Method of producing saturated carboxylic acid derivatives

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing saturated carboxylic acids and derivatives thereof, comprising the following steps: (a) reacting an unsaturated fatty acid derivative, in which the carboxyl group is prepared for reaction to form a modified carboxyl group so as to prevent or, in any case, minimise any possible reactions of the carboxyl group modified that way, when realising the method, with an oxidising compound in the presence of a catalyst capable of catalysing oxidation of the ethylene double bond of the unsaturated fatty acid derivative to obtain an intermediate product of a vicinal diol reaction; and (b) reaction of said intermediate compound with oxygen or an oxygen-containing compound in the presence of a catalyst which is capable of catalysing oxidation of hydroxyl groups of the vicinal diol to carboxyl groups, characterised by that both steps (a) and (b) are realised in the absence of an added organic solvent and that, the ratio of water to diol at step (b) is less than 1:1.

EFFECT: improved method.

31 cl, 2 ex

 

The technical FIELD

The present invention relates to a process for the preparation of saturated carboxylic acids and their derivatives, which includes stages:

(a) interaction derived unsaturated fatty acid with an oxidizing compound in the presence of a catalyst capable of catalyzing an oxidation reaction of a double ethylene communication derived unsaturated fatty acid with the intermediate reaction product vicinal diol; and

(b) interaction of intermediate compounds with oxygen or a compound containing oxygen, in the presence of a catalyst capable of catalyzing an oxidation reaction of hydroxyl groups of the vicinal diol to carboxyl groups.

PRIOR art

The method according to the type specified above, is defined as the oxidative degradation of unsaturated fatty acids. During the first reaction is an intermediate compound, which is a vicinal diol, in which two hydroxyl groups are bound to carbon atoms that are the source associated double ethylene bond.

Ways oxidative degradation of fatty acids and their derivatives, such as, for example, esters of fatty acids, are known from the literature. For example, a method of the type specified above is described in patent number EP 0666838. In the mentioned patent method of oxidizing destructs and is characterized by both stages (a) and (b) is carried out in the absence of any added organic solvent and the fact that during stage (b) water is added to the reaction mixture obtained in the reaction stage (a) to obtain the ratio of water/diol in the range from 1:1 to 5:1 before the interaction of the reaction mixture with oxygen or a compound containing oxygen, in the presence of compounds of cobalt as a catalyst.

This method does not involve any treatment of the intermediate reaction product (vicinal diol) and does not require the addition of solvents to implement the oxidation of diols, which occurs in the presence of water. However, the characteristics of the intermediate compound, which is formed in the end of the first stage, in particular its high viscosity, lead to the necessity of adding large quantities of water to ensure the implementation of the second stage of the method.

From the point of view of industrial production this fact is particularly disadvantageous, since it implies the need to have reactors with large volumes. Moreover, at the end of the way if you have a large amount of residual water treatment for the regeneration of dissolved catalysts, as well as its subsequent removal, associated with the presence of organic residue, are extremely about emerytalne.

Finally, the mixture obtained according to patent no EP 0666838, have a pasty, oily and sticky texture.

In order to overcome these disadvantages and other disadvantages which will be explained in the following description, was developed by the method described in the present invention.

The INVENTION

The method according to the present invention actually can get saturated carboxylic acids and their derivatives, using as starting substances unsaturated fatty acids without any need of adding significant quantities of water at the stage (b) the reaction of oxidative degradation, in addition to moderate quantities of water solution in which the dissolved catalyst. The present invention relates to a process for the preparation of saturated carboxylic acids and their derivatives, which includes stages:

(a) interaction derived unsaturated fatty acid with an oxidizing compound in the presence of a catalyst capable of catalyzing an oxidation reaction of a double ethylene communication derived unsaturated fatty acid with the intermediate reaction product vicinal diol; and

(b) interaction of the specified intermediate compounds with oxygen or a compound containing oxygen, in the presence of a catalyst capable of catalyzing the reaction ocil is of the hydroxyl groups are vicinal diol to carboxyl groups,

characterized in that the two stages (a) and (b) is carried out in the absence of added organic solvent and the fact that water is not added to the reaction mixture resulting from stage (a), during stage (b), except water solution in which the dissolved catalyst to obtain a mass ratio of water/diol less than 1:1, preferably less than 0.7:1, most preferably less than 0.5:1.

Under derived unsaturated fatty acids involve unsaturated fatty acid in which the carboxyl group is prepared to interact with the formation of the modified carboxyl groups in such a way as to prevent or, in any case, to minimize any possible reaction of the carboxyl group-modified thus, in the process of implementing method.

