The method of obtaining the highest oxo-alcohols

 

(57) Abstract:

The invention relates to a method for producing alcohols from 7-18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst of the organic phase with 50 - 220oC and a pressure of 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde. The cobalt catalyst was prepared by reacting an aqueous solution of cobalt salt with synthesis gas in the presence of an organic solvent, immiscible or only to a small extent miscible with water. The organic phase containing the cobalt catalyst, obtained by extraction of the formed cobalt catalyst from the aqueous phase using immiscible or only to a small extent miscible with water, the organic extracting agent. Getting a cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins is carried out in one stage, preferably in a single reactor. The flow of all flows of reagents is carried out using a mixing nozzle. As the organic solution is. the technical result - the simplification of the technology, improving the economic performance of the process. 20 C.p. f-crystals.

The invention relates to a method for producing alcohols from 7 to 18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst in the organic phase at temperatures of from 50 to 220oC and pressures from 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde, and cobalt catalyst was prepared by reacting an aqueous solution of cobalt salt with synthesis gas in the presence of an organic solvent, not or only to a small extent miscible with water and the organic phase containing the cobalt catalyst, obtained by extraction of the formed cobalt catalyst from the aqueous phase using not or only to a small extent miscible with water, the organic extracting agent.

Additionally, the invention relates to the use of the obtained alcohols to obtain esters of carboxylic acids as plasticizers used in plastics.

Hydroformylating olefins with carbon monoxide and hydrogen by receiving imeushego, as, for example, compounds of cobalt and rhodium, known as oxazines. Usually when hydroformylating olefins with obtaining aldehydes strive to achieve high proportion of unbranched aldehydes - intermediates in obtaining economic importance of alcohols intended for plasticizers used in plastics, and alcohols for detergents.

If the linear olefins and olefins with terminal double bonds (so-called olefins) very well be hydroformylation in the presence of modified phosphine rhodium or cobalt catalysts (see J. Falbe, ed. : "New Synthesis With Carbon Monoxide", Springer Verlag, Berlin, 1980 , pp. 55 FF.), for weakly reactive olefins, olefins with nekozawa a double bond, and branched olefins with nekozawa double bond is preferably used not modified cobalt and rhodium catalysts.

In the presence of modified catalysts for olefins with nekozawa double bond and branched olefins very slowly or only partially amenable to hydroformylating. This eliminates the possibility of using modified catalysts for effective Ekonomicheskaya polymer and isomeric mixtures of olefins, containing olefins with terminal double bonds and olefins with nekozawa double bond and branched olefins with nekozawa a double bond, preferably carried out with the aid of a modified cobalt catalysts. Compared to rhodium catalysts using cobalt catalysts, based on the same source of olefin, get a bigger yield particularly desirable unbranched aldehydes.

Examples for typical polymer and isomeric mixtures of olefins, which are preferably transformed to the corresponding oxo-aldehydes by hydroformylation in the presence of cobalt catalyst, are dimers, trimers and tetramer of propene, n-butenes (1 - and 2-butene and ISO-butene.

According to the known methods hydroformylation in the presence of cobalt catalyst is carried out in the form of a multi-stage process that contains the following four stages: obtaining a catalyst (pre-carbonylation), extraction of the catalyst, hydroformylating olefins and catalyst removal from the reaction product (ECOBALTICA).

Since the development of oxosynthesis single technological stage of hydroformylation.

In the first process stage, the preliminary carbonyliron, based on the aqueous solution of cobalt salt by reacting with carbon monoxide and hydrogen are necessary for hydroformylation catalyst complex (HCO(CO)4). According to the application DE 2139630 preliminary carbonylation preferably carried out at temperatures from 100 to 160oWith and under the pressure of the synthesis gas from 200 to 300 bar in the presence of activated carbon, zeolites or basic ion exchangers loaded with cobalt CARBONYLS.

In the application DE 2244373 describes an improved, continuous carbonylation, which achieves a significant reduction of the reaction time by filing the original of the substances, i.e., synthesis gas and an aqueous solution of cobalt salt, parallel through a zone in which provide turbulent flow, in the presence of hard or not miscible with water oxygenated organic solvents. As a pre-emptive execution result applying pressure pipes turbulence to ensure turbulent flow and additive alcohols or aldehydes with 4 to 10 carbon atoms as the organic solvent.

