CZ200725A3 - Process for preparing mixtures of conjugated fatty acids - Google Patents

Abstract

It is a method of producing mixtures of conjugated fatty acids with a linear chain of carbon chain length up to C.sub.18.n. and the total number of double bonds 2 or 3, and a derivative thereof, wherein a first step of direct isomerization of the vegetable oil is effected by the action of heat and an alkaline medium on the salts of the conjugated fatty acids; the derivatization step, followed by optionally purifying the derivative, wherein the steps, in particular the isomerization step, are carried out under vacuum to reduce oxygen and / or air access.

Description

Technical field

The invention relates to a process for the production of mixtures of conjugated fatty acids and their derivatives from oils of the milk thistle fruit (Silybum marianum (L.) GAERTNER) and the honey bee (Dracocephalum moldavica L.) which are used as raw materials for the production of cosmetics and food and feed accessories.

BACKGROUND OF THE INVENTION

The fruit of the milk thistle and the honey bee contain a number of biologically active substances. Oils are an important group of these substances in terms of their positive effects on human health. The general characteristic of these oils is the high content of polyunsaturated fatty acids, especially from the group of ω-3 or ω-6. These acids belong to the group of so-called essential fatty acids, whose intake in the human diet is necessary for the proper functioning of the whole organism. It is known in the art (Karlson P. et al .: Pathobiochemistry, 2nd edition, Academia Praha 1987) that essential fatty acids are essential building blocks for a number of other highly biologically active substances from the prostaglandins, prostacyclins, thromboxanes, leukotrienes, etc. that directly affect the course of biochemical processes in human tissues.

According to CZ 295611, oils in the milk thistle fruit and the bee colonies are contained to a significant extent, corresponding to a weight content of from about 15% to about 35% by weight. depending on climatic conditions, variety and other factors. Oils obtained by pressing the whole fruits of the abovementioned plant species contain as their main component fatty acid esters, predominantly in the form of triacylglycerols, to a lesser extent diacylgylcerols and monoacylglycerols. In addition to these substances, free fatty acids and small amounts of phytosterols, phytosqualenes, phospholipids, terpenic derivatives, dyes, etc., as well as degradation products of all these are present in the oxides. The basic difference in the qualitative composition of the oils of both plant species is the fact that while in the milk thistle oil we find high levels of linoleic acid or 9 (Z), 12 (Z) -octadeca-9,12-dienoic acid (commonly over 50% by weight), the volley from the fruits of the Moldovan apiary is predominantly α-linolenic acid or 9 (Z), 12 (Z), 15 (Z) -ocadadeka9,12,15-trienic acid (normally over 60% by weight).

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In addition to linoleic acid and α-linolenic acid, the geometric and positional isomers of these acids, the so-called conjugated fatty acids, are important for the human body. They are formed, for example, in the digestive tract of ruminants. These conjugated fatty acids are then excreted into milk fat, which thus becomes one of the most important sources of these substances for the human body. A number of positive effects on human health have been reported for conjugated fatty acids that are readily incorporated into metabolic processes in the human body. According to the state of the art, the most important properties include, in particular, an overall improvement in fat metabolism leading to the optimization of fat stores in the human body (WO 2004/096748) and anticancer effect (Agarashi M., Miyazawa T .: Cancer Letters 148 (2000)). , 173-179), anti-decalcifying effect of the bone (US published application US 20050171368), reducing the risk of cardiovascular diseases (European published application EP 1 526 126), strengthening the immune system (international published application WO 03/090739), etc. of these effects, the conjugated fatty acids have potent antioxidant effects and can therefore be considered effective adaptogens (MacDonald AB: J Am. Coll. Nutr. 19 (2) (2000), 111S-118S). In the topical application, the effect of natural UV protection factor of conjugated fatty acids, given by the amount and position of double bonds in the molecules of these substances, is also applied.