The fatty acid can be either monounsaturated or polyunsaturated. Examples of unsaturated fatty acids are 9-tetradecenoic acid (myristoleate acid), 9-hexadecanoate acid (palmitoleic acid), 9-octadecenoate acid (oleic acid), 12-hydroxy-9-octadecenoate acid (ricinoleic acid), 9-Aksenova acid (gadolinia acid), 13-docosanoate acid (erucic acid), 15-tetracosanoic acid (acetabula acid), 9,12-octadecadienoic acid (linol the Wai acid) and 9,12,15-octadecatrienoic acid (linolenic acid).

Can also be used a mixture of derivatives of unsaturated fatty acids, such as, for example, mixtures presented in vegetable oils such as soybean oil, olive oil, castor oil, sunflower oil, peanut oil, rapeseed oil, corn oil, palm oil, etc.

Especially preferred is the use of monounsaturated fatty acids. Especially preferred is oleic acid and erucic acid, especially their esters, and most preferred are the methyl ester.

The carboxyl group of the unsaturated fatty acids can be modified through interaction with alcohol (with receipt of ester), amine (obtaining amide), etc. In the case of esterification of the ester group includes preferably1-C9alkyl group, more preferably methyl, ethyl, propyl. Especially preferred is methyl oleate, in particular the methyl oleate obtained by transesterification of methanol with the triglycerides contained in sunflower oil with high oleic acid content.

Oxidizing a substance used for carrying out stage (a) of the method according to the invention, is a preferably aqueous solution of hydrogen peroxide in concentrations from 30% to 70%, predpochtitelno 35% to 60% and even more preferably from 40% to 49.9%.

Preferably the catalyst of stage (a) refers to a group consisting of tungsten and molybdenum, especially acids and alkali metal salts of these acids. The specified catalyst is present in amounts of from 0.03 wt.% up to 2 wt.%, more preferably from 0.07 wt.% up to 1.8 wt.% and even more preferably from 0.08 wt.% up to 1.5 wt.% relatively derived unsaturated fatty acids.

To improve the distribution of the catalyst in the reaction mixture may preferably be added dispersing agent such as surfactant (belonging to the classes of anionic, cationic, nonionic and amphoteric (zwitter-ionic) surfactants).

As for the catalyst in stage (b), it is preferably belongs to the class of compounds based on cobalt, such as cobalt acetate, cobalt chloride and cobalt sulfate or mixtures thereof, used in quantities of from 0.1 mol.% up to 3 mol.%, preferably from 0.2 mol.% up to 2 mol.% and more preferably from 0.3 mol.% to 1.5 mol.% relative to the diol obtained in stage (a).

As the catalyst of stage (b) to the compounds based on cobalt can be added to compounds of tungsten and molybdenum and their acid and alkali metal salts of these acids, preferably up to 2 mol.% relative to the diol.

In the preferred example is sushestvennee method according to the invention at the beginning of stage (a) add a small amount of intermediate compounds, which should be formed at the end of the stage (a) (the so-called "reactive support), because the original presence of intermediate compounds, which should be formed, contributes to the activation reaction.

"Reactive support may be preferably added in an amount of not more than 5%, more preferably not more than 3 wt.%.

Preferably in the case when the reactive support is not available in the initial reaction mixture, it is useful to add some amount of H2O2and wait for the temperature increase in the exothermic process. When this happens, it means that there is an interaction of unsaturated fatty acids with H2O2and , therefore, formed dihydroxide, which activates the reaction.

In the preferred form of the method according to the invention during a stage (a) nitrogen purge with the purpose of distillation of the water formed in this way. Thus prevent excessive dilution of H2O2.

In the preferred form of the method according to the invention at the end of stage (a) water present in the reaction mixture, and the catalyst dissolved in it, is removed. The catalyst is then recovered in a known methods. In the case of tungsten acid can, for example, the concentration of the activated water (driving part) and then acidified them with hydrochloric acid to precipitate tungstic acid. Consequently, it is possible to regenerate the catalyst, which can thus be reused for subsequent reactions.

The removal of water at the end of stage (a) also represents an additional advantage. The catalyst for stage (a) may in fact present during stage (b) of the method together with the addition of catalyst required for this second stage of the method. When removing water at the end of stage (a) and the catalyst dissolved in it actually becomes possible to add the two catalysts in the stoichiometric proportions required for the optimization stage (b).