On the second technolog extracted from the aqueous phase with an organic phase, preferably using exposed hydroformylation of olefin. According to the application DE 2106252 it is advisable, along with the olefin to use the reaction products and by-products of hydroformylation for the extraction of the catalyst, if they are water-insoluble and liquid under the reaction conditions. The extraction of the catalyst is carried out preferably in counter-current at temperatures from 20 to 100oWith pressure synthesis gas from 100 to 400 bar. After separation of the phases loaded cobalt catalyst in the organic phase is served on a third process stage, hydroformylation.

The application DE 2139630 it is known that in the third process stage, hydroformylation, you can hydroformylating loaded cobalt catalyst for olefins in the reactor high pressure synthesis gas at temperatures of from 70 to 170oC and pressures from 100 to 400 bar with the corresponding aldehydes. Part of the formed aldehyde under the conditions of hydroformylation, in particular at high temperatures, can be gidrirovanii with obtaining alcohol.

Exhaust from the reactor product containing in addition to the valuable products of aldehyde and alcohol and by-products, not hydroformylating obrabotki catalyst.

On the fourth process stage, demobilization, the organic phase is withdrawn from the reactor product is released from the complexes of cobalt carbonyl in the presence of free from complex compounds of process water by treatment with oxygen or air. In accordance with the international application 93/24438 demobilization carried out at temperatures from 60 to 100oC and pressures from 1 to 20 bar. This cobalt catalyst destroy by oxidation, and the resulting cobalt salt is transferred to the aqueous phase. The resulting aqueous solution of the cobalt salt of process demobilization return to the first process stage preliminary carbonylation.

Another form of execution of the method described in international application 93/24437 and in the application EP 0183546. Here before the destruction of the cobalt catalyst oxidation spend gas clean synthesis gas or nitrogen.

The reaction products remaining in the organic phase after separation of the gas phase at later stages of processing such as hydrogenation and distillation, turn to the corresponding alcohols.

Known multi-stage methods of obtaining oxo-aldehydes in the presence of cobalt is investing cobalt catalyst need two technically complex technological stage - preliminary carbonylation and extraction of the catalyst. Because of what is happening on two process stages of the processes of transformation of substances, i.e. the transition of a gas in a liquid at a pre-carbonyliron and the liquid in the liquid at the extraction of catalyst required two separate solid compression apparatus, such as, for example, a boiler with a stirrer or Packed columns. Very hydroformylation then carried out in a separate reactor operating under pressure. The removal of the cobalt catalyst requires additional node setup.

Known multistage methods hydroformylation thus in addition to the large technological efforts also require large investments.

The present invention therefore is to develop a new way of hydroformylating olefins followed by hydrogenation of the resulting aldehydes, which is more simple in terms of technology and more economical.

It has been unexpectedly found that the formation of the cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins can be accomplished in one-step FTUS catalyst and hydroformylation carried out in a one-step process, preferably the reactor.

Thus, there is no more technically complex allocation for individual devices. This is of particular economic importance, since reducing the number of process steps means a significant reduction of investment cost. In the proposed method of pre-carbonylation, extraction and hydroformylation occur simultaneously and partially in situ. Moreover, the proposed single-stage process is preferably carried out continuously, and received after demobilization solution of cobalt salt, preferably circulate.

Therefore, an object of the present invention is a method of producing alcohols from 7 to 18 carbon atoms by hydroformylation corresponding olefins with synthesis gas in the presence containing cobalt catalyst in the organic phase at temperatures of from 50 to 220oC and pressures from 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde, and cobalt catalyst was prepared by reacting an aqueous solution of cobalt salt with synthesis gas in the presence of an organic solvent, not or only to a small extent curable mixture is gosia cobalt catalyst from the aqueous phase using not or only to a small extent miscible with water, the organic extracting agent, characterized in that the formation of the cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins is carried out in a one-step process.

Preferably the formation of the cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins produced in one reactor.

Additionally, an object of the present invention is obtained by application according to the invention of alcohols to obtain esters of carboxylic acids as plasticizers used in plastics.

The proposed method is preferably carried out in continuous mode.

As cobalt salts preferably used water-soluble cobalt salts, such as formate and acetate. Especially proved cobalt acetate, which is preferably used in the form of an aqueous solution containing cobalt, from 0.2 to 2 wt.%, particularly preferably from 0.5 to 1.5 wt.%, in terms of metal.

