the olefin to be hydroformylated and the aldehydes and/or alcohols formed during the hydroformylation is preferably employed.
Thus, an olefin and/or an aldehyde and/or an alcohol, particularly preferably the reaction product from the 1-stage process, is preferably employed as the organic extractant which is only slightly miscible with water or not at all.
Suitably, the organic solvent which is only slightly miscible with water or not at all and the organic extractant which is only slightly miscible with water or not at all are identical.
Particular importance is attached in the process according to the invention to the metering of the starting materials into the reactor of the 1-stage process. The metering device should ensure good phase-mixing and the generation of the largest possible phase exchange area.

For the metering of the starting materials, the metering devices known in industry, such as, for example, turbulence pipes filled with packing or mixing nozzles for multiphase systems, can be employed. The metering is preferably carried out with a mixing nozzle while maintaining turbulent flow.
The aqueous cobalt salt solution, olefin, synthesis gas, an organic solvent, which is only slightly miscible with water or not at all, and an organic extractant, which is only slightly miscible with water or not at all, can be introduced into the reactor of the 1-stage process simultaneously, in particular by means of a mixing nozzle.
In another variant of the process according to the invention, an organic solvent, which is only slightly miscible with water or not at all, and an organic extractant, which is only slightly miscible with water or not at all, can be initially introduced into the reactor of the 1-stage process, and the aqueous cobalt salt solution, olefin and synthesis gas can be fed to the reactor of the 1-stage process simultaneously, in particular by means of a mixing nozzle.
In a further embodiment of the present invention, an organic extract, which is only slightly miscible with water or not at all, can be initially introduced into the reactor of the 1-stage process, and the aqueous cobalt salt solution, olefin, synthesis gas and an organic solvent, which is only slightly miscible with water or not at all, can be fed to the reactor of the 1-stage process simultaneously, in particular by means of mixing nozzle.
Preferably, the aqueous cobalt salt solution, olefin and synthesis gas are fed simultaneously to the reactor of the 1-stage process, particularly preferably by means of a mixing nozzle.

The 1-stage process, which comprises the precarbonylation, the catalyst extraction and the hydroformylation, can be carried out in a reactor at temperatures from 100 to 250 C and under pressures from 100 to 400 bar. Temperatures from 160 to 220°C and synthesis gas pressures from 200 to 300 bar have proved particularly suitable.
The carbon monoxide/hydrogen volume ratio in the synthesis gas is in general between 2:1 and 1:2, in particular 1:1. The synthesis gas is advantageously used in a slight excess over the amount stoichiometrically required.
The 1-stage process can, for example, be carried out in the generally known cylindrical upright high-pressure bubble column reactors, with or without an internally fitted coaxial insertion pipe.
In a preferred embodiment of the process according to the invention, the reactor space of the 1-stage process is subdivided by at least one partition device.
This partition device can, for example, be a perforated plate or a sieve tray and is suitably arranged perpendicular to the direction of flow of the stream of reactants and products.
As a result of the cascading of the reactor, the back-mixing is greatly reduced as compared with the simple bubble column, and the flow behavior approaches that of a tubular reactor. This process engineering measure has the consequence that both the space-time yield and the selectivity of the hydroformylation are improved.
In a suitable embodiment of the process according to the invention, the reactor product (organic and aqueous phases), it being possible to take the aqueous phase off wholly or partially at the bottom of the reactor, can be let down, after leaving the reactor, to 10 to 15 bar and be passed into the decobalting necessary for removing the cobalt

catalyst. In the decobalting stage, the discharge product can be freed of cobalt carbonyl complexes in the presence of an aqueous acidic cobalt salt solution (process water) by means of air or oxygen at temperatures from 50 to 180°C. The aqueous acidic cobalt salt solution (process water) has a cobalt content from 0.2 to 2.0 % by weight, calculated as metal, and a pH from 3 to 4. The pH can, for example, be adjusted with acetic acid. The decobalting can expediently be carried out at temperatures from 120 to 150°C, in order to ensure that the acetals formed by secondary reactions in the 1-stage process are broken down again as completely as possible to the desired valuable products, namely aldehyde and alcohol.
The decobalting is preferably carried out in a pressure vessel which is filled with packing such as, for example, raschig rings and in which the greatest possible phase exchange area is generated. The organic product phase now freed of cobalt compounds can be separated from the aqueous phase in a downstream separation vessel. The aqueous phase, which contains the cobalt compounds extracted from the organic phase, for example in the form of cobalt acetate or cobalt formate, is preferably recycled to the 1-stage process and again used as starting material for the preparation of the cobalt catalyst.
Suitably, the process according to the invention is thus carried out in such a way that the reaction product of the 1-stage process is treated, for the oxidation of the cobalt catalyst, with air with addition of aqueous acidic cobalt salt solution and, after separation into an organic phase containing the reaction products and an aqueous phase containing the cobalt salt, the aqueous phase is recycled to the 1-stage process.
Subsequently, the organic phase remaining after the removal of the cobalt catalyst can be hydrogenated and the alcohols thus obtained can be recovered from the hydrogenation product, for example by distillation.

