MXPA97009932A

MXPA97009932A - Procedure for obtaining oxo-alcoholsuperio

Info

Publication number: MXPA97009932A
Application number: MXPA/A/1997/009932A
Authority: MX
Inventors: Gubisch Dietmar; Kaizik Alfred; Scholz Bernhard; Armbrust Klaus; Nehring Rudolf
Original assignee: Degussa Ag*
Priority date: 1996-12-24
Filing date: 1997-12-09
Publication date: 1998-10-30

Abstract

The invention relates to a process for obtaining alcohols with 7 to 18 carbon atoms, by hydroformylating the corresponding olefins with synthesis gas, in the presence of an organic phase containing a cobalt catalyst, at temperatures of 50 at 220 [deg.] C. and pressures of 100 to 400 bar and then a hydrogenation of the aldehyde-like aldehydes, the cobalt catalyst being formed with synthesis gas, reacting an aqueous saline solution of cobalt in the presence of an organic solvent that is not miscible or only slightly miscible with water , and obtaining the organic phase containing the cobalt catalyst by extraction of the aqueous phase of the cobalt catalyst formed with an organic miscible extraction agent or only slightly miscible with water. The formation of the cobalt catalyst, the extraction to the organic phase of the formed cobalt catalyst and the hydrofomilation of the corresponding olefins are carried out in a one-step process. The oxo-alcohols which are obtained with the aid of the process according to the invention are used for the preparation of carboxylic acid esters as plastic softeners.