Due to changes in dietary habits, general environmental degradation and increased risks due to lifestyle changes and the like, it is desirable to supplement the human diet with conjugated fatty acids to the extent necessary. Although the first attempts have been made to genetically modify plants where conjugated fatty acids and their derivatives would be produced by natural biochemical processes (international published application WO 2004/005442) or studied microorganisms capable of synthesizing conjugated fatty acids by biochemical conversion of natural substances (international published application WO 03/080850), the main source for the artificial preparation of conjugated fatty acids still remains chemical reactions using suitable natural oils and fats as the source material. A number of technologies have been developed for the artificial preparation of conjugated fatty acids from these sources. The vast majority of them are based on the reorganization of the position and geometry of the double bonds in the polyunsaturated fatty acid molecules under the influence of heat. In order to achieve the reaction as rapid as possible, it is suitable to carry out the reaction in an alkaline medium (see International Publication No. WO 03/046115). From the point of view of arrangement, these reactions are carried out both batchwise and in cascade or continuous mode (WO 03/035811). The general complication of these processes is the fact that the fatty acid double bonds are very sensitive to oxidation processes, so to achieve the highest yields and purity of the final products, the reactions themselves have to be carried out with the restriction of oxygen access to the reactants, as reported by Brimberg UI, Kamal-Eldin A .: Eur. J. Lipid Sci. Technol. 105 (2003) 17-22). This effect can be achieved in several ways. The most widespread of these is the application of a suitable inert atmosphere during the reaction itself and subsequent processing of the reaction mixture to the final product. The disadvantage of this process is the need to carefully fill the gas phase above the reaction mixture with an inert gas, which makes it necessary to include this gas in the process and to check the completeness and filling condition before and during all processes.

Another alternative is to carry out the reactions and processing of the products without the presence of a gas phase. Continuous process design is suitable for this process, but it is difficult to regulate, and also due to the fact that during the processes, due to elevated temperatures and the reaction chemistry itself, the expansion of the reaction mixtures is applied, which must be taken into account and appropriately eliminated. .

The obtained products - free fatty acids or their esters - are often additionally freed of undesirable components, which are most often degradation products of substances, primarily present in the starting material or formed only during the reaction itself. Standard techniques such as vacuum distillation (see, for example, International Publication No. WO 2005/067888), simple crystallization (see, for example, International Publication No. WO 2004/055142), or liquid-liquid extraction, are most commonly used for this refining step. a liquid (see, eg, WO 03/104472), and the like. The common denominator of these processes is again the need to eliminate oxidation processes and the need to minimize thermal or alkaline or acidic exposure. In the opposite environment, subsequent reactions are applied which lead to further reorganization of positions or arrangement of double bonds in fatty acid molecules, eventually to the overall degradation of unsaturated fatty acid molecules or their derivatives.

In order to eliminate, under acceptable conditions, the negative effect of oxidation during the reaction leading to the formation of conjugated fatty acids from the oils of the milk thistle and molded apiary, as well as the subsequent processing of the reaction mixture into final products, the need arose in principle. At the same time, it was desirable to apply a sufficiently effective technique to remove any degradation products from the reaction products that would preserve the chemical nature of the products without further alteration due to subsequent reactions or other degradation processes.

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SUMMARY OF THE INVENTION

These drawbacks are largely overcome by a process for the production of mixtures of conjugated fatty acids up to Cu length and total number of double bonds of 2 or 3, and derivatives thereof, first carrying out the step of direct isomerization conversion of vegetable oil by heat and alkaline to conjugated salts. fatty acids, in the next step the fatty acids are released by the action of a mineral acid, after which the mixture of the fatty acids obtained is subjected to a derivatization step followed by optional purification of the derivatives, whereby the individual steps, in particular isomerization step, .

Preferably, the oil is oil of the milk thistle fruit or the honey bee or a mixture thereof.

In particular, all steps of preparing the conjugated fatty acid mixtures and derivatives thereof are carried out in a vacuum environment, i.e. first in an alkaline environment under heat treatment, followed by treatment of the reaction mixture and then esterification with a suitable type of alcohol, preferably ethanol.