The organic solvent may be exposed hydroformylating about the during hydroformylation the reaction products.

Thereby, an organic solvent, not or only to a small extent miscible with water, preferably represents an olefin, and/or the aldehyde and/or alcohol, particularly preferably the reaction product of one-stage process.

Necessary for the extraction of the cobalt catalyst from the aqueous phase extracting agent can be any organic solvent that is not or only to a small extent miscible with water, if it has sufficient dissolving power for the cobalt catalyst. Preferably, however, use the mixture subjected to hydroformylation of olefin and formed during hydroformylation aldehydes and/or alcohols.

Therefore as the organic solvent, is not or only to a small extent miscible with water, preferably olefin, and/or the aldehyde and/or alcohol, particularly preferably the reaction product of one-stage process.

Best organic solvent, not or only to a small extent miscible with water, is identical with an organic extracting agent, not or only to a small extent miscible with water.

For the dosage of the original substance can be used known in the art dispensers, such as, for example, filled with elements of the nozzle turbulent pipe or mixing nozzles for multi-phase systems. The dosage is preferably carried out by mixing nozzle with preservation of turbulent flow.

An aqueous solution of cobalt salts, olefin, synthesis gas, organic solvent, not or only to a small extent miscible with water, and the organic extracting agent, not or only to a small extent miscible with water, can be fed into the reactor single-stage process at the same time, in particular through the mixing nozzle.

In another embodiment, the proposed method, an organic solvent, not or only to a small extent miscible with water, and the organic extracting agent, not or only to a small extent miscible with water, can be fed into the reactor by one-stage process, and then simultaneously adding thereto an aqueous solution of cobalt salts, olefin and synthesis gas, in particular, the settlement of extracting agent, not or only to a small extent miscible with water, can be fed into the reactor by one-stage process, and then simultaneously added to an aqueous solution of cobalt salts, olefin, synthesis gas and an organic solvent, not or only to a small extent miscible with water, in particular through the mixing nozzle.

Preferably an aqueous solution of cobalt salts, olefin and synthesis gas fed into the reactor single-stage process at the same time, particularly preferably by means of a mixing nozzle.

Single-stage process that includes pre-carbonyl extraction of the catalyst and hydroformylation can be carried out in a reactor at temperatures from 100 to 250oC and at pressures from 100 to 400 bar. Especially proven in temperatures from 160 to 220oC and pressure of the synthesis gas from 200 to 300 bar. The volume ratio of carbon monoxide and hydrogen in the synthesis gas typically ranges from 2 : 1 to 1 : 2, in particular 1:1. The synthesis gas is mainly used in a small excess relative to the stoichiometric required amount.

One-step process can be performed, for example, in the well-known cylindrical, ASS="ptx2">

In a preferred embodiment of the proposed method reaction chamber one-stage process divides at least one separation device.

This separation device may represent, for example, a perforated plate or mesh plate and it is advisable to install vertically to the flow direction of the reactant and the product.

The cascade reactor design is greatly reduced back mixing compared to a simple bubble column, a description of the current approaches to the characterization of the tubular reactor. Such a technological measure will improve both the yield on the volume/time and the selectivity of hydroformylation.

In a suitable embodiment, the proposed method extracted from the reactor (organic and aqueous phases) product, and the aqueous phase can be prevented completely or partially at the bottom of the reactor, the reactor exit you can bring to the pressure from 10 to 15 bar and serve the product in the necessary removal of the cobalt catalyst in the process of demobilization. At the stage of demobilization exhaust product can be released from the complexes of cobalt carbonyl in the presence of water, Ki 180oC. Aqueous, acidic solution of a cobalt salt (process water) has a content of cobalt, from 0.2 to 2.0 wt.%, in terms of metal, and the pH value from 3 to 4. The pH value can be set, for example, using acetic acid. Demobilization expediently carried out at temperatures from 120 to 150oTo ensure formed in the single-stage process due to consecutive reactions acetal was cut back as much as possible fully to the desired valuable products of aldehyde and alcohol.

Demobilization preferably carried out in the filled elements of nozzles, such as, for example, ring process, pressure vessel, which is created as large as possible surface exchange phases. Exempt from cobalt compounds organic phase product connected to the separation tank can be separated from the aqueous phase. The aqueous phase containing extracted from the organic phase cobalt compounds, for example, in the form of cobalt acetate or cobalt formate, preferably back to the single-stage process and again used as the starting material to obtain a cobalt catalyst.

