DD267055A1 - PROCESS FOR OBTAINING BORDER-ACTIVE LIPIDS - Google Patents

Abstract

The invention relates to the production of surface active lipids in the form of structural lipids from animal tissue of the meat processing industry after proteolytic hydrolysis, preferably by Abproduction of enzymatic meat processing. In the 1st stage, the neutral fats are separated from the minced meat by means of thermal treatment. Non-specific proteinases and peptidases, optionally in conjunction with limited lipolysis, are used according to the invention. The resulting soluble peptides are separated and extracted with binary or ternary solvent mixtures with simultaneous lipid fractionation. The separation of the surface-active lipids is then carried out by vacuum distillation under a nitrogen atmosphere.

Description

Field of application of the invention

The invention; It relates to a process for the production of surfactant lipids from membranes of animal vaults obtained as waste products in the industry with differentiated composition and different interfacial tension-lowering potential of the lipids Preferred application of the invention is the lipid recovery from enzymes of enzymatic meat processing. Preferred application field of the final products is the use in the food industry as emulsifiers and component of emulsifier-stabilizer mixtures (compounds).

Characteristic of the known technical solutions

Polar lipids (predominantly phospholipid) are overgrowths of inch membranes and lipoproteinone. In a range of animal and vegetable products (eg egg yolk, soybean, cottonseed, wheat germ) the proportion of these polar lipids is relatively high; therefore, these raw materials are usually starting material for economically viable recovery of these classes of substances.

In meat, the proportion of polar and other special neutral lipids (eg phospholipids, sterol esters) is not only low, but at the same time it is covered by massive amounts of neutral fats (triglycerido). The small