Under the reaction conditions of the process according to the invention, the corresponding alcohols are also partially formed by hydrogenation in addition to the aldehydes. After the decobalting, the aldehydes and alcohols can be separated from the organic reactor product and be further processed individually. Prefer-ably, however, the complete organic reactor product is processed to give the corresponding alcohol by known processes, for example by hydrogenation and subsequent distillation.
The alcohols produced by the process according to the invention are particularly suitable as plasticizer alcohols and detergent alcohols. The aldehydes can also be used for the production of carboxylic acids. Plasticizer alcohols are converted by esterification, for example with phthalic anhydride (PA), to the usual plasticizers for polyvinyl chloride (PVC).
By means of the process according to the invention, olefins having 6 to 17 carbon atoms can be hydroformylated and the aldehydes thus obtained can be hydrogenated.
The process according to the invention is particularly suitable for the hydroformylation of isomeric olefin mixtures which are produced by oligomerization of propene and butenes. Typical oligomerization products, which can be employed as raw material base for the hydroformylation, include for example dipropene, tripropene and tetrapropene as well as dibutene, tributene and tetrabutene.
Preferably, alcohols having 9 to 13 C atoms are produced from the corresponding olefins by means of the process according to the invention, in particular isononanols from dibutenes.

The oligomerization products of n-butenes are available on a large industrial scale via the known oligomerization processes, for example the Octol® process of Huls and the Dimersol® process of IFP (J. Schulze, M. Homann: "C4-Hydrocarbons and Derivates", pages 69 et seq., Springer Verlag, Berlin/Heidelberg, 1989).
The aldehydes obtained in the process according to the invention can be hydrogenated to the desired alcohols by the known hydrogenation processes in the gas phase or liquid phase (SRI International, Report No. 21 C, April 1986, pages 53 et seq.). Suitable catalysts for the hydrogenation of aldehydes are in particular, copper chromite catalysts, nickel catalysts and copper-zinc catalysts. In part, the hydrogenation of the aldehydes to the alcohols already takes place in the 1-stage process.
The present invention is explained in more detail by the examples which follow:
Comparison example: Known process for the production of isononanol from dibutene
Precarbonylation:
1000 ml of water containing cobalt acetate (about 1.0 % by weight of cobalt, calculated as metal) are initially introduced into a 2 1 stirred stainless steel autoclave. Synthesis gas at a CO/H2 volume ratio of 1: 1 is introduced at 170°C and 280 bar into the autoclave with stirring (1000 rpm). The formation of the cobalt carbonyl complexes during the precarbonylation can be monitored analytically by sampling offset in time. After a precarbonylation time of 6 hours, about 65 % of the cobalt salt employed is converted to the active cobalt catalyst, namely the cobalt hydridocarbonyl complexes.

A marked shortening of the precarbonylation time can be obtained by addition of alcohols which are poorly miscible with water or not all, such as, for example, 2-ethylhexanol or isononanol. If the precarbonylation is carried out with a cobalt saltfwater/isononanol mixture (250 ml isononanol and 750 ml of aqueous cobalt acetate solution with 1 % by weight of cobalt, calculated as metal) under the abovementioned conditions, 65 % conversion of the cobalt salt employed to cobalt carbonyl complexes is reached already after 5 minutes. Catalyst extraction:
After completion of the precarbonylation, the autoclave is, for carrying out the catalyst extraction, let down to a synthesis gas pressure of 100 bar and cooled to a temperature of about 60°C. Under these conditions, the cobalt carbonyl complex is extracted, after addition of 500 ml of di-n-butene, into the di-n-butene functioning as an organic phase with intensive stirring (1000 rpm). After an extraction time of about 10 minutes, the extraction mixture is left to stand for a further 10 minutes for the purpose of phase separation, with the stirrer switched off. The olefmic phase contains 0.22 % by weight of cobalt as cobalt carbonyl complex (HCo(CO)4). The - aqueous phase contains, in addition to 0.35 % by weight of cobalt as cobalt(II) salt, also about 0.57 % by weight of cobalt as non-extracted cobalt carbonyl complex. This means that only about 12 % of the extractable cobalt carbonyl complex was extracted into the olefinic phase. Hydroformulation:
After the catalyst extraction, the aqueous phase is let out of the autoclave, and a further 500 ml of di-n-butene are fed in. Subsequently, the olefinic phase loaded with cobalt hydridocarbonyl complex is hydroformylated with synthesis gas at a CO/H2 volume ratio of 1:1 at a temperature of 175°C and a pressure of 260 bar. After a reaction time of 4 hours, virtually no further synthesis gas is absorbed and the hydroformylation is complete.