Description

PROCEDURE FOR OBTAINING OXO-SUPERIOR ALCOHOLS The present invention relates to a process for obtaining alcohols with 7 to 18 carbon atoms by hydroformylating the corresponding olefins with synthesis gas, in the presence of an organic phase containing a cobalt catalyst, at temperatures of 50 to 220 ° C and pressures of 100 to 400 bar and then a hydrogenation of the aldehydes thus obtained, forming the cobalt catalyst with synthesis gas, reacting an aqueous saline solution of cobalt in the presence of an organic solvent that is not mixed or little is mixed with water, and the organic phase containing the cobalt catalyst is obtained by extraction of the aqueous phase of the cobalt catalyst formed with an organic extraction agent that is not mixed or mixed very little with water. In addition, the invention relates to the use of alcohols obtained for the production of esters of carboxylic acids as softeners for plastics. Hydroformylation of olefins with carbon monoxide and hydrogen to obtain richer carbon atom aldehydes in the presence of transition metal catalysts, such as cobalt and rhodium compounds, is known as oxosynthesis. In general, in the hydroformylation of olefins to aldehydes, a high production of straight chain aldehydes is sought: the intermediates in the production of the industrially important softening alcohols for plastics and alcohols for washing agents. While linear and terminal olefins (so-called α-olefins) can be hydroformylated very well with rhodium catalysts, or phosphine-modified cobalt (J. Falbe, Ed: "New Synthesis With Carbon Monoxide", Springer-Verlag, Berlin 1980, pp. 55 et seq.), For less reactive olefins, for non-terminal olefins, as well as for non-terminal and branched olefins, unmodified cobalt and rhodium catalysts are preferably used. In the presence of modified catalysts, the non-terminal and branched olefins are hydroformylated very slowly, or only partially. The foregoing excludes a possible use of modified catalysts for industrial hydroformylation of non-terminal and branched olefins. The hydroformylation of polymeric and isomeric mixtures of olefins, which contain terminal and non-terminal olefins, as well as non-terminal and branched olefins, is advantageously carried out with unmodified cobalt catalysts. Compared with rhodium catalysts, with cobalt catalysts, starting from a starting olefin, high yields of straight chain aldehydes are particularly demanded. Examples of polymeric and isomeric mixtures of typical olefins are those which are preferably converted by hydroformylation with cobalt catalysts to the corresponding oxo-aldehydes, the dimers, trimers and tetramers of propene, of the n-butenes (1- and 2- butene) and of iso-butene. According to known methods, hydroformylation with cobalt catalysts is carried out as a multi-stage process, which includes the following four levels: obtaining the catalyst (precarbonylation), the extraction of the catalyst, the hydroformylation of olefin and the removal of the catalyst from the reaction product (de-cobalt). Since the development of oxosynthesis, each stage of the hydroformylation process with cobalt catalysts was continuously improved and modified. In the first stage of the process, precarbonylation, starting from an aqueous cobalt saline solution, reacting with carbon monoxide and hydrogen, gives the catalytic complex (HCo (CO) 4) necessary for hydroformylation. According to DE-OS 21 39 630, the precarbonylation is preferably carried out at temperatures of 100 to 160 ° C and under synthesis gas pressures of 200 to 300 bar., in the presence of activated carbon, zeolites or basic ion exchangers, which are loaded with cobaltocarbonyl. DE-OS 22 44 373 discloses an improved continuous carbonylation process, in which a clear clipping of the reaction time is achieved by passing the synthesis gas and cobalt aqueous saline solutions, in equi-current, in the presence of organic solvents that contain oxygen, not irascible or difficult to mix with water, through an area in which a turbulent flow is maintained. An advantageous embodiment is the use of a turbulence tube under pressure to maintain the turbulent flow and the addition of alcohols or aldehydes with 4 to 10 carbon atoms as organic solvent. In the second stage of the process, the extraction of the catalyst, the cobalt catalyst obtained in the first stage of the process is extracted from the aqueous phase with an organic phase, preferably with the olefin by hydroformylating. According to DE-OS 21 06 252 it is convenient to use the reaction products and by-products of hydroformylation for the extraction of the catalyst, in addition to the olefin, if the selected reaction conditions are insoluble in water and low liquids. The extraction of the catalyst is preferably carried out in countercurrent, at temperatures of 20 to 100 ° C and under synthesis gas pressures of 100 to 400 bar. After phase separation, the organic phase charged with the cobalt catalyst is brought to the third stage of the process, hydroformylation. From DE-OS 21 39 630 it is known that in the third stage of the process, the hydroformylation, the olefins charged with the cobalt catalyst can be hydroformylated in a high pressure reactor, with synthesis gas, at temperatures of between 70 and 170 ° C and pressures of 100 to 400 bar, to obtain the corresponding aldehydes. A part of the aldehyde formed, under the conditions of hydroformylation, in particular at high temperatures, can be hydrogenated to alcohol. The discharge of the reactor, which contains in addition to the valuable aldehyde and alcohol products, also secondary products, non hydroformylated residual olefin and cobalt catalyst, is decompressed to 1 to 15 bar and is then taken to the processing stage of the reactor. catalyst. In the fourth stage of the process, the de-boiling, the organic phase of the reactor discharge is released from the cobaltocarbonyl complexes in the presence of complex-free process water, by means of an oxygen or air treatment. According to WO 93/24438, the de-cobalt is carried out at temperatures of 60 to 100 ° C and at pressures of 1 to 20 bar. In