CS259440B1 - FosfoV.pld and co-production methods - Google Patents

Abstract

The solution relates to phospholipid concentrates containing 60 to 99% by weight of salts of phosphatisic, bis(diacylglycerol) phosphoric acids and their lysoderivatives and a method of producing these concentrates. They are prepared by extracting neutral products of phosphorylation of partial acylglycerols with aqueous solutions of methanol, ethanol or a ternary mixture of methanol-ethanol-water. The ratio of individual phospholipids can be influenced by the composition of the extraction agent. The obtained phospholipid concentrates with a reduced content of ballast substances can be used as antioxidants and stabilizers for oils and fats containing unsaturated fatty acids.

Description

The invention relates to phospholipid concentrates with a low content of neutral lipids and a method for their production by single- or multi-stage extraction of neutralized products of phosphorylation of partial acylglycerols.

Phosphatidic acid salts are produced by phosphorylation of a mixture of partial acylglycerols either with phosphorus pentoxide previously dispersed in triacylglycerols of saturated fatty acids (Czech Patent AO 203 421) or by dispersion of metaphosphoric and polyphosphoric acids prepared "in situ" in the phosphorylated raw material and subsequent neutralization with an appropriate base, such as gaseous ammonia, calcium hydroxide or basic amino acids. Such products contain, in addition to the desired salts of phosphatidic and bis (diacylglycerol) phosphoric acids and, as a rule, a small amount of unreacted diacylglycerols, also neutral triacylglycerols, which in the optimal case are around 35, but often up to 50% by weight. In addition, the sensory properties of these triacylglycerols deteriorate, and this is reflected in the deteriorated quality of the resulting mixture of phospholipids and neutral lipids, so that the final products can only be used for food purposes in small quantities, so as to avoid deterioration of color or taste. Another undesirable component of the products phosphorylation are glycerol phosphates formed by phosphorylation of glycerol, whether present in the raw material or produced, by secondary disproportionation reactions, and inorganic phosphates formed by neutralization of degradation residues of phosphorylation agents. The listed undesirable components both reduce the content of phospholipids in the product and worsen its application properties. However, reducing their content by treating the raw materials or modifying phosphorylation processes is not possible and only refining neutral phosphorylation products remains viable.

Phospholipid concentrates produced by the process according to the invention, containing 60 to 99% by weight, do not have these disadvantages. salts of phosphatidic acids, bis (diacylglycerol)-phosphoric acids and their lysoderivatives with a molar ratio of mono- and diesters of trihydrogenphosphoric acid in the range of 1:1 to 20:1, further 0.1 to 10% by weight of partial acylglycerols with 8 to 24 carbon atoms in the acyl chain, 0.1 to 10% by weight of free fatty acids and the remainder up to 100% by weight of triacylglycerols. They are prepared by extraction of neutral products of phosphorylation of a technical mixture of partial acylglycerols with 8 to 24 carbon atoms in the acyl chain with 1 to 30% (by weight) solutions of water in methanol or ethanol or equally concentrated solutions of water in a binary methanol-ethanol mixture, in which both alcohols are represented in a weight ratio of 9:1 to 1:9.

The composition of the extraction agent and its ratio to the extracted raw material affect the composition and yield of the extract. With increasing water concentration in the agent, the solubility of triacylglycerols decreases and the proportion of desired salts of phosphatidic acids in the extract increases. The extraction yield decreases with increasing polarity of the extraction agent. It is very advantageous that in the process according to the invention, the composition of the phospholipid part of the product can be influenced by the composition of the agent — with its increasing polarity, the proportion of monoesters of trihydrogenphosphoric acid increases, so that their desired ratio to diesters in the final product is ensured by a certain composition of the extraction agent. Single-stage extraction is used when the starting raw material contains a smaller amount of phospholipids. For more complete evaluation of raw material with a higher content of phospholipids, multi-stage extraction is preferably used. The ratio of extraction agent to substrate is chosen to be greater than 5 : : 1, but usually not greater than 15 : 1 and extractions are carried out at 15 to 45 ^° C.

One of the suitable methods for separating the used solvents from the obtained phospholipid concentrates is their distillation on a film evaporator under reduced pressure so that the temperature during distillation does not exceed 80 °C. The product is thus obtained as a light yellow viscous liquid. In the production of high-percentage concentrates (with a content of over 85% by weight of phospholipids), it is advantageous to adjust the rheological properties of the product by adding refined vegetable oil directly to the evaporated mixture. This prevents the phospholipid concentrate from sticking in the film evaporator and facilitates further manipulation, including dosing during applications.