Decobalting:
For the decobalting, the autoclave is let down and the product mixture is cooled to about 100°C. By treating the reaction mixture with air below 100°C in the presence of dilute acetic acid, the cobalt carbonyl complexes are oxidized and the resulting cobalt salts are extracted back into the aqueous phase.
According to an analysis by gas chromatography, the organic phase has the following composition in % by weight:
12.5 % of Cg-hydrocarbons, 44.5 % of isononanals, 29.5 % of isononanols, 3.5 % of esters (isononyl formates), 5 % of acetals and 5 % of higher-boiling residue.
Hydrogenation:
The isononanals and isononyl formates are hydrogenated to the isononanols in the presence of a copper chromite catalyst at 20 to 30 bar and 150 to 250°C in the gas phase.
Example 1: Production of isononanols from dibutene
The process according to the invention is carried out in a continuous pilot plant which essentially consists of a high-pressure tubular reactor (90 mm diameter, 3600 mm length) and a downstream decobalting vessel (20 1 capacity) packed with raschig rings, and a phase separation vessel. The reactor space of the high-pressure reactor is cascaded by means of perforated plates built in perpendicular to the direction of flow. A 3-component mixing nozzle is used for the metering of the starting materials. The reactor contents can be heated or cooled by the installed heating and cooling devices as required.

Since the precarbonylation is accelerated in the presence of an alcohol and/or aldehyde, isononanol or an isononanal/isononanol mixture can be initially introduced as a starting aid into the reactor at the beginning of the 1-stage process according to the invention. After the reactor has been brought to the operating temperature of 160 to 180°C, a di-n-butene from the Huls Octol process, aqueous cobalt acetate solution with 1 % by weight of cobalt, calculated as metal, and synthesis gas at a CO/H2 volume 10 ratio of 1:1 are continuously fed to the reactor via the mixing nozzle.
The throughputs are set as follows: 5.0 kg/h of di-n-butene and 0.45 kg/h of cobalt acetate solution. The reactor is pressure-controlled with synthesis gas to a constant reaction pressure of 280 bar at a synthesis gas - throughput of 2.5 to 3.5 m (s.t.p.)/h. The selected di-n-butene throughput corresponds to a space-time loading (LHSV) relative to the reactor volume of about 0.3 h"1 (0.3 m3 of d-n-butene per m3 of reactor volume and per hour).
The organic phase is continuously taken off at the top of the reactor and let down to 10 to 15 bar into the decobalting stage. The aqueous phase fed as cobalt acetate solution to the reactor is taken off as process water containing cobalt complex at the bottom of the reactor under level control and likewise let down into the decobalting stage.
In the decobalting stage, the two liquid phases, together with the gas arising on the letdown (unconverted synthesis gas), are freed of cobalt catalyst by oxidation of the cobalt carbonyl complexes at 140°C by means of air or oxygen in the presence of aqueous acidic cobalt salt solution (process water) and then separated in a downstream separation vessel. The organic cobalt-free phase is further processed, but the aqueous cobalt salt solution is recycled via the mixing nozzle to the 1-stage process. The unconverted synthesis gas is used again or discarded.