It is therefore advisable Platonova catalyst processed air with addition of water, acidic solution of cobalt salt, and after separation of containing reaction products of the organic phase containing the cobalt salt in the aqueous phase, the aqueous phase is returned to the single-stage process.

Then remaining after removal of the cobalt catalyst in the organic phase can be gidrirovanii, and thus obtained the alcohols can be derived from the product of the hydrogenation, for example, by distillation.

Under the reaction conditions of the proposed method along with aldehydes in the hydrogenation partially form the corresponding alcohols. Aldehydes and alcohols after demobilization can be separated from the exhaust from the reactor organic product and separately subjected to further processing. However, preferably the entire exhaust from the reactor organic product converted to the corresponding alcohol by known methods, for example, by hydrogenation, followed by distillation.

Obtained by the proposed method alcohols especially suitable as alcohols intended for plasticizers used in plastics, and alcohols for detergents. Additionally, the aldehydes can be used for obtaining carboxylic acids.

Alcohols, prednos acid, turn in standard plasticizers for polyvinyl chloride (PVC).

Using the proposed method can be hydroformylating olefins from 6 to 17 carbon atoms and gidrirovanii thus obtained aldehydes.

The proposed method is especially suitable for hydroformylation isomeric mixtures of olefins, obtained by oligomerization of propene and butenes. Typical oligomers used as raw material for hydroformylation include, for example, di-, tri - and tetraploid, as well as di-, tri - and tetrabutyl.

Preferably using the proposed method are alcohols with 9 to 13 carbon atoms from the corresponding olefins, in particular, isononanol from debutto.

Oligomers of n-butenes can be obtained in krupnoseriynom scale using known methods of oligomerization, for example, a process called Octal company Hulls or method with the name of Demersal company IFP (see Th.Schulze, M. Homann: "C4-Hydrocarbons and Derivates", page 69 FF., the Springer Verlag, Berlin/Heidelberg, 1989).

Obtained by the proposed method aldehydes by means of known methods of hydrogenation can be gidrirovanii in gas or liquid phases in the desired alcohols (see SRI Internat, the catalysts based on copper chromite, Nickel, copper and zinc. Partial hydrogenation of aldehydes to alcohols takes place in a one-step process.

The following examples explain the present invention.

Comparative example: a method of obtaining isononanol from dibucaine

Preliminary carbonylation:

In the autoclave with stirrer (volume 2 l) stainless steel serving 1000 ml containing cobalt acetate water (about 1.0 wt.% cobalt in terms of the metal). With stirring (1000 rpm) autoclave serves synthesis gas with a volume ratio of CO and H21 : 1 at a temperature of 170oC and a pressure of 280 bar. By time-shifted sampling can be performed analytical tracking the formation of carbonyl complexes of cobalt during the pre-carbonyl. After preliminary carbonylation within 6 hours, about 65% of the cobalt salt to make the active cobalt catalyst complexes of gidrocarbonata cobalt.

A significant reduction of the period prior to the carbonylation can be achieved by adding not or hardly miscible with water, alcohols, such as, for example, 2-ethylhexanol or iznaola (250 ml isononanol and 750 ml of an aqueous solution of cobalt acetate with 1% wt. cobalt, in terms of the metal) in the above conditions, a 65% conversion of used cobalt salt complexes of cobalt carbonyl is reached in 5 minutes.

Extraction of the catalyst:

Upon completion of the preliminary carbonylation for carrying out extraction of the catalyst, the pressure of the synthesis gas in the autoclave is reduced to 100 bar and a temperature up to about 60oC. under these conditions, the complex of cobalt carbonyl after addition of 500 ml of di-n-butene with vigorous stirring (1000 rpm) is extracted in acting as the organic phase di-n-butene. After extraction within about 10 min of extraction, the mixture is left to stand off the stirrer for 10 minutes to separate the phases. Olefinic phase contains 0.22 weight. % of cobalt in the form of a complex of cobalt carbonyl (HCO(CO)4). The aqueous phase in addition to 0.35 wt.% cobalt as cobalt (II) salt also contains 0,57 weight. % of cobalt in the form of extracted complex of cobalt carbonyl. This means that only about 12% of the extracted complex of cobalt carbonyl was extracted in the olefin phase.

