CZ303221B6 - Process for preparing mixtures of conjugated fatty acids - Google Patents

Abstract

The present invention relates to a process for preparing mixtures of conjugated fatty acids with a linear chain having up to 18 carbon atoms and total number of double bonds 2 or 3 or derivatives thereof, wherein the preparation process is characterized in that first the step of a direct isomerization conversion of vegetable oil is carried out by the action of heat and alkali medium on salts of conjugated fatty acids, in the following step fatty acids are liberated by the action of a mineral acid, subsequently the mixture of the obtained fatty acids is subjected to a derivatization step with an optional subsequent purification of the derivatives, whereby access of oxygen and/or air is restricted in the individual steps by application of vacuum under the value of absolute pressure less than 10 kPa, particularly in the isomerization step on order to increase yield and purity of the products.

Description

Process for preparing conjugated fatty acid mixtures

Technical field

The present invention relates to a process for the production of mixtures of conjugated fatty acids and their derivatives from oils of the milk thistle (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 supplements. .

BACKGROUND OF THE INVENTION

The fruit of the milk thistle and the bee colonies contain a number of biologically active i? 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. From the state of the art (Karlson P. et al .: Pathobiochemistry, 2nd edition, Academia

Prague 1987), it is known that essential fatty acids are the basic building blocks for a number of other highly biologically active substances from the prostaglandins, prostacyclins, thromboxanes, leukotrienes, etc., which directly influence 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 diacylglycerols and monoacylglycerols. In addition to these substances, free fatty acids and small amounts of phytosterols, tytosqualenes, phospholipids, terpenic derivatives, dyes, etc. are present in the oils as well as degradation products of all these substances. The basic difference in the qualitative composition of the oils of both plant species is the fact that while in the oil of milk thistle we find in the representation of fatty acids high levels of linoleic acid or 9 (Z), 12 (Z) -octadeca-9,12 ”dienoic (commonly over 50% by weight), α-linolenic acid or

9 (Z), 12 (Z), 15 (Z) -octadeca-9,12,15-triene (typically above 60 wt%).

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 (International Publication No. 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. Cell Nutr. 19 (2) (2000), 11S-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.

- I CZ 303221 B6

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 bio5 chemical processes (international publication 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 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 must be carried out with limited 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 include the application of a suitable inert atmosphere during the reaction itself and subsequent treatment with the reaction mixture to give 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 actual reaction. 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 the positions or arrangement of double bonds in fatty acid molecules, eventually to the overall degradation of the 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 the molded bee, 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.

-2GB 303221 B6

SUMMARY OF THE INVENTION

To a large extent, these processes are eliminated by a process for the production of mixtures of conjugated fatty acids having a linear chain length of up to C ₁₈ and a total number of double bonds of 2 or 3 or derivatives thereof, first carrying out the step of direct isomerization of vegetable oil by heat and alkali. medium on salts of conjugated fatty acids, in the next step the fatty acids are released by the action of mineral acid, then the mixture of obtained fatty acids is subjected to the derivatization step, followed by optional purification of the derivatives, restricting oxygen and / or air in individual steps, in particular in the isomerization step, by applying a vacuum at an absolute pressure of less than 10 kPa.

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.

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

After carrying out the appropriate laboratory, and subsequently pilot and operational tests, 25 it was found that all processes as described and under the conditions indicated were 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. the positional and geometric isomers of polyunsaturated fatty acids, wherein the double bonds in its molecules are in conjugated positions. These are in particular linear chain conjugated fatty acids having 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 the saturated fatty acids 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 seems to be the most versatile, which does not cause excessive corrosion, especially of metal parts of apparatuses, and the waste products of the reaction (inorganic salts of trihydrogenphosphoric acid) can be used

as a quality industrial fertilizer in agriculture. 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 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 (Park CW). 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.

2o The method of adsorption of degradation products and sensory unacceptable substances, such as dyes and odors, on a suitable type of sorbents was used for purification of crude conjugated fatty acid esters. Inorganic silica-based sorbents which are capable of effectively trapping undesirable substances, in particular of a polar nature, appear to be advantageous. 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 to 25 ° C, in a continuous configuration excluding air oxygen and / or air, thus avoiding oxidative degradation of the product and its product 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 freed from 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 can be carried out in an arrangement wherein the sorbent is packed into a container of suitable shape (hereinafter referred to as the column), after which residual air is sucked off 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 inert compounds) has been developed on a commercial scale. In this method, 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. The advantageous application property 50 is understood in particular to mean that the conjugated fatty acid esters of the inclusion compound can only be released in the final dosage form, optionally when the dosage form is used. Urea and thiourea were used as suitable excipients.

-4GB 303221 B6

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) 10

A 50 liter reactor was charged with 50 liters of propane-1,2-diol and 32 kg of sodium hydroxide. The reactor was evacuated to an absolute pressure of 5.0 kPa, heated to 120 ° C, and at this temperature and an absolute pressure of 5.0 kPa the mixture was stirred for 30 minutes in the reactor to distill off the resulting water and fill the space above the reaction mixture. vapors for 1515 pan-1,2-diol. Thereafter, a charge (150 liters) of the processed milk thistle oil feedstock, characterized by a 53% by weight Iinolic acid content, was added to the reactor contents. The reactor was maintained at a temperature of 120 ° C and an absolute pressure of 5.0 kPa. 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 was 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 while 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 ₃₅ Palmitic 7.75