this way, the cobalt catalyst is oxidatively destroyed and the resulting cobalt salts are extracted back into the aqueous phase. The aqueous cobalt salt solution resulting from the de-cobalt is returned to the first stage of the process, precarbonylation. Another embodiment is described in WO 93/24437 and EP-OS 0 183 546. Here, before the oxidative destruction of the cobalt catalyst, gas washing is carried out with synthesis gas or nitrogen. The products of the reaction in the remaining organic phase, after separating the gas phase, are transformed into the corresponding alcohols in other processing steps, such as hydrogenation and distillation. The processes for obtaining various known oxo-aldehyde steps, in the presence of cobalt catalysts, present a series of technical disadvantages. Thus, in order to obtain the cobalt catalyst necessary for hydroformylation, two technically expensive process steps, precarbonylation and catalyst extraction are required. Due to the processes of transition of substances that take place in a lot of stages of the process, transition of gas / liquid substances in the precarbonylation and transition of liquid / liquid substances in the extraction of the catalyst, two pressure-resistant devices are required, separated from each other, such as for example stirring boiler or columns with filling bodies. The hydroformylation itself then occurs again in a separate pressure reactor. The removal of the cobalt catalyst is linked to another part of the installation. Hydroformylation processes of various known stages, therefore, require, in addition to a large amount of technical work, a large investment. Therefore, the present invention is based on the objective of developing a new hydroformylation process of olefins with a subsequent hydrogenation of the aldehydes obtained, which is easier to carry out from a technical and economic point of view. Surprisingly, it has been discovered that the formation of the cobalt catalyst, the extraction to the organic phase of the formed cobalt catalyst and the hydroformylation of the corresponding olefins can be carried out in a one-step process. That is to say, the first three steps of the process of the conventional processes, the precarbonylation, the extraction of the catalyst and the hydroformylation, are carried out in a one-stage process, preferably in a reactor. This eliminates the costly separation of devices from the process steps. The above is of a particular economic interest, since the reduction of the stages of the process means a considerable reduction of the investment costs. In the process according to the invention, precarbonylation, extraction and hydroformylation take place in parallel and, in part, in situ. In addition, the process of a stage according to the invention is preferably carried out continuously, preferably by circulating the cobalt salt solution which is produced after the de-cobalt. Therefore, it is the object of the present invention a process for obtaining alcohols with 7 to 18 carbon atoms, by hydroformylation of the corresponding olefins, with synthesis gas, in the presence of an organic phase containing a cobalt catalyst , at temperatures of 50 to 220 ° C and pressures of 100 to 400 bar and then a hydrogenation of the aldehydes thus obtained, forming the cobalt catalyst with synthesis gas, reacting an aqueous cobalt saline solution in the presence of an organic solvent not miscible or slightly miscible with water, and obtaining the organic phase containing the cobalt catalyst by extracting the aqueous phase of the formed cobalt catalyst, with an organic extraction agent immiscible or not very miscible with water, which is characterized because the formation of the cobalt catalyst, the extraction to the organic phase of the cobalt catalyst formed and the hydroformila The corresponding olefins are made in a one-step process. Preferably, the formation of the cobalt catalyst, the extraction to the organic phase of the formed cobalt catalyst and the hydroformylation of the corresponding olefins are carried out in a single reactor. Furthermore, the object of the present invention is the use of the alcohols obtained according to the same, for the production of esters of carboxylic acids as softeners for plastics. The process according to the invention is preferably carried out continuously. Suitable cobalt salts are preferably water-soluble cobalt salts, such as formates and acetates. Cobalt acetate has been particularly suitable, which is preferably used as an aqueous solution with a cobalt content of 0.2 to 2% by weight, particularly preferably 0.5 to 1.5% by weight, calculated as metal. The organic solvent can be the olefin by hydroformylating and / or an aldehyde and / or an alcohol, the aldehyde and the alcohol preferably being the reaction products that were formed during hydroformylation. That is, the organic solvent immiscible or slightly miscible with water is preferably an olefin and / or an aldehyde and / or an alcohol, particularly preferred is the reaction product of the one-step process. The extraction agent required for the extraction of the aqueous phase from the cobalt catalyst can be any organic solvent immiscible or difficult to mix with water, provided that it has a sufficient solubility for the cobalt catalyst. However, a mixture of the olefin by hydroformylating and the aldehydes and / or alcohols formed during hydroformylation is preferably used. That is to say, as an organic extraction agent which is immiscible or not very miscible with water, an olefin and / or an aldehyde and / or an alcohol is preferably used, particularly the product of the reaction of the one-stage process. More preferably, the organic solvent immiscible or slightly miscible with water and the organic extraction agent immiscible or slightly miscible with water, are identical. In the process according to the invention, particular importance is attached to the dosage of the starting substances in the reactor of the one-stage process. The dosing device must guarantee a good mixing of the phases and the creation of a phase exchange surface as high as possible.