Hydroformylation:

After extraction of the catalyst, the aqueous phase is removed from the autoclave and serves more than 500 ml of di-n-butene. ZAT is a gas with a volume ratio of CO and H21: 1 at a temperature of 175oC and a pressure of 260 bar. After reaction for 4 hours actually no longer absorbed into synthesis gas, hydroformylation completed.

Demobilizacija:

For demobilization relieve the pressure in the autoclave and the mixture of products is cooled to about 100oC. treating the reaction mixture with air at a temperature below 100oIn the presence of dilute acetic acid oxidizes the carbonyl complexes of cobalt, and the cobalt salt is transferred to the aqueous phase.

According to gas chromatographic analysis of the organic phase has the following composition:

12.5 wt.% hydrocarbons of 8 carbon atoms, to 44.5 wt.% isononanol and 29.5 wt.% isononanol, 3.5 wt.% esters (isononanoate), 5 weight. % acatalog and 5 wt.% the high-boiling residue.

Hydrogenation:

Isononanol and sonomicrometry in the presence of a catalyst based on copper chromite hydronaut in the gas phase with obtaining isononanol at a pressure of from 20 to 30 bar and a temperature of from 150 to 250oC.

Example 1: getting isononanol from dibucaine

The proposed method is carried out at a pilot plant continuous operation, consisting mainly of tubular reaction is analyticaly (capacity 20 l) and tank phase separation. It turns out the cascade design of the reaction chamber of the reactor pressure vessels using five installed vertically to the direction of flow of perforated plates. For the dosage of the original substances using a three-component mixing nozzle. The contents of the reactor can be heated or cooled by the installed heating or refrigerating devices.

Because pre-carbonylation in the presence of alcohol and/or aldehyde is accelerated, at the beginning of the proposed single-stage process can be fed into the reactor isononanol or a mixture of isononanol and isononanol as an initiator of the reaction. After heating the reactor to operating temperature in the range from 160 to 180oWith through a mixing nozzle into the reactor continuously served di-n-butene from a process called Octal company Huls, an aqueous solution of cobalt acetate with 1% wt. cobalt, calculated on the metal, and the synthesis gas with a volume ratio of CO and H21: 1.

Set the following costs: 5,0 kg/h of di-n-butene and 0.45 kg/h of a solution of cobalt acetate. Synthesis gas regulate a constant reaction pressure in the reactor at 280 bar at a flow rate of synthesis gas from 2.5 to 3.5 rules. m3/H. Ukazaniya reactor and hour).

The organic phase is continuously away from the upper part of the reactor and serves on stage demobilization while reducing the pressure to 10 to 15 bar. Fed to the reactor in the form of a solution of cobalt acetate aqueous phase when the level control divert at the bottom of the reactor in the form of process water containing complexes of cobalt, and also serves on the stage of demobilization upon release of pressure.

At the stage of demobilization both the liquid phase together with generated when the discharge pressure gas (not paragonimiasis synthesis gas) at a temperature of 140oWith using air or oxygen in the presence of water, an acidic solution of cobalt salt (process water) by oxidation of the carbonyl complexes of cobalt released from the cobalt catalyst, and then divide them connected in the separation tank. Free from cobalt organic phase is subjected to further processing, and an aqueous solution of cobalt salt through the mixing nozzle return in a one-step process. Not paragonimiasis synthesis gas used on or remove.

Under the reaction conditions reach a degree of conversion of di-n-butene above 90%. Removed from a reactor, the crude product after dicobalt is erode, 29.7 wt.% isononanol, 53,1% wt. isononanol, 4,2 weight. % esters (isononylphenol) and 6.0 wt.% the high-boiling residue.

The high-boiling residue can be easily separated from the valuable products by distillation.

After demobilization the crude product on subsequent well-known stages of processing by hydrogenation, followed by distillation to make isononanol (mixture of isomers),

Hydrogenation of the crude product is carried out in the gas phase at a pressure of from 20 to 25 bar and a temperature of from 170 to 250oIn the presence of a catalyst based on copper chromite.

Example 2: getting isotridecanol of tri-n-butene

The proposed method is carried out on the described in example 1 experimental setup the same way.