Under the selected reaction conditions, di-n-butene conversions of more than 90 % are achieved.
The discharged crude product after the decobalting has, according to an analysis by gas chromatography, the following composition in % by weight: 7.0 % of CB-hydrocarbons, 29.7 % of isononanals, 53.1 % of isononanols, 4.2 % of esters (isononyl formates) and 6.0 % of high-boiling residue.
The high-boiling residue can very simply be separated from the valuable products by distillation.
After the decobalting, the crude product is converted to isononanol (mixture of isomers) by hydrogenation and subsequent distillation in known downstream processing steps. The hydrogenation of the crude product is carried out in the gas phase at 20 to 25 bar and 170 to 250°C in the presence of a copper chromite catalyst.
Example 2: Production of isotridecanol from tri-n-butene
The process according to the invention is carried out in the same way in the pilot plant described in Example 1.
Since the precarbonylation is accelerated in the presence of an alcohol and/or aldehyde, iso-tridecanol and/or an iso-tridecanol/iso-tridecanal mixture can be initially introduced as a starting aid at the beginning of the 1-stage process according to the invention.

After the reactor has been brought to the operating temperature of 160 - 180°C, the starting materials tri-n-butene from the Huls Octol process, aqueous cobalt acetate solution with 1 % by weight of cobalt, calculated as metal, and synthesis gas at a CO/H2 volume ratio of 1:1 are continuously fed to the reactor via the mixing nozzle.
The throughputs are set as follows: 1.65 kg/h of tri-n-butene and 0.15 kg/h of cobalt acetate solution. The reactor is pressure-controlled with synthesis gas to a constant reaction pressure of 280 bar and a synthesis gas throughput of 0.8 to 1.2 m (s.t.p)/h. The selected tri-n-butene throughput corresponds to a space-time load relative to the reactor volume (LHSV) of about 0.1 h" (0.1 m of tri-n-butene per m of reactor volume and per hour).
The reactor product is further processed as described in Example 1.
Under the selected reaction conditions, tri-n-butene conversions of at least 80 % are achieved.
The discharged crude product after the decobalting has, according to an analysis by gas chromatography, the following composition in % by weight: 16.5 % by weight of C12hydrocarbons, 73.5 % of iso-tridecanals and iso-tridecanols and 10.0 % of high-boiling residue.
After the decobalting, the crude product is converted to iso-tridecanols (mixture of isomers) in downstream known processing steps by hydrogenation in the presence of a copper chromite catalyst at 20 to 30 bar and 150 to 250°C in the liquid phase and subsequent distillation.



WE CLAIM:
1. A process for the production of alcohols having 7 to 18 C atoms by
hydroformylation of the corresponding olefins with a synthesis gas in the presence of
an organic phase containing a cobalt catalyst at temperatures from 50 to 220°C and
pressures from 100 to 400 bar and subsequent hydrogenation of the aldehydes thus
obtained, the cobalt catalyst being formed by reacting an aqueous cobalt salt solution
in the presence of an organic solvent, which is only slightly miscible with water or not
at all, with synthesis gas, and the organic phase containing the cobalt catalyst being
obtained by extraction of the cobalt catalyst formed from the aqueous phase by means
of an organic extractant which is only slightly miscible with water or not at all, which
comprises carrying out the formation of the cobalt catalyst, the extraction of the cobalt
catalyst formed into the organic phase and the hydroformylation of the corresponding
olefins in a 1-stage process.
2. The process as claimed in claim 1, wherein the formation of the cobalt catalyst, the extraction of the cobalt catalyst formed into the organic phase and the hydroformylation of the corresponding olefins are carried out in one single reactor.
3. The process as claimed in claims 1 and 2, wherein alcohols having 9 to 13 C atoms are produced from the corresponding olefins.
4. The process as claimed in claim 3, wherein isononanols are produ- 25 ced from dibutenes.
5. The process as claimed in any of claims 1 to 4, wherein the process is carried out continuously.

6. The process as claimed in any of claims 1 to 5, wherein the reactor space of the 1-stage process is subdivided by at least one partition device.
7. The process as claimed in any of claims 1 to 6, wherein the - aqueous cobalt salt solution, olefin, synthesis gas, an organic solvent, which is only slightly miscible with water or not at all, and an organic extractant, which is only slightly miscible with water or not at all, are simultaneously fed to the reactor of the 1-stage process,
8. The process as claimed in claim 7, wherein the aqueous cobalt salt solution, olefin, synthesis gas, an organic solvent, which is only slightly miscible with water or not at all, and an organic extractant, which is only slightly miscible with water or not at all, are fed to the reactor of the 1-stage process by means of a mixing nozzle.
9. The process as claimed in any of claims 1 to 6, wherein an organic solvent, which is only slightly miscible with water or not at all, and an organic extractant, which is only slightly miscible with water or not at all, are initially introduced into the reactor of the 1-stage process and the aqueous cobalt salt solution, olefin and synthesis gas are simultaneously fed to the reactor of the 1-stage process.
10. The process as claimed in claim 9, wherein an organic solvent, which is only
slightly miscible with water or not at all, and an organic extractant, which is only
slightly miscible with water or not at all, are initially introduced into the reactor of the
1-stage process and the aqueous cobalt salt solution, olefin and synthesis gas are fed to
the reactor of the 1-stage process by means of a mixing nozzle.