For dosing the starting substances, dosing devices known in the art can be used, for example, turbulence tubes filled with filler bodies or mixing nozzles for multi-stage systems. The dosage is preferably carried out with a mixing nozzle, maintaining a turbulent flow. Aqueous cobalt saline solution, olefin, synthesis gas, an organic solvent immiscible or only slightly miscible with water and an organic extraction agent immiscible or only slightly miscible with water can be fed simultaneously, in particular by means of a nozzle of mixing, to the reactor of the one-stage process. In another variant of the process according to the invention, an organic solvent that is immiscible or only slightly miscible with water and an organic extraction agent that is not miscible or only slightly miscible with water and can simultaneously feed into the reactor can be disposed of in the one stage process. to the one-stage process reactor, in particular by means of a mixing nozzle, the aqueous cobalt saline solution, the olefin and the synthesis gas. In another embodiment of the present invention, an organic extraction agent that is not miscible or only slightly miscible with water and can simultaneously feed into the reactor of the one-stage process, in particular by means of a nozzle, can be previously arranged in the reactor of the one-stage process. mixture, the aqueous cobalt saline solution, the olefin, the synthesis gas and an organic solvent not miscible or only slightly miscible with water. Preferably, cobalt aqueous salt solution, olefin and synthesis gas are fed simultaneously to the one-stage process reactor, in particular by means of a mixing nozzle, the cobalt aqueous salt solution, the olefin and the synthesis gas. The one-stage process, which includes precarbonylation, catalyst extraction and hydroformylation, can be carried out at temperatures of 100 to 250 ° C and under pressures of 100 to 400 bar. Temperatures of 160 to 220 ° C and pressures of synthesis gas of 200 to 300 bar have been particularly proven. The volume ratio of carbon monoxide to hydrogen in the synthesis gas is generally between 2: 1 and 1: 2, in particular 1: 1. The synthesis gas is preferably used in a slight excess with respect to the amount that is stoichiometrically required. The one-stage process can be carried out, for example, in high-pressure, vertical, cylindrical bubble column reactors, generally known, without or with an integrated coaxial insertion tube. In the preferred embodiment of the process according to the invention, the reactor space of the one-stage process is divided by at least one separating device. This separating device may be, for example, a perforated disk or a screen bottom and is suitably arranged perpendicular to the direction in which the flow of reactants and products flows. Through the cascaded reactors, the back-mixing is strongly reduced with respect to the simple bubble column and the flow behavior is close to that of a tube reactor. This technical 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 discharge of the reactor (organic and aqueous phase), the aqueous phase being able to be completely or partially removed at the bottom of the reactor, after leaving it, it can be decompressed at 10 to 15 bar and take the de-cobalt necessary to remove the cobalt catalyst. In the de-cobalt stage, the product discharge, in the presence of an aqueous cobalt acid aqueous solution (process water), with air or oxygen, at temperatures of 50 to 180 ° C, can be released from the cobaltocarbonyl complexes. Aqueous cobalt acid aqueous solution (process water) has a cobalt content of 0.2 to 2.0% by weight, calculated as metal, and a pH of 3 a. This one can be adjusted, for example, with acetic acid. The de-cobalt, conveniently, can be carried out at temperatures of 120 to 150 ° C, to ensure that the acétals that are formed in the process of a stage due to sequential reactions are decomposed as much as possible to obtain the desired valuable products aldehyde and alcohol. The de-cobalt is preferably carried out in a pressure vessel filled with filling bodies, such as for example Raschig rings, creating in said container a phase exchange surface as high as possible. The organic phase now released from cobalt compounds can be separated from the aqueous phase in a subsequently connected 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 fed back to the one-stage process and is again used as the starting substance for the obtaining the cobalt catalyst. In a more suitable manner, therefore, the process according to the invention is carried out in such a way that the product of the reaction of the one-stage process, for the oxidation of the cobalt catalyst with air, is treated by adding saline solution. Aqueous cobalt acid and after separation in an organic phase containing the reaction products and an aqueous phase containing the cobalt salt, the aqueous phase is fed back to the one-stage process. Next, the organic phase remaining after removing the cobalt catalyst can be hydrogenated and the alcohols thus obtained can be obtained from the product of the hydrogenation, for example, by distillation. Under the reaction conditions of the process according to the invention, in addition to aldehydes, the corresponding alcohols are also partially hydrogenated. The aldehydes and alcohols, after de-cobalting, can be separated from the reactor discharge and processed individually. However, preferably all the organic discharge of the reactor is processed to the corresponding alcohols according to known procedures, for example, by hydrogenation and subsequent distillation. The alcohols obtained according to the process according to the invention are particularly suitable as softening alcohols and washing agents. The aldehydes can also be used for the production of carboxylic acids. The softening alcohols are converted by esterification, for example with phthalic acid anhydride (PSA), into customary softeners for polyvinyl chloride (PVC).