The production process and composition of the phospholipid concentrates according to the invention are apparent from the following Examples 1 to 5.

Example 1 550 kg of the product of phosphorylation of partial acylglycerols prepared from rapeseed oil are pumped into a reactor with a volume of 5.5 m ³ .

The product contains:

40.0% by weight of triacylglycerols,

2.1% by weight of ammonium salts of fatty acids,

5.1% by weight diacylglycerols,

50.4% by weight of ammonium salts of phosphatidic acids, in which the ratio of mono- and diesters of trihydrogenphosphoric acid was 3:1,

1.4% by weight of ammonium salts of glycerol phosphoric acids,

1.0% by weight of inorganic phosphates.

3,600 kg of 90% (wt.) aqueous ethanol are pumped in and the reactor contents are stirred at a temperature of 21.5 °C for 1 hour with a propeller stirrer and the mixture is circulated by bypass. After phase separation, which lasts 1 hour, the upper ethanol phase is pumped into a storage tank and another 3,600 kg of 90% (wt.) ethanol is pumped into the remaining lipid mixture. The reactor contents are stirred for 1 hour at 21.5 °C in the same way as in the previous step and after 1 hour of sedimentation at the same temperature, the upper ethanol phase is pumped back into the storage tank. The combined ethanol solutions are concentrated by atmospheric distillation at 80 °C to approximately 1/3 of the volume and the remaining ethanol and water are distilled off from the mixture thus obtained on a film evaporator at a temperature of 70 degrees Celsius and a pressure of 6.6 kPa.

A light yellow viscous liquid (201 kg) is obtained containing:

6.8% by weight of triacylglycerols,

2.3% by weight of ammonium salt of fatty acid,

10.0% by weight of diacylglycerols,

80.9% by weight of phospholipids with a ratio of mono- and diesters of trihydrogenphosphoric acid of 4.6:1.0.

The product does not contain glycerol phosphoric acid salts or inorganic phosphates. This phospholipid concentrate has been used as an antioxidant and stabilizer of edible fats and vegetable oils.

Example 2

The reactor with a volume of 5.5 m ³ is pumped

550 kg of neutral product of partial acylglycerol phosphorylation (based on rapeseed oil with low erucic acid content) with the following composition:

27.4% by weight of triacylglycerols,

0.1% by weight of ammonium salts of fatty acids,

0.7% by weight of diacylglycerols,

1.1% by weight of ammonium salts of glycerolphosphoric acids,

70.7% by weight of ammonium salts of phosphatidic acids with a ratio of mono- and diesters of trihydrogenphosphoric acid of 4:1.

3,600 kg of 90% (w/w) aqueous ethanol are pumped to the raw material and the resulting mixture is stirred at 20 °C for 1 hour with a propeller stirrer and bypass circulation. After sedimentation lasting 1 hour, the upper ethanol layer is pumped into a storage tank and the residue in the reactor is extracted twice more under the same conditions with the same amount of 90% (w/w) ethanol at 20 °C. Approximately 75 percent of the extraction agent is distilled off from the combined three ethanol solutions in the form of an azeotropic ethanol-water mixture by atmospheric distillation and the remainder of the solvent is distilled off on a film evaporator at a temperature of 70 °C and a pressure of 6.4 to 5.8 kPa. 241 kg of a light yellow, clear and very viscous liquid with the following composition is obtained:

9.5% by weight of triacylglycerols,

1.4% by weight fatty acids,

3.1% by weight diacylglycerols,

86.0% by weight of ammonium salts of phosphatidic acids with a ratio of mono- and diesters of trihydrogenphosphoric acid of 6:1.

The product does not contain glycerolphosphoric acid salts. Part of the product was used as an antioxidant in feed mixtures for early piglet rearing (COS 1, ČOS 2) and for early lamb rearing (ČOJ). The second part was used as an improving additive in the production of long-life bakery products.

Example 3

225 kg of neutral product of partial acylglycerol phosphorylation (based on sunflower oil) with the following composition is pumped into a homogenizer with a volume of 2.4 m ³ , which has three independent mixing systems built in:

43.1 % mass 0.9 % mass lira and, 4.5 % mass 1.5 % mass 1.1 % mass 48.9 % mass ky 'selin

of trihydrogenphosphoric acid diesters 2:1.