The subsequent refining of the final product is carried out on a selective sorbent or its crystallization in the form of inclusion compounds (so-called clathrates or interstitial compounds).

After carrying out the appropriate laboratory and subsequently pilot and operational tests, it has been found that all processes as described and under the conditions indicated are carried out with a high yield and purity of the product, regardless of the type of oil used.

SUMMARY OF THE INVENTION It is an object of the present invention to apply a vacuum to the isomerization reaction in which the position and geometry of the double bonds of polyunsaturated fatty acids from Milk Thistle or Molded Bee Oil is applied to the reaction mixture to significantly reduce oxygen access and / or air causing degradation of the target products.

Restriction of oxygen and / or air is understood to mean that its residual presence above the reaction mixture does not cause measurable degradation of the target products.

Preferably, the pressure above the reaction mixture is maintained at a level of less than 10 kPa, more preferably less than 5 kPa.

Target products are conjugated fatty acids, i.e., positional and geometric isomers of polyunsaturated fatty acids, where the double bonds in their molecules are in conjugated positions. These are, in particular, conjugated fatty acids with a total number of carbons up to C 18 and a total number of double bonds of 2 or 3.

A mixture of conjugated fatty acids is understood to mean, in addition to these acids, a minority of saturated and fatty acids with one double bond.

The vacuum is preferably used also in the next technological step, where the reaction mixture is worked up by shaking with an aqueous mineral acid solution, thereby releasing the conjugated fatty acids from their salts.

Depending on the nature of the equipment, sulfuric acid, hydrochloric acid or phosphoric acid can be used as suitable mineral acids. For the common material design of stainless steel or enamelled reactors, trihydrogenphosphoric acid appears to be the most versatile, which does not cause excessive corrosion, especially of metal components of the apparatus, and the waste products of the reaction (inorganic salts of trihydrogenphosphoric acid) can be used as a quality agricultural fertilizer. After separation of the aqueous phase, the crude product is stripped of water by distilling off at elevated temperature under vacuum. More preferably, the water content after drying is reduced below 0.1 wt%. and the product is further subjected to an esterification reaction with a suitable alcohol type under mineral acid catalysis. Given the intended use of the final product in dietary supplements, it is preferred to use ethanol as a suitable alcohol for the actual esterification. Esters of conjugated fatty acids appear to be advantageous in terms of physical properties and chemical stability. In contrast to the free conjugated fatty acids, their lower alcohol esters occur at room temperature in a liquid state, which is advantageous in terms of handling, dosing and application to the final dosage form. It has also been shown that the stability of conjugated fatty acid esters with respect to oxidation is higher than that of free acids, which is advantageous especially in the subsequent processing of these substances into the final dosage form and to ensure its stability and hence the declared active ingredient content. et al .: J. Agric Food Chem 50 (2002), 2977-2983).

Preferably, all of the operations described above are carried out in batch stirred reactors which allow the formation of a saturated vapor layer of the reaction mixture components above the reaction mixture itself at a given pressure in the reactor, thereby protecting the reaction mixture from residual oxygen and / or air.

For purification of crude conjugated fatty acid esters, adsorption method of degradation products and sensory unacceptable substances such as e.g.