With the aid of the process according to the invention, olefins with 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 obtained by the oligomerization of propene and butenes. Typical oligomerisates which can be used as a raw material base for hydroformylation include, for example, di-, tri- and tetra-propene, as well as di-, tri- and tetra-butene. Preferably, with the aid of the process according to the invention, alcohols with 9 to 13 carbon atoms are obtained from the corresponding olefins, in particular isononanols from dibutenes. The oligomerizations of n-butenes, through the known oligomerization processes, for example, through the Octol® process of Hüls and the Dimersol® process of IFP, are accessible on a large scale (J. Schulze, M. Homann: " C4-Hydrocarbons and Derivats ", pp. 69 et seq., Springer Verlag, Berlin / Heidelberg, 1989). The aldehydes obtained in the process according to the invention can be hydrogenated according to the known hydrogenation processes, in the gaseous or liquid phase, to obtain the desired alcohols (SRI International, Report No. 21 C, April 1986, pp. 53 And next) . As a catalyst for the hydrogenation of aldehydes, copper, nickel and copper-zinc chromite catalysts are particularly suitable. In part, the hydrogenation of the aldehydes to the alcohols takes place already in the one-stage process. The present invention is illustrated in more detail on the basis of the following examples.

Comparative Example: Known procedure for the preparation of isononanol from dibutene Precarbonylation: 1000 ml of water containing cobalt acetate (approximately 1.0% by weight cobalt) are placed in a stirred autoclave of 2 1 of refined steel. calculated as metal). Under stirring (1000 r.p.m.) synthesis gas is fed into the autoclave with a CO / H2 volume ratio of 1: 1 at 170 ° C and 280 bar. By taking samples displaced in time, the formation of cobaltocarbonyl complexes during precarbonylation can be followed analytically. After a precarbonylation time of 6 hours, approx. 65% of the cobalt salt used in the activated cobalt catalyst, the cobaltohydridocarbonyl complexes. A clear cut of the precarbonylation time can be achieved by adding alcohols that are not miscible or difficult to mix with water, such as 2-ethylhexanol or isononanol. If the precarbonylation is carried out with a mixture of cobalt / isononanol salt water (250 ml of isononanol and 750 ml of cobalt acetate aqueous solution with 1% by weight of cobalt, calculated as metal) under the conditions indicated above, achieves a transformation of 65% of the cobalt salt used in cobaltocarbonyl complexes already after 5 minutes.