The temperature of the reaction method according to the present invention is in the range from 50°C to 90°C. the Time required for the reaction stage (a) of the method according to the present invention is in the range from 2 to 10 hours, whereas the time required for carrying out stage (b)is in the range from 3 to 12 hours.

The method according to the invention can be performed preferably at atmospheric pressure or, in any case, at low pressures (20 bar (2 MPa), preferably not more than 15 bar (1.5 MPa), and more preferably not more than 10 bar (1 MPa)), thereby confirming a particular advantage from the standpoint of industrial production. Different from the final product of the method described in patent number EP 0666838, which is a pasty, oily and sticky mixture, the final product of the method according to the present invention is a transparent oil containing a derivative of dicarboxylic acid, monocarboxylic acid, and a number of esters of vicinal diol formed at the end of stage (a). In the case where a derivative of the original fatty acid is a pure methyl oleate specified oil respectively contains a complex onomatology ester of azelaic acid (complex onomatology broadcast decollate resulting from oxidative degradation), pelargonium acid, as well as a number of ester methyl ester dihydroxystearic acid with monomethylaniline and/or pelargoniums acid.

Individual components can be further purified using techniques, which use different solubility of the products obtained and various derivatives and/or using distillation, and in any case using traditional methods.

Before the above purification method may be useful for the esterification of the mixture as a whole, or acid within it.

Specified oil can be in any case used by itself or can be a raw material for the formation of lubricating oil sludge is biodiesel, or intermediate substance in the reaction of obtaining prepolymers.

INFORMATION CONFIRMING the POSSIBILITY of carrying out the INVENTION

Example 1

Stage (a) (Reaction with H2About2)

Into the reactor were introduced:

1,000 g of crude methyl oleate (methyl esters from sunflower oil with high oleic acid content: 92% of methyl oleate; 1% merlinoite; 4% methylvalerate; 3% methyltaurine),

- 10 grams of tungstic acid,

- 50 g of the crude methyldihydromorphine (intermediate compound obtained at the end of stage (a), formed from the previous reaction, the so-called "reactive support).

The temperature was increased to 65°C. and was added 250 cm3to 49.9%-aqueous solution of N2About2within 3 hours during the reaction, nitrogen was purged for distillation of the water formed in the way. Approximately 70 cm3water drove for 3 hours After addition of H2O2added approximately 7 g of sodium bicarbonate dissolved in 100 cm3water for making tungsten acid tungstate, which is more soluble in water, and the aqueous phase was separated in a hot state (at approximately 60°C) from the organic phase. Thus, separated approximately 150 g of an aqueous solution containing the catalyst, and received approximately 1150-1200 g oil the phase. This oil phase 50 g was retained as a "reactive support" for the subsequent reaction.

The oil phase contained 75-80% methyldihydromorphine, a small amount of H2O2(1-2%), palmitate and stearate, who was not involved in the reaction, methyl-9,10-epoxyester, which is an intermediate product of the reaction, pelargonium acid and monomethylaniline, which is already formed in this reaction stage, and acetals, which are the result of secondary reactions.

Stage (b) (Reaction with O2)

To the oil phase was added an aqueous solution of the catalyst prepared as follows:

(1150 g of oil phase)

and 15.1 g of Na2WO4was dissolved in 200 cm3water.

- 6,9 g OSA2(0.03 mol) was dissolved in 100 cm3water.

The two solutions were mixed, followed by precipitation of cobalt hydroxide. Co(II) was then oxidized to Co(III) by adding the stoichiometric amount of H2O2. Adding HCl, the product is then acidified to a pH of 3, dissolving thus dark green precipitate. The product in the end brought up to specified volume with the help of 400 cm3of distilled water.

Then the temperature was raised to about 75-80°C, after which 30 were barbotirovany O2at a speed of 30 l/h of the Reaction lasted approximately 5-6 hours Beginning oxidation was found for treason who, s the color of the catalyst solution from green to yellow.

At the end of the reaction the aqueous phase containing the catalyst was separated in a hot state, for processing in subsequent stages.

The oil phase (a little more than 1150 g) contained pelargonium acid, monomethylaniline, a small amount of azelaic acid and dihydroxytestosterone acid which has not reacted, metrpolitan and mailstart presented in esters from the outset, and a mixture of complex monoamino and diesters methyldihydromorphine with pelargonium and monometallism atlanata.

The oil phase was treated with sodium carbonate or ammonium to turn monomethylaniline acid and pelargoniums acid into the corresponding water-soluble salts of sodium or ammonium. Two salt was separated from the residue by adding water.