dyes and odors, on a suitable sorbent type. Inorganic minerals appear to be advantageous in this respect. · • · an an an an an an an an an an an an an an an an an an an Silica-based sorbents which are capable of effectively trapping undesirable substances, in particular of a polar nature. The advantage of this method of refining conjugated fatty acid esters is that the process can be carried out at room temperature, in particular at 15-25 ° C, in a continuous configuration excluding air oxygen and / or air, thus avoiding oxidative degradation of the product as well as its possible chemical changes due to subsequent reactions, activated in particular by elevated temperature or by the presence of an alkaline or acidic environment. In this step, the refined product is stripped of both the residual alcohol content used for the esterification and the residual water content and can be directly filled into the final package. More preferably, the refining process may be carried out in an arrangement where the sorbent is packed into a container of suitable shape (hereinafter referred to as the column) from which residual air is subsequently evacuated under vacuum and the crude product is pumped through the sorbent column to obtain the piston flow of the liquid phase in the sorbent layer. In this arrangement, the sorbent is deactivated gradually from the feed direction of the crude product, and thus its full maximum capacity can be utilized to capture undesirable components. Alternatively, a process for refining conjugated fatty acid esters by crystallization to form inclusion compounds (so-called clathrates or interstitial compounds) has been developed on an industrial scale. In this process, the conjugated fatty acid ester molecules are enclosed in the excipient crystals, the crystals of which form cavities of suitable geometric shapes and dimensions. The result is inclusion compounds which are crystalline in nature and exhibit advantageous physical, chemical and application properties. Substances which, due to the shape of their molecule, cannot be enclosed in the excipient crystals, such as fatty acid degradation products, dyes and some ballast substances, remain in the mother liquors and are subsequently removed from the inclusion compounds themselves, for example by filtration. The advantageous physical properties of the inclusion compounds are understood in particular to be their crystalline form, which is advantageous in terms of both handling and application to the final dosage form. It is known in the art, see Park C. W. et al., J. Agric. Food Chem. 50 (2002), 2977-2983 that the advantageous chemical properties are in particular the high oxidation stability of conjugated fatty acid esters in the form of inclusion compounds. Advantageous application properties are understood in particular to mean that the conjugated fatty acid esters of the inclusion compound can only be released in the final dosage form, possibly when using the dosage form. Urea and thiourea were used as suitable excipients.

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The free conjugated fatty acids and their esters produced by the above processes are prepared in a manner that allows their application to food supplements, feed supplements, and cosmetics known from U.S. Patent No. 6,015,833.

Examples

Example 1 (production of conjugated fatty acids from oil of milk thistle fruit)

The batch (150 liters) of the raw material processed - oils from the milk thistle fruit, characterized by a linoleic acid content of 53% by weight. - was added to a mixture of 50 liters of propane-1,2-diol and 32 kg of sodium hydroxide, which had previously been held at 120 ° C and a reactor absolute pressure of 30 kPa for 30 minutes in a 1000 L batch stirred tank reactor. to distill off the resulting water reactions and fill the space above the reaction mixture with propane-1,2-diol vapors. After the batch of feedstock was added, the reactor was separated from the surrounding space in terms of mass transfer and the reaction mixture was agitated with a frame stirrer at 40 rpm and its temperature raised to 150 ° C. After 5 hours, the reaction mixture was cooled to 105 ° C and a solution of 24 kg of 85 wt% phosphoric acid was added. in 160 liters of water. Stirring of the reaction mixture was stopped at this stage to separate the liquid phases. The separation was complete after 10 hours when the temperature of the reaction mixture reached 50 ° C and the absolute pressure was 12.3 kPa. The lower aqueous phase was separated and the upper organic phase was heated at 90 ° C and an absolute pressure of 3.0 kPa with stirring with a frame stirrer at 40 rpm for 3 hours to distill off the residual water content. After cooling to 20 ° C, 122 kg of a mixture of crude conjugated fatty acids was obtained.

Gas chromatographic analysis of the product thus obtained on the composition of conjugated fatty acids gave the following values:

TABLE 1

Fatty acid: _ Area%:

Myrist 0.09

Palmitová 7,75

Stearová 4,13

Oil 21,62 · · · · · · · · · · ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ,6 ·· ·· ··· ·· ·

Linolová 0.37 a-Linolen 0.78 9 (Z), 11 L (E) -octadeca-9.1 L-diene 25.96 11 (Z), 13 (E) -octadeca-1,13-diene 1.46 10 (E), 12 (Z) -octadeca-10,12-diene 25.70 8 (Z), 10 (Z) -octadeca-8,10-diene 0.68 9 (Z), 11 (Z) -octadeka-9.11-pulp 0.73 10 (Z), 12 (Z) -octadeca-10,12-diene 0.02 9 (E), 11 L (E) -octadeca-9, 11-diene 0.52 Behenová 1.17 Lignocerová 0.28

Analysis of the product thus obtained for the water content by the K. Fischer titration method yielded a residual water content of 0.07% by weight.