Catalyst extraction: After finishing the precarbonylation, the autoclave is decompressed for the extraction of the catalyst at a synthesis gas pressure of 100 bar and cooled to a temperature of approx. 60 ° C. Under these conditions, the cobaltocarbonyl complex, after adding 500 ml of di-n-butene, under intense stirring (1000 r.p.m.) is extracted into the di-n-butene which functions as the organic phase. After an extraction time of approx. 10 minutes, the extraction mixture is left to rest for another 10 minutes with the agitator off, in order to separate the phases. The olefin phase contains 0.22% by weight of cobalt as a cobaltocarbonyl complex (HCo (CO)). The aqueous phase contains, in addition to 0.35% by weight of cobalt as cobalt (II) salt, also approx. 0.57% by weight of cobalt as non-extracted cobaltocarbonyl complex. This means that only approx. 12% of the removable cobaltocarbonyl complex.

Hydroformylation: After extraction of the catalyst, the aqueous phase is let out of the autoclave and another 500 ml of di-n-butene are added. Subsequently, the olefin phase loaded with cobalt hydrocarbonyl complex is hydroformylated with synthesis gas with a CO / H2 volume ratio of 1: 1, at a temperature of 175 ° C and at a pressure of 260 bar. After a reaction time of 4 hours, virtually no more synthesis gas is absorbed and the hydroformylation is complete.

Descobaltado: For decocking, the autoclave is decompressed and the product mixture is cooled to approx. 100 ° C. By treating the reaction mixture with air at 100 ° C in the presence of dilute acetic acid, the cobaltocarbonyl complexes are oxidized and the resulting cobalt salts are again quenched into the aqueous phase. The organic phase has, according to a gas chromatography analysis, the following composition in% by weight: 12.5% of C8 hydrocarbons, 44.5% of isononanals, 29.5% of isononanols, 3.5% of esters (isononylformates), 5% of acetals and 5% higher boiling residue.

Hydrogenation: The isononanals and isononylformates are hydrogenated in the gas phase, in the presence of a cobalt chromite catalyst, at 20 to 30 bar and 150 to 250 ° C, to obtain the isononalols.