From 1150 g of the reaction product was received approximately 300 g of residue and approximately 850 g of the mixture of acids. By subsequent distillation of the mixture of acids has received approximately 350 g pelargonii acid and 450 g monomethylaniline.

The above result corresponds to a yield of approximately 70% for both products.

Example 2

Stage (a)

Into the reactor were introduced:

1,000 g of crude methyl oleate (methyl esters from sunflower oil with high oleic acid content: 84% of methyl oleate; 9% of merlinoite; 4% methylvalerate; 3% meth is stearate),

- 10 grams of tungstic acid,

- 50 g of the crude methyldihydromorphine (intermediate compound obtained at the end of stage (a), formed from the previous reaction, the so-called "reactive support).

The temperature was increased to 60-62°C and was added to 250 cm349.9 percent aqueous solution of H2O2within 3 hours the Reaction was carried out as described in Example 1.

After the formation of salts of tungstic acid with sodium bicarbonate solution aqueous phase containing tungstate, separated, whereas the organic phase (approximately 1150 g of oil phase)containing 70-75% of methyldihydromorphine, was ready for the subsequent oxidation stage.

Stage (b)

To the oil phase was added an aqueous solution of salts of Co (II) as catalyst (5 g CoCl2·6H2O (0.02 mol) in 400 cm3distilled water).

The temperature was maintained at about 75-80°C. and then was barbotirovany O2at a speed of 30 l/h for 6 hours

At the end of the reaction the aqueous phase containing the catalyst was separated in a hot state, for processing in subsequent stages.

Received approximately 1150 g of oil phase, which mainly consisted of pelargoniums acid and monomethylaniline in the quantity corresponding to the output approximately 65-70% for both products.

1. A method of obtaining a saturated carboxylic acids and the derivatives thereof, incorporating the following stages:
(a) interaction derived unsaturated fatty acid in which the carboxyl group is prepared to interact with the formation of the modified carboxyl groups in such a way as to prevent or, in any case, to minimize any possible reaction of the carboxyl group-modified thus, in the implementation of the method, with the oxidizing compound in the presence of a catalyst capable of catalyzing an oxidation reaction of a double ethylene communication derived unsaturated fatty acid with the intermediate reaction product vicinal diol; and
(b) interaction of the specified intermediate compounds with oxygen or a compound containing oxygen, in the presence of a catalyst capable of catalyzing an oxidation reaction of hydroxyl groups of the vicinal diol to carboxyl groups,
characterized in that the two stages (a) and (b) is carried out in the absence of added organic solvent and the fact that the ratio of water/diol in the reaction stage (b) is less than 1:1.

2. The method according to claim 1, where at the end of stage (a) remove the water present in the reaction mixture, and the catalyst dissolved in it.

3. The method according to claim 1, where the aqueous solution of catalyst added to the beginning of stage (b), and the only water you add is what I water solution, where dissolved catalyst.

4. The method according to claim 1, where in the early stage (a) of the intermediate compound, which should be formed at the end of stage (a), add in the amount of less than 5 wt.%.

5. The method according to claim 4, where the intermediate connection type in the amount less than 3 wt.%.

6. The method according to claim 1, where the catalyst of stage (a) refers to a group consisting of compounds of tungsten and molybdenum, in particular acids and alkali metal salts of these acids.

7. The method according to claim 6 where the catalyst is present in an amount of from 0.03 to 2 wt.% relatively derived unsaturated fatty acids.

8. The method according to claim 6 where the catalyst is present in amount of from 0.07 to 1.8 wt.% relatively derived unsaturated fatty acids.

9. The method according to claim 6 where the catalyst is present in amount of from 0.08 to 1.5 wt.% relatively derived unsaturated fatty acids.

10. The method according to claim 1, where the catalyst of stage (b) is selected from the group consisting of compounds of cobalt.

11. The method according to claim 10, where compounds of cobalt selected from the group consisting of cobalt acetate, cobalt chloride and cobalt sulfate.

12. The method according to claim 10, where compounds of cobalt are present in amounts of from 0.1 to 3 mol.% relative to the diol.

13. The method according to claim 10, where compounds of cobalt are present in an amount of from 0.2 to 2 mol.% relative to the diol.

14. The method according to claim 10, where is soedineniya cobalt present in an amount of from 0.3 to 1.5 mol.% relative to the diol.