Because pre-carbonylation in the presence of alcohol and/or aldehyde is accelerated, at the beginning of the proposed single-stage process can be fed into the reactor from-tridecanol and/or a mixture of ISO-tridecanol and ISO-tridecanol as an initiator of the reaction.

After heating the reactor to operating temperature in the range from 160 to 180oWith into the reactor through the mixing nozzle continuously served the original substances tri-n-butene from when the synthesis gas with a volume ratio of CO and H21 : 1.

Set the following costs: 1,65 kg/h tri-n-butene and 0.15 kg/h of a solution of cobalt acetate. Synthesis gas regulate a constant reaction pressure in the reactor at 280 bar at a flow rate of synthesis gas from 0.8 to 1.2 standards. m3/hours Specified consumption, tri-n-butene corresponds to a flow rate of about 0.1 h-1(0.1 m3tri-n-butene on m3the reactor volume and time).

Exhaust from the reactor product is further processed as described in example 1.

Under the reaction conditions reach a degree of conversion of tri-n-butene at least 80%. Removed from a reactor, the crude product after demobilization according to gas chromatographic analysis has the following composition: 16.5 wt.% hydrocarbons of 8 carbon atoms, is 73.5 wt.% ISO-tridecanol and ISO-tridecanol and 10.0 wt.% the high-boiling residue.

After demobilization the crude product on subsequent well-known stages of processing by hydrogenation in the presence of a catalyst based on copper chromite at a pressure of from 20 to 30 bar and a temperature of from 150 to 250oIn the liquid phase, followed by distillation convert to ISO-tridecanol (mixture of isomers).

1. A method of producing alcohols from 7-18 carbon atoms by hydroformylation phase at 50 - 220oC and a pressure of 100 to 400 bar, with subsequent hydrogenation of the thus obtained aldehyde, and cobalt catalyst was prepared by reacting an aqueous solution of cobalt salt with synthesis gas in the presence of an organic solvent, not or only to a small extent miscible with water and the organic phase containing the cobalt catalyst, obtained by extraction of the formed cobalt catalyst from the aqueous phase using not or only to a small extent miscible with water, the organic extracting agent, characterized in that the formation of the cobalt catalyst, extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins can be accomplished in one-step process.

2. The method according to p. 1, characterized in that the formation of the cobalt catalyst, the extraction of the formed cobalt catalyst in the organic phase and hydroformylation corresponding olefins is carried out in one reactor.

3. The method according to PP. 1 and 2, characterized in that the alcohols with 9 to 13 carbon atoms from the corresponding olefins.

4. The method according to p. 3, otsab carried out in a continuous mode.

6. The method according to PP.1-5, characterized in that the reaction chamber of the single-stage process divides at least one separation device.

7. The method according to PP.1-6, characterized in that the aqueous solution of cobalt salts, olefin, synthesis gas, organic solvent, not or only to a small extent miscible with water, and the organic extracting agent, not or only to a small extent miscible with water, are fed into the reactor single-stage process at the same time.

8. The method according to p. 7, characterized in that the aqueous solution of cobalt salts, olefin, synthesis gas, organic solvent, not or only to a small extent miscible with water, and the organic extracting agent, not or only to a small extent miscible with water, are fed into the reactor single-stage process by means of a mixing nozzle.

9. The method according to PP.1-6, characterized in that the organic solvent is not or only to a small extent miscible with water, and the organic extracting agent, not or only to a small extent miscible with water, are fed into the reactor by one-stage process, and then simultaneously added an aqueous solution of cobalt salt, ol is small extent miscible with water, served in a single-stage reactor process, and then added an aqueous solution of cobalt salts, olefin and synthesis gas through a mixing nozzle.

11. The method according to PP.1-6, characterized in that the organic extracting agent, not or only to a small extent miscible with water, is fed into the reactor by one-stage process, and then simultaneously added an aqueous solution of cobalt salts, olefin, synthesis gas and an organic solvent, not or only to a small extent miscible with water.

12. The method according to p. 11, characterized in that the organic extracting agent, not or only to a small extent miscible with water, is fed into the reactor by one-stage process, and then added an aqueous solution of cobalt salts, olefin, synthesis gas and an organic solvent, not or only to a small extent miscible with water, through the mixing nozzle.

13. The method according to PP.1-12, characterized in that the organic solvent is not or only to a small extent miscible with water, is an olefin and/or aldehyde and/or alcohol.