Example 1: Obtaining isononanols from dibutene The process according to the invention is carried out in a continuous installation for tests, which basically consists of a high-pressure reactor (diameter 90 mm, length 3600 mm) and a container of subsequently connected descobalt (capacity 20 1), filled with Raschig rings, as well as a phase separation vessel. Through five perforated sheets, installed perpendicular to the fluid direction, the space of the high pressure reactor is arranged in cascade. For the dosing of the starting substances, a 3-substance mixing nozzle is used. The content of the reactor, according to the requirements, can be heated or cooled through the installed heating and cooling devices. Since the precarbonylation is accelerated in the presence of an alcohol and / or an aldehyde, at the beginning of the one-stage process, it is possible to initially dispose in the reactor isononanol or an isononanal / isononanol mixture as starting aid. After the reactor was brought to the operating temperature of 160 to 180 ° C, di-n-butene from the Octol de Hüls process, an aqueous solution of cobalt acetate, is continuously fed to the reactor through the mixing nozzle. with 1% by weight of cobalt, calculated as metal, and synthesis gas with a CO / H2 volume ratio of 1: 1. The following flow rates are adjusted: 5.0 kg / h of di-n-butene and 0.45 kg / h of cobalt acetate solution. The reactor is regulated in terms of pressure by synthesis gas at a constant reaction pressure of 280 bar, with a synthesis gas flow rate of 2.5 to 3.5 Nm3 / h. The selected di-n-butene flow rate corresponds to a space-time load referred to the reactor volume (LHSV) of approx. 0.3 h "1 (0.3 m3 di-n-butene per m3 of reactor volume and hour) The organic phase is continuously extracted from the reactor head and compressed in the de-boiling stage at 10 to 15 bar. The cobalt acetate solution is fed to the reactor as a cobalt complex-containing process water and is also compressed in the de-cobalt stage, in the de-cobalt stage, both liquid phases, together with the gas that is added to the reactor. produces decompression (untransformed synthesis gas), at 140 ° C with air or oxygen, in the presence of aqueous cobalt acid aqueous solution (process water), through oxidation of the cobalt complexes, is released from the catalyst The cobalt-free organic phase is then processed, whereas the cobalt aqueous saline solution is fed back to the one-stage process through the tober. Mixing The untransformed synthesis gas is still used or discarded. Under the selected reaction conditions, transformations of di-n-butenes of more than 90% are achieved. The discharge of the crude product after desolvating presents, according to a gas chromatography analysis, the following composition in% by weight: 7.0% of C8 hydrocarbons, 29.7% of isononanals, 53.1% of isononanols, 4.2% of ester (isononilformiate) and 6.0% residue of high boiling temperature. The high boiling temperature residue can be separated very simply from the valuable products by distillation. After de-cobalting, the crude product is converted to isononanol (isomeric mixture) by hydrogenation and subsequent distillation, through known subsequent 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: Obtaining isotridesanol from tri-n-butene The process according to the invention is carried out in the same way in the test installation described in example 1. As the precarbonylation is accelerated in the presence of an alcohol and / or aldehyde, at the beginning of the process of a stage according to the invention, iso-tridecanol and / or an iso-tridecanol / iso-tridecanal mixture can be initially arranged in the reactor as starting aid. After the reactor was brought to the operating temperature of 160-180 ° C, the tri-n-butene starting materials from the Octol process from Hüls, aqueous acetate solution are fed continuously through the mixing nozzle. of cobalt with 1% by weight of cobalt, calculated as metal, and synthesis gas with a CO / H2 volume ratio of 1: 1. The following flow rates are adjusted: 1.65 kg / h of tri-n-butene and 0.15 kg / h of cobalt acetate solution. The reactor is regulated in terms of pressure with synthesis gas at a constant reactor pressure of 280 bar, with a synthesis gas flow rate of 0.8 to 1.2 Nm3 / h. The selected tri-n-butene flow corresponds to a space-time load of the reactor volume (LHSV) of approx. 0.1 h "1 (0.1 m3 of tri-n-butene per m3 of reactor volume and hour) The discharge of the reactor is further processed as described in example 1. Under the selected reaction conditions, triac transformations are achieved. -n-butene of at least 80% The crude product discharge after de-cobalting, presents according to a gas chromatography analysis the following composition in% by weight: 16.5% of C8 hydrocarbons, 73.5% of iso-tridechannels and iso -tridecanols, as well as 10.0% residue of high boiling temperature After de-cobalting, the crude product is transformed in the presence of a cobalt chromite catalyst, at 20 to 30 bar and 150 to 250 ° C, in iso-tridecanols (isomeric mixture) in the liquid phase and following distillation, through known subsequent processing steps.

Claims

NOVELTY OF THE INVENTION Having described the foregoing invention, property is claimed as contained in the following: CLAIMS

1. A process for obtaining alcohols with 7 to 18 carbon atoms, by hydroformylating the corresponding olefins with synthesis gas, in the presence of an organic phase containing a cobalt catalyst, at temperatures of 50 to 220 ° C. and pressures of 100 to 400 bar and then a hydrogenation of the aldehydes thus obtained, the cobalt catalyst being formed with synthesis gas, reacting an aqueous saline solution of cobalt in the presence of an organic solvent immiscible or only slightly miscible with water, and obtaining the organic phase containing the cobalt catalyst by extraction of the aqueous phase of the cobalt catalyst formed with an organic agent of non-miscible extraction or only slightly miscible with water, characterized in that the formation of the cobalt catalyst, the extraction to the organic phase of the cobalt catalyst formed and the hydroformylation of the corresponding olefins was effected They are in a one-stage process.

2. A process according to claim 1, characterized in that the formation of the cobalt catalyst, the extraction into the organic phase of the cobalt catalyst formed and the hydroformylation of the corresponding olefins are carried out in a single reactor.

3. A procedure according to the claims 1 and 2, characterized in that alcohols with 9 to 13 carbon atoms are obtained from the corresponding olefins.