The remainder of up to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterols, phytosqualenes, etc.)

Example 2 (Esterification of free conjugated fatty acids)

A batch (100 kg) of the crude conjugated fatty acid mixture was dissolved in a batch stirred reactor under stirring with a frame stirrer at 12 rpm at 25 ° C at an absolute pressure of 5.0 kPa in 120 liters of 95% w / w ethanol. to fill the space above the ethanol vapor solution, and after 30 minutes, 15 kg of a 37 wt. Thereafter, the reactor space was isolated from the environment in terms of mass transfer, and the reaction mixture was heated to 70 ° C at 40 rpm with stirring with a frame stirrer. After 4 hours of reaction time, the reaction mixture was cooled to 50 ° C, 100 liters of water were added to the reaction mixture, and after stirring the reaction mixture was stopped to separate the liquid phases. The separation was complete after 2 hours when the temperature of the reaction mixture reached 28 ° C and the absolute pressure was 9.6 kPa. The lower aqueous phase was separated and the upper organic phase containing crude ethyl esters of conjugated fatty acids was heated at 40 ° C and an absolute pressure of 50 kPa with stirring for 2 hours to remove residual ethanol from the product by distillation. After cooling to · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Q φφφφφφφφφ ^J ··· ··· ·· φφ φφ · 20 ° C to obtain 106 kg of a mixture of crude ethyl esters of conjugated fatty acids.

Gas chromatographic analysis of the thus obtained product on the composition of conjugated fatty acids gave the following values:

TABLE2

Fatty acid: Area percentage: Myrist 0.08 Palmitová 7.71 Stearová 4.09 Oil 21.26 Linolová 0.35 a-Linolen 0.76 9 (Z), 11 (δ-octadeca-9.11-diene) 26.57 11 (Z), 13 (E) -octadeca-11,13-diene 0.85 10 (E), 12 (Z) -octadeca-10,12-diene 26.76 8 (Z), 10 (Z) -octadeca-8,10-diene 1.31 9 (Z), 11 (Z) -octadeca-9.11-diene 0.72 10 (Z), 12 (Z) -octadeca-10,12-diene 0.06 9 (£), 11 (£) -octadeca-9,11-diene 0.41 Behenová 1,22 Lignocerová 0.31

Analysis of the product so obtained for the water content by the K. Fischer titration method gave a residual water content of 0.05% by weight.

The remainder of up to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterols, phytosqualenes, etc.)

Example 3 (Purification of crude ethyl esters of conjugated fatty acids by crystallization as inclusion compounds)

A batch (25 kg) of the crude conjugated fatty acid ethyl esters was added in a batch stirred tank reactor with stirring at 60 rpm to a solution of 50 kg of urea in 500 L of 95 wt% ethanol. at the boiling point of the solution at atmospheric pressure, so that the space above the solution was filled with vapor

4444 ·· · ♦

4 4 4 · ·· · · ·

44 «444 4

W 4 4 4 4 · · 44 44 ··

444 ··· ··· ··· 44 ··· ··· ethanol. The reactor space was immediately isolated from the environment in terms of mass transfer and the reaction mixture was cooled to 10 ° C with stirring and maintained at this temperature for 6 hours. Subsequently, the precipitated crystalline product was collected on a suction cup and dried at 40 ° C in a box drier at an absolute pressure of 3.0 kPa for 12 hours to remove residual ethanol from the product. A total of 46 kg of purified conjugated fatty acid ethyl esters were obtained as an urea inclusion compound.