14. The method according to p. 13, wherein the organic solvent is not or only in a small flat. the manual on PP.1-12, characterized in that the organic extracting agent, not or only to a small extent miscible with water, is an olefin and/or aldehyde and/or alcohol.

16. The method according to p. 15, characterized in that the organic extracting agent, not or only to a small extent miscible with water is a reaction product of one-stage process.

17. The method according to PP.1-16, characterized in that the solvent is not or only to a small extent miscible with water, and extracting agent, not or only to a small extent miscible with water, are identical.

18. The method according to PP.1-17, characterized in that the aqueous solution of cobalt salts, olefin and synthesis gas is simultaneously fed into the reactor by one-stage process.

19. The method according to p. 18, characterized in that the aqueous solution of cobalt salts, olefin and synthesis gas are fed into the reactor single-stage process by means of a mixing nozzle.

20. The method according to PP.1-19, characterized in that the reaction product of the single-stage process for the oxidation of the cobalt catalyst is treated air with addition of water, an acidic solution of cobalt salt, and posdnous phase return in one-step process.

21. The method according to PP.1-20, characterized in that after removal of the cobalt catalyst in the organic phase hydronaut, and thus obtained the alcohol is removed from the hydrogenation product.

 

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FIELD: organic chemistry, in particular production of high oxoalcohols.

SUBSTANCE: invention relates to method for production of high oxoalcohol from isomeric olefin mixture containing from 5 to 24 of carbon atoms. Claimed method includes hydroformylation in presence of catalyst at elevated temperature and elevated pressure. Hydroformylation in carried out in one step, and ones-through olefin conversion is limited in range of 40-90 %. Obtained reaction mixture after catalyst separation is preferably transferred to selective hydration carrying out at 120-220°C and pressure of 5-30 bar in presence of supported catalyst containing copper, nickel and chromium as active ingredients. Hydration product mixture is separated by distillation, and olefin fraction is recycled into hydroformylation step. As starting materials for hydroformylation mixtures of C8-, C9-, C12- or C16-olefins are used.

EFFECT: high olefin conversion ratio, selectivity, and capability.

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EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for synthesis of 1,3-propanediol by the hydroformylation reaction of ethylene oxide with the simultaneous hydrogenation step. Method involves the following steps: (a) contacting a mixture consisting of ethylene oxide, carbon monoxide, hydrogen, water-nonmixing reaction solvent and the hydroformylation catalyst composition; (b) heating this reaction mixture to obtain a monophase mixture of the reaction products comprising 1,3-propanediol wherein separation of phases can be induced by decreasing the temperature; (c) inducing for separation of phases by at least one method chosen from the group comprising: (1) decreasing temperature with combination of addition agent inducing separating into layers to the mixture; (2) reducing temperature in combination with the first addition of co-solvent at first increasing capacity for mixing followed by removal of co-solvent increasing capacity for mixing; (3) the following addition of co-solvent at first increasing capacity for mixing followed by removal of co-solvent increasing capacity for mixing, and (4) addition agent inducing separating phases to the products mixture wherein separating phases results to arising the first phase containing the main part of reaction solvent, at least, 50 wt.-% of the catalyst composition plus unreacted ethylene oxide, and the second phase that comprises the main part of 1,3-propanediol. Extraction of the catalyst residue is carried out preferably from the second phase and its recirculation to the step (a). The end product is isolated by distillation with recycle of unreacted compounds. Invention provides carrying out the process for a single step and simplifying technology for separating reactions products.

EFFECT: improved method for synthesis.

11 cl, 3 tbl, 1 dwg, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to technology of production of higher aldehydes and alcohols via hydrofomylation of olefins. C6-C24-olefins are subjected to hydrofomylation on cobalt or rhodium catalyst to achieve degree of conversion 20 to 98%, whereupon catalyst is removed from the product, regenerated and returned to hydrofomylation reactor. Resulting liquid mixture is separated by distillation into low-boiling olefins- and paraffins-containing fraction and bottom fraction containing aldehydes or aldehydes/alcohols mixture. In the case of alcohols being desired product, product fraction is subjected to hydrogenation on hydrogenation catalyst including copper, nickel, chromium, zinc, molybdenum, or mixture thereof, after which hydrogenate is routed to distillation. Olefins contained in low-boiling fraction are subjected to hydrofomylation comprising above-indicated stages. Bottom fractions obtained in all process stages are processed together in common reaction product separation stage.