11. The process as claimed in any of claims 1 to 6, wherein an organic extractant, which is only slightly miscible with water or not at all, is initially introduced into the reactor of the 1-stage process and the aqueous cobalt salt solution, olefin, synthesis gas and an organic solvent, which is only slightly miscible with water or not at all, are fed simultaneously to the reactor of the 1-stage process.
12. The process as claimed in claim 11, wherein an organic extractant, which is only slightly miscible with water or not at all, is initially introduced into the reactor of the 1-stage process and the aqueous cobalt salt solution, olefin, synthesis gas and an organic solvent, which is only slightly miscible with water or not at all, are fed to the reactor of the 1-stage process by means of a mixing nozzle.
13. The process as claimed in any of claims 1 to 12, wherein the organic solvent, which is only slightly miscible with water or not at all, is an olefin and/or an aldehyde and/or an alcohol.
14. The process as claimed in claim 13, wherein the organic solvent, which is only slightly miscible with water or not at all, is the reaction product from the 1-stage
process.
15. The process as claimed in any of claims 1 to 14, wherein the organic extractant, which is only slightly miscible with water or not at all, is an olefin and/or an aldehyde and/or an alcohol.
16. The process as claimed in claim 15, wherein the organic extractant, which is only slightly miscible with water or not at all, is the reaction product from the 1-stage process.

17. The process as claimed in any of claims 1 to 16, wherein the solvent, which is only slightly miscible with water or not at all, and the extractant, which is only slightly miscible with water or not at all, are identical.
18. The process as claimed in any of claims 1 to 17, wherein the - aqueous cobalt salt solution, olefin and synthesis gas are simultaneously fed to the reactor of the 1-stage process.

19. The process as claimed in claim 18, wherein the aqueous cobalt salt solution, olefin and synthesis gas are fed to the reactor of the 1- stage process by means of a mixing nozzle.
20. The process as claimed in any of claims 1 to 19, wherein the reaction product of the 1-stage process is treated with air, with addition of aqueous acidic cobalt salt solution, for oxidizing the cobalt catalyst and, after separation into an organic phase containing the reaction products and an aqueous phase containing the cobalt salt, the aqueous phase is recycled to the 1-stage process.
21. The process as claimed in any of claims 1 to 20, wherein the organic phase,
remaining after the removal of the cobalt catalyst, is hydrogenated and the alcohols
thus obtained are recovered from the hydrogenation product.


Documents:

1832-mas-1997- abstract.pdf

1832-mas-1997- claims duplicate.pdf

1832-mas-1997- claims original.pdf

1832-mas-1997- correspondence others.pdf

1832-mas-1997- correspondence po.pdf

1832-mas-1997- description complete duplicate.pdf

1832-mas-1997- description complete original.pdf

1832-mas-1997- form 1.pdf

1832-mas-1997- form 26.pdf

1832-mas-1997- form 3.pdf

1832-mas-1997- form 4.pdf


Patent Number 207685
Indian Patent Application Number 1832/MAS/1997
PG Journal Number 26/2007
Publication Date 29-Jun-2007
Grant Date 20-Jun-2007
Date of Filing 19-Aug-1997
Name of Patentee DEGUSSA AG
Applicant Address BENNIGSENPLATZ 1, D-4047 DUSSELDORF.
Inventors:
# Inventor's Name Inventor's Address
1 Dr.DIETMAR GUBISCH LEVERKUSENER STRASSE 14, D-45772 MARL
2 KLAUS ARMBRUST ROEDDER 16 B, D-48249 DULMEN.
3 Dr.ALFRED KAIZIK GENDARFER STRASSE 30, D-45772 MARL.
4 Dr.BERNHARD SCHOLZ BRUGGENPOTH 55, D-45768 MARL
5 Dr.RUDOLF NEHRING GRIESHEIMER STRASSE 12, D-45772 MARL
PCT International Classification Number C07C31/125
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 196 54 340.1 1996-12-24 Germany