Gas chromatographic analysis of the product thus obtained on the composition of conjugated fatty acids gave the following values:

TABLE 3

Fatty acid: Area percentage: Myrist 0.15 Palmitová 14.27 Stearová 8.56 Oil 28.70 Linolová 0.33 a-Linolen 1,21 9 (Z), 11 L (E) -octadeca-9.1 L-diene 18.69 10 (E), 12 (Z) -octadeca-10,12-diene 18.36 8 (Z), 10 (Z) -octadeca-8,10-diene 0.82 9 (Z), 11 (Z) -octadeca-9.11-diene 0.81 9 (E), 11 L (E) -octadeca-9, 11-diene 0.67 Behenová 1.98 Lignocerová 0.31

The total urea content of the product was determined gravimetrically as 75% by weight. The residual ethanol content of the product was determined by gas chromatography as 0.58% by weight.

The remainder of up to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterols, phytosqualenes, etc.)

Example 4 (production of conjugated fatty acids from oil from the fruits of the Moldovan Apiary) 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 • 4 4 4 4 4 · 4 ·· · 4 4 ·· ··· 4 4 4

A batch (150 liters) of the processed raw material - oils from the fruits of the Moldovan bee colonist, characterized by a linolenic acid content of 62% by weight. - was added to a mixture of 60 liters of propane-1,2-diol and 37.5 kg of sodium hydroxide, previously held at 120 ° C and at a reactor absolute pressure of 5.0 kPa, in a 1000-liter batch stirred reactor. 30 minutes to distill off the resulting water and fill the space above the reaction mixture with propane-1,2-diol vapor. After the batch of feedstock was added, the reactor was separated from the surrounding space in terms of mass transfer and the reaction mixture was stirred with a frame stirrer at 40 rpm and its temperature raised to 170 ° C. After 3 hours, the reaction mixture was cooled to 105 ° C and a solution of 30 kg of 85% by weight phosphoric acid in 160 L of water was added. Stirring of the reaction mixture was stopped at this stage to separate the liquid phases. The separation was complete after 20 hours when the temperature of the reaction mixture reached 35 ° C and the absolute pressure was 5.6 kPa. The lower aqueous phase was separated and the upper organic phase was heated at 90 ° C and an absolute pressure of 3.0 kPa with stirring with a frame stirrer at 40 rpm for 3 hours to distill off the residual water content. After cooling to 20 ° C, 118 kg of a crude conjugated fatty acid mixture were obtained.

Gas chromatographic analysis of the thus obtained product on the composition of conjugated fatty acids gave the following values:

TABLE4

Fatty acid: Area percentage: Palmitová 5.67 Stearová 2.55 Oil 9.87 Linolová 1.14 a-Linolen 0.41 9 (Z), 11 (£) -octadeca-9.11-diene 8.36 11 (Z), 13 (E) -octadeca-1,13-diene 0.12 10 (E), 12 (Z) -octadeca-10,12-diene 9.05 9 (£), 11 (£) -octadeka-9.11-diene 0.25 Behenová 0.05 Sum of conjugated octadecatriene 58.59

• β ·· · 99 9999

9 9 9 99

9 9 9 9 9 9 9 9 9

9 9 9 9 9

999 99 99

Analysis of the product so obtained for the water content by the K. Fischer titration method gave a residual water content of 0.09% by weight.

The remainder of up to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterols, phytosqualenes, etc.)

Example 5 (Purification of crude ethyl esters of conjugated fatty acids by sorption on a solid sorbent)

A batch (180 kg) of the crude conjugated fatty acid ethyl esters was pumped at 25 ° C by a piston-membrane pump onto a 30 cm diameter evacuated chromatography column packed with 20 kg silica gel with a 0.063-0.200 mm grain size and a mean pore size of 10 nm. the absolute column pressure was 3.5 kPa. The pumping speed of the feed material was kept constant at 25 liters per hour. The product (eluate) - purified ethyl esters of conjugated fatty acids was collected from the bottom of the column. After all of the feed material had been pumped, the liquid phase residue from the column was pushed to the product by argon at a pressure of 0.3 MPa. A total of 162 kg of purified conjugated fatty acid ethyl esters were obtained.