After pumping in 1,460 kg of a 10% (wt.) solution of water in methanol, the contents of the homogenizer are intensively mixed simultaneously with all reagents for 25 minutes at 23 °C. After 1 hour of sedimentation, the upper alcohol phase is pumped into the storage tank and the lower lipid phase is extracted for another 25 minutes with the same amount of the same reagent, maintaining all conditions as in step 1. According to TLC-FID analysis, the combined methanol solutions contained 95% by weight of phosphatidic acid salts, and therefore 15 kg of refined sunflower oil is added directly to the evaporated mixture during the distillation of solvents on a film evaporator. This procedure yields 71 kg of light yellow, clear and relatively low-viscosity liquid with the following composition:

5 9

22.8% by weight of triacylglycerols,

0.8% by weight of ammonium salts of fatty acids,

1.6% by weight of diacylglycerols,

74.8 wt. % ammonium salts of phosphatidic acids with a molar ratio of mono- and diesters of trihydrogenphosphoric acid of 19.2 : 1.0.

Neither glycerol phosphates nor inorganic phosphates were found in this mixture.

kg of the final product was used for the preparation of proteophospholipids intended for enteral nutrition. The rest of the product was used as a biologically active ingredient in preparations for the prevention and treatment of circulatory diseases.

Example 4

To 550 kg of raw material of the same composition as in Example 3, 3,600 kg of 70% (wt.) aqueous ethanol are pumped into a reactor with a volume of 5.5 m ³ . The reactor contents are stirred for 90 minutes with a propeller stirrer and bypass circulation at 23 °C and then allowed to sediment for 60 minutes. TLC-FID analysis revealed that the lipids in the pumped-over alcoholic solution were composed of 98.5 wt. % of phosphatidic acid salts and only 1.5 wt. % of acylglycerols. Therefore, when evaporating the solvents on a film evaporator (at 70 °C and pressure

5.8 to 5 kPa) is added to the evaporated ¹ solution of 20 kg of refined sunflower oil. A phospholipid concentrate with the following composition is obtained:

23.7% by weight of triacylglycerols,

0.3% by weight fatty acids,

0.4% by weight, diacylglycerols,

75.6% by weight of ammonium salts of phosphatidic acids with a molar ratio of mono- and diesters of trihydrogenphosphoric acid of 20:1.

The phospholipid concentrate, in which no glycerol phosphates or inorganic phosphates were detected, was used as a biologically active additive in cosmetic emulsions.

Example 5

In a homogenizer with a volume of 2.4 m ³ , 220 kg of the same raw material as in example 1 are mixed for 30 minutes at 21 ^° C, with all three mixers running, with 1,450 kg of a ternary mixture of 70% by weight ethanol, 10% by weight methanol and 20% by weight water. Then the reactor contents are left to sediment for 1 hour and the upper alcohol layer is pumped into a storage tank. Evaporation of the solvents on a film evaporator at 75 ° C and a pressure of 6.4 to 5.6 kPa yields a yellow, very viscous liquid, which is liquid only at temperatures above 65 ° C. The obtained phospholipid concentrate contains:

1.2% by weight of triacylglycerols,

1.1% by weight of fatty acids,

2.7% by weight of diacylglycerols,

95.0% by weight of phosphatidic acid salts with a molar ratio of mono- and diesters of trihydrogenphosphoric acid of 17.8:1.

Neither glycerolphosphoric acid salts nor inorganic phosphates were detected in the product, which weighed 40.5 kg. The concentrate was used as an antioxidant in food products containing fats with unsaturated fatty acids.

Phospholipid concentrates according to the invention can be used as antioxidants and stabilizers for food products and feed mixtures, as non-toxic emulsifiers and biologically active substances and additives in the food industry, cosmetics and for the production of complex compounds of phospholipids with amino acids and proteins.

Claims (2)

Subject Phospholipid concentrates containing neutral lipids, characterized in that they contain 60 to 99 wt. salts of phosphatidic, bis (diacylglycerol) phosphoric acids and their lysoderivatives with a molar ratio of mono- and diesters of trihydrogenphosphoric acid. % in the range of 1: 1 to 20: 1, further 0.1 to 10 wt. % of partial acylglycerols with 8 to 24 carbon atoms in the acyl chain, 0.1 to 10 wt. % free fatty acids and the remainder to 100 wt. triacylglycerols having 8 to 24 carbon atoms in the acyl chain. 2. A process for the preparation of phospholipid concentrates according to claim 1 obtained by one or more stages of extraction, characterized in that the neutral product of the partial acylglycerol phosphorylation is treated with a 1 to 30% by weight solution of water in methanol or ethanol or in binary mixtures thereof. : 9 to 9: 1 followed by distilling off the solvent at a temperature of up to 80 ° C.