4. A process according to claim 3, characterized in that isononanols are obtained from dibutenes.

5. A method according to claims 1 to 4, characterized in that the process is carried out continuously.

6. A process according to claims 1 to 5, characterized in that the space of the reactor of the one-stage process is subdivided by at least one separating device.

7. A process according to claims 1 to 6, characterized in that the aqueous cobalt saline solution, the olefin, the synthesis gas, an organic solvent immiscible or only slightly miscible with water and a non-miscible organic extraction agent or only little miscible with water are simultaneously fed to the reactor of the one-stage process.

8. A process according to claim 7, sarasterized because the aqueous saline solution of cobalt, the olefin, the synthesis gas, a non-miscible organic solvent Or only slightly miscible with water and an organic miscible agent or only slightly miscible with water are fed to the reactor of the one-stage process by means of a mixing nozzle.

9. A method according to the claims 1 to 6, sarasterized because an organic solvent immiscible or only slightly miscible with water and an organic extraction agent immiscible or only slightly miscible with water are previously arranged in the reactor of the one-stage process and the aqueous saline solution of cobalt, the olefin and synthesis gas are simultaneously fed to the reactor of the one-stage process.

10. A procedure according to the claim 9, characterized in that an organic solvent immiscible or only slightly miscible with water and an organic extraction agent immiscible or only slightly miscible with water are previously placed in the reactor of the one-step process and the aqueous saline solution of cobalt, the olefin and the synthesis gas are fed to the one-stage process reactor by means of a mixing nozzle.

11. A process according to claims 1 to 6, characterized in that an organic extraction agent that is immiscible or only slightly miscible with water is previously placed in the reactor of the one-stage process and the aqueous cobalt saline solution, the olefin, the Synthetic gas and an organic solvent not miscible or only slightly miscible with water are simultaneously fed to the reactor of the one-stage process.

12. A method according to claim 11, sarasterized because an organic extraction agent immiscible or only slightly miscible with water is previously available in the reactor of the one-stage process and the aqueous saline solution of cobalt, the olefin, the synthesis gas and a non-miscible organic solvent or only little miscible with water are fed to the reactor of the one-stage process by means of a mixing nozzle.

13. A process according to claims 1 to 12, characterized in that the organic solvent immiscible or only slightly miscible with water is an olefin and / or an aldehyde and / or an alcohol.

14. A process according to claim 13, characterized in that the organic solvent that is not miscible or only slightly miscible with water is the reaction product of the one-step process.

15. A process according to claims 1 to 14, characterized in that the non-miscible organic agent or only slightly miscible with water is an olefin and / or an aldehyde and / or an alcohol.

16. A process according to claim 15, characterized in that the organic extraction agent, which is immiscible or only slightly miscible with water, is the reaction product of the one-step process.

17. A process according to claims 1 to 16, characterized in that the organic solvent immiscible or only slightly miscible with water and the organic extraction agent immiscible or only slightly miscible with water are identical.

18. A process according to claims 1 to 17, sarasterized in that the aqueous cobalt salt solution, the olefin and the synthesis gas are simultaneously fed to the one-stage process reactor.

19. A procedure according to the claim 18, characterized in that the aqueous cobalt salt solution, the olefin and the synthesis gas are fed to the one-stage process reactor by means of a mixing nozzle.

20. A process according to claims 1 to 19, sarasterized in that the reaction product of the one-stage process, for the oxidation of the cobalt catalyst with air, is treated by adding cobalt aqueous acid salt solution and after separation into the cobalt. an organic phase containing the products of the reaction and an aqueous phase containing the cobalt salt, the aqueous phase is fed back to the one-stage process.

21. A process according to claims 1 to 20, characterized in that the remaining organic phase is hydrogenated after removal of the cobalt catalyst and the alcohols thus obtained are obtained from the hydrogenation product.

22. The use of the alcohols obtained according to claims 1 to 21 for obtaining carboxylic acid esters as a plasticizer.