EFFECT: increased yield of desired product due to improved technology.

19 cl, 3 dwg, 2 tbl, 6 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component and a iron component alloyed with ligand selected from group consisting of T-heterocycle residue, phosphine, and porphyrin. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen (H2/CO molar ratio being between 2:1 and 6:1), inert solvent, and above-defined catalyst composition, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 1500 to 2500 psig (1034 to 17420 kPa) to form biphasic mixture of reaction products composed of (i) upper phase including at least wt 50% of solvent, at least 50 wt % of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing more than 50% of 1,3-butanediol.

EFFECT: achieved single-stage production of 1,3-butanediol with minimum amounts of impurities and by-products, and increased stability of catalyst.

10 cl, 4 dwg, 4 tbl, 20 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides alternative bimetallic catalyst composition comprising a cobalt component constituted by a number of non-alloyed cobalt carbonyl compounds and a ruthenium component including ruthenium carbonyl compound alloyed with N-heterocyclic ligand selected from group of bidentate and multidentate N-heterocyclic ligands. 1,3-Butanediol production process comprises providing reaction mixture containing ethylene oxide, carbon monoxide, hydrogen, inert organic solvent, and above-defined catalyst, and heating this reaction mixture to temperature from 30 to 150°C at pressure from 100 to 4000 psig (690 to 27580 kPa) over a period of time long enough to obtain biphasic mixture of products composed of (i) upper phase including major part of solvent, at least wt 50% of catalyst composition plus unreacted ethylene oxide and (ii) lower phase containing major part of 1,3-butanediol.

EFFECT: increased yield of product under mild conditions and increased stability of catalyst.

8 cl, 5 dwg, 19 tbl, 98 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved method for preparing 1,3-dioles comprising (i) bringing into contact oxirane, carbon monoxide, and hydrogen at 30 to 150°C and pressure 3 to 25 MPa in essentially water-immiscible solvent in presence of effective amount of homogenous bimetallic hydroformylation cobalt carbonyl-containing catalyst and cocatalyst based on metal selected from ruthenium group and which is bound to phosphine ligand optionally in presence of promoter, wherein molar ratio of ligand to this cocatalyst metal atom is within a range of 0.2:1.0 to 0.4:1.0, under reaction conditions effective to obtain reaction products mixture containing aliphatic 1,3-diol; (ii) adding aqueous solution to reaction product mixture obtained and extracting major part of aliphatic 1,3-diol into said aqueous solution at temperature below 100°C to form aqueous phase containing aliphatic 1,3-diol in higher concentration that that of aliphatic 1,3-diol in reaction product mixture and organic phase containing at least part of bimetallic hydroformylation catalyst; (iii) separating aqueous phase from processing phase; and (iv) optionally recycling at least part of catalyst-containing organic phase to stage (i). Invention also relates to catalyst composition for hydroformylation of ethylene oxide into aliphatic 1,3-propanediol, which composition is obtained via a method comprising (i) preparation of complex A by bringing cocatalyst ruthenium-group metal compound into contact with phosphine ligand at ligand-to-cocatalyst metal atom from 0.2:1.0 to 0.4:1.0; (ii) preparation of complex B by subjecting complex A to redox reaction with cobalt carbonyl.

EFFECT: enabled less costly single-step hydroformylation process.

8 cl, 2 dwg, 4 tbl, 52 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to synthesis of aliphatic 1,3-diol, especially 1,3-propanediol from ethylene oxide and syngas in one step. More specifically, invention relates to catalytic composition, which ensures good yield under mild conditions in single-step 1,3-propanediol synthesis process and manifests advantages regarding expenses and efficiency. Catalytic composition comprises cobalt component including one or more non-alloyed cobalt compounds and ruthenium component including mainly ruthenium carbonyl compound alloyed with phospholanoalkane ligand. Single-step 1,3-propanediol synthesis process is carried out in presence of catalytic composition at 30 to 150°C and pressure at least 690 kPa over a period of time long enough to obtain two-phase reaction product mixture including upper phase containing major part of solvent, at least 50% of catalytic composition and unconverted ethylene oxide and lower phase containing major part of 1,3-propanediol.

EFFECT: enhanced process efficiency and reduced expenses.

10 cl, 4 tbl, 17 ex

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