Stearová 4,13

Oil 21.62

Linoleic 0.37 α-Linoin 0.78

9 (2), 1 l (£) -octadeca-9,11-diene 25,96 (Z), 13 (£) -octadeca-11,13-diene 1,46

10 (E), 12 (Z) -octadeca-10,12-diene 25.70

8 (2), 10 (2) -octadeca-8,10-diene 0.68

9 (2), 1 L (2) -octadeca-9,1 L-diene 0.73 *

10 (Z), 12 (Z) -octadeca-10,12-diene 0.02

9 (£), 11 (£) -octadeca-9.11-diene 0.52

Behenová 1,17

Lignocer 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 to 100% (by weight) consists of minor components such as other fatty acids and substances of a different nature (higher saturated hydrocarbons, phytosterol, phytosqualene, etc.).

io 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 20 ° C, 106 kg of a mixture of crude 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 2

Fatty acid content and composition in ethyl esters of conjugated fatty acids expressed as free fatty acids

Fatty acid: _ Area%:

Myrist 0.08 Palmitová 7.71 Stearová 4.09 Oil 21.26 Linolová 0.35 a-Linolen 0.76 9 (Z), 11 L (E) -octadeca-9.1 L-diene 26.57

-6GB 303221 B6 l (Z), 13 (£) -octadeca-l 1,13-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

Lignocer 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 conjugated fatty acid ethyl esters 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 ethanol vapor. 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 separated off and dried at 40 ° C in a box dryer at an absolute pressure of 30 mbar 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 content and composition in ethyl esters of conjugated fatty acids expressed as free fatty acids

Fatty acid: Content in area percentages: Myrist 0.15 Palmitová 14.27 Stearová 8.56 Oil 28.70 Linolová 0.33 a-Linolen 1,21

9 (2), 11 (?) -Octadeca-9,11-diene 18.69

10 (2S), 12 (Z) -octadeca-10,12-diene 18.3 6

8 (2), 10 (Z) -octadeca-8,10-diene 0.82

9 (Z), 11 (Z) -octadeca-9.11-diene 0.81

9 (£), 11 (£) -octadeca-9.11 -day 0.67

Behenová 1,98

Lignocer 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 to be 0.58% by weight by gas chromatography.

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, phytosquenes, etc.) io

Example 4 (Production of conjugated fatty acids from oils from the fruit of the Moldovan bee)

A 60 liter reactor was charged with 60 liters of propane-1,2-diol and 37.5 kg of sodium hydroxide. The reactor was evacuated to an absolute pressure of 5.0 kPa, heated to 120 ° C and at this temperature and an absolute pressure of 5.0 kPa the mixture was stirred in the reactor for 30 minutes to distill off the resulting water reactions and fill the space above the reaction mixture. with propane-1,2-diol. Subsequently, a batch (150 liters) of the processed raw material of the oil of the Moldovan Apiary - characterized by a linolenic acid content of 62% by weight, was added to the reactor contents. The reactor was maintained at a temperature of 120 ° C and an absolute pressure of 5.0 kPa. 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 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 20 hours when the temperature of the reaction mixture reached 35 ° C and absolute pressure

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

Table 4

Fatty acid:

Palmitová

Stearová

Oil

Area percentage:

5.67

2.55

9.87

8GB 303221 B6

Linol 1,14 α-Linolenic 0,41

9 (Z), 11 (£) -octadeca-9,11-diene 8,36 l (Z), 13 (£) -octadeca-1 1,13-diene 0,12

10 (E), 12 (Z) -octadeca-10,12-diene 9.05

9 (£), 11 (£) -octadeca-9.11-diene 0.25

Behenová 0,05

Sum of conjugated octadecatriene 58.59

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 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 conjugated fatty acid ethyl esters by sorption on solid sorbent)

A batch (180 kg) of the crude conjugated fatty acid ethyl ester 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 10 mm mean pore size. 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 content and composition in ethyl esters of conjugated fatty acids expressed as free fatty acids

Fatty acid:

Myrist

Palmitová

Stearová

Oil

Linoleum and Linolen

Area percentage:

0.06

7.42

4.98

20.04

1.43

0.81

9 (Z), 11 (£) -octadeca-9,11-diene 28,44 (Z), 13 (£) -octadeca-11,13-diene 0,67

10 (E), 12 (Z) -octadeca-10,12-diene 28.52

8 (Z), 10 (2) -octadeca-8,10-diene 0.81

9 (2), 11 (2) -octadeca-9.11-diene 0.77

10 (Z), 12 (2) -octadeca-10,12-diene 0.12

9 (E), 11 L (E) -octadeca-9, 11-diene 0.33

Behenová 2,13

Lignocer 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.) to Industrial usability

Conjugated fatty acids and their derivatives obtained from oils of the milk thistle and molded apricots 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.

Claims (11)

30 PATENT CLAIMS A process for producing a mixture of linear chain conjugated fatty acids having a carbon chain length up to and having a total number of double bonds of 2 or 3 or derivatives thereof, wherein the first step is a direct isomerization conversion of vegetable oil under heat and alkaline conditions to conjugated fatty acid salts. in the next step the fatty acids are released by the action of the 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 oxygen and / or air is restricted in individual steps to increase yields and purity especially in the isomerization step, by applying a vacuum at an absolute pressure of less than 10 kPa. - 10GB 303221 B6 Method according to claim 1, characterized in that the vegetable oil is oil from the milk thistle fruit and / or the Moldovan apiary. 5 Process according to any one of the preceding claims 1 and 2, characterized in that derivatization of the free fatty acids means their esterification. The method of claim 3, wherein the esterifying alcohol is ethanol. io 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. 15 Dec The method of claim 5, wherein the inert solid carrier is a silica sorbent. The method of claim 5 or 6, wherein the purification of the conjugated fatty acids is carried out 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. 25 The method according to claims 1 to 8, characterized in that the absolute pressure value under vacuum application is less than 5 kPa. 10. The process of claim 1 wherein the purification of the conjugated fatty acid derivatives is performed by crystallization thereof with an inert substance forming a co-inclusive material. 30 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.