Gas chromatographic analysis of the product thus obtained on the composition of conjugated fatty acids gave the following values:

TABLE 5

Fatty acid: Area percentage: Myrist 0.06 Palmitová 7.42 Stearová 4.98 Oil 20.04 Linolová 1.43 a-Linolen 0.81 9 (Z), 11 L (E) -octadeca-9.1 L-diene 28.44 11 (Z), 13 (E) -octadeca-11,13 -dieno 0.67 10 (E), 12 (Z) -octadeca-10,12-diene 28.52 8 (Z), 10 (Z) -octadeca-8,10-diene 0.81 9 (Z), 11 (Z) -octadeca-9,1-diene 0.77 10 (Z), 12 (Z) -octadeca-10,12-diene 0.12

99 99 9 99 99 99 99

999 999 999

999 9 9 99 99

9 (E, 11) (E) -octadeca-9, 11-diene 0.33 Behenová 2.13 Lignocerová 0.49

Analysis of the product thus obtained for the water content by the K. Fischer titration method yielded a residual water content of 0.04% by weight.

The remainder of up to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterols, phytosqualenes, etc.)

Industrial applicability

Conjugated fatty acids and their derivatives derived from milk thistle and molded apricot oils with a defined ratio of individual fatty acids are suitable for subsequent use in food supplements, feed supplements and cosmetics.

Conjugated fatty acids show potent antioxidant activity, antitumor activity, immune system enhancement effect, improved fat metabolism, anticancerogenic effect, anti-decalcification effect, reduced risk of cardiovascular disease and other positive effects on human and mammal health in general.

The preparation of conjugated fatty acids and their derivatives using vacuum minimizes the consumption of inert gases and co-organic solvents and thus does not burden the environment. Due to the very gentle conditions of production and cleaning of the final products, their yield is very high and thus the maximum use of feedstocks, which come from natural renewable sources, is maximized.

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4 4 4 4

4 4 4 4

4 4 4 4 4

4 4 4 4 * 44

Claims (12)

PATENT CLAIMS Process for the production of mixtures of linear chain conjugated fatty acids having a carbon chain length of up to C 18 and a total number of double bonds of 2 or 3, and derivatives thereof, wherein the first step is a direct isomerization conversion of vegetable oil under heat and alkaline conditions to conjugated fatty acid salts. acid, in the next step the fatty acids are released by the action of a mineral acid, after which the mixture of the fatty acids obtained is subjected to a derivatization step, followed by optional purification of the derivatives, characterized in that individual steps, in particular isomerization step, performed under vacuum. Method according to claim 1, characterized in that the vegetable oil is oil of the milk thistle fruit and / or the Moldovan apiary. Process according to any one of the preceding claims 1 to 2, characterized in that derivatization of the free fatty acids means their esterification. The method of claim 3, wherein the esterifying alcohol is ethanol. The method of claim 1, wherein the purification of the conjugated fatty acid derivatives is carried out by adsorption of degradation products and undesirable substances on an inert solid support. The method of claim 5, wherein the inert solid carrier is a silica sorbent. Process according to claim 5 or 6, characterized in that the purification of the conjugated fatty acids takes place at a temperature of 15 to 25 ° C. Method according to claims 5 to 7, characterized in that the free volume of the sorbent is de-oxygenated and / or air-free by vacuum prior to purification of the conjugated fatty acids or derivatives thereof. φ · * · • φ φ • • · · · Method according to claims 1 and 8, characterized in that the absolute pressure value under vacuum application is less than 10 kPa, more preferably less than 5 kPa. The process according to claim 1, characterized in that the purification of the conjugated fatty acid derivatives is carried out by crystallization with an inert substance forming together inclusion compounds. 11. The method of claim 10, wherein the inert substance for forming inclusion compounds of conjugated fatty acid derivatives is urea. The method of claim 10, wherein the inert substance for forming inclusion compounds of conjugated fatty acid derivatives is thiourea.