15. The method according to claim 10, where the catalyst is selected from the group consisting of tungsten and molybdenum and their acids and alkali metal salts of these acids, are added to a catalyst from the group of compounds of cobalt.

16. The method according to claim 10, where the catalyst is selected from the group consisting of compounds of tungsten and molybdenum, is added to the catalyst from the group of compounds of cobalt in amounts up to 2 mol.% relative to the diol.

17. The method according to claim 1, where the oxidizing compound is a peroxide.

18. The method according to 17, where the hydrogen peroxide is present in an aqueous solution at a concentration of from 30% to 70%.

19. The method according to 17, where the hydrogen peroxide is present in an aqueous solution at a concentration of from 35% to 60%.

20. The method according to 17, where the hydrogen peroxide is present in an aqueous solution at a concentration of from 40% to 49.9%.

21. The method according to claim 1, wherein both stages (a) and (b) is carried out at a pressure of not more than 20 bar (2 MPa).

22. The method according to item 21, where the pressure is 15 bar (1.5 MPa).

23. The method according to item 21, where the pressure is not more than 10 bar (1 MPa).

24. The method according to item 23, wherein both stages (a) and (b) is carried out at atmospheric pressure.

25. The method according to claim 1, where the derivative of unsaturated fatty acids is a derivative of monounsaturated fatty acids.

26. The method according A.25 where derived monounsaturated fatty acids obtained p is the esterification mixtures, including mixtures, present in vegetable oils selected from the group consisting of soybean oil, olive oil, castor oil, sunflower oil, peanut oil, rapeseed oil, corn oil and palm oil.

27. The method according A.25 where monounsaturated fatty acid selected from the group consisting of: 9-tetradecenoic acid (myristoleate acid), 9-hexadecenoic acid (palmitoleic acid), 9-octadecenoic acid (oleic acid), 12-hydroxy-9-octadecenoic acid (ricinoleic acid), Aksenova acid (gadolinio acid), 13-docosenoic acid (erucic acid), 15-tetracosanoic acid (acetabulosa acid).

28. The method according A.25, where the carboxyl group derived unsaturated fatty acid modified through interaction with alcohol with the formation of ester.

29. The method according A.25, where the carboxyl group derived unsaturated fatty acid modified through interaction with alcohol with the formation of ester, and the ester group include C1-C9 alkyl group.

30. The method according A.25, where the carboxyl group derived unsaturated fatty acid modified through interaction with alcohol with the formation of ester, and the ester group is selected from the group consisting of the of utila, ethyl, propyl.

31. The method according A.25 where modified unsaturated fatty acid is a methyl oleate obtained by transesterification of methanol with the triglycerides contained in sunflower oil with high oleic acid content.



 

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9 cl, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: subject of invention is continuous carbonylation of long-chain aliphatic hydrocarbons to produce alcohols, acids, and other oxygen-containing products such as esters. Process comprises paraffin dehydrogenation, carbonylation, and fraction distillation-mediated end product recovery. Advantageously, mixture of paraffins containing different number of carbon atoms isolated from kerosene fraction is processed. Non-converted paraffins are recycled into dehydrogenation zone. Prior to be fed into carbonylation zone, stream is processed by selectively hydrogenating diolefins. In the carbonylation stage, homogenous catalytic system is used containing palladium/imidazole or palladium/triphenylphosphine complex, aliphatic acid (preferably formic acid), and solvent. Catalytic system further includes promoter selected from group: lithium iodide, zirconium chloride, tin chloride, and lithium bromide.

EFFECT: simplified technology, increased conversion of raw materials and selectivity in formation of desired products.

14 cl, 2 dwg, 1 tbl, 11 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing calcium stearate used for stabilization of plastic masses, in manufacture of paint and varnish materials, vitamin and medicinal preparations. Preparing calcium stearate is carried out by interaction of stearic acid and calcium oxide or hydroxide in the equimole ratio of reagents. The process is carried out in the solid phase under atmosphere pressure and intensive stirring without heating in the presence of zeolite of CaX type taken in the amount 6.7-16 wt.-%. Method provides simplifying technology due to a single stage process and improvement of economical indices.

EFFECT: improved preparing method.

7 tbl, 3 ex

The invention relates to chemical technology, in particular to an improved method for producing a saturated monocarboxylic acids WITH4-C8by oxidation of the corresponding aldehydes with oxygen, aldehydes impose additional isopropanol at a volume ratio of isopropanol to the aldehyde, equal 0,0007-0,0038, and the reaction is carried out at a temperature of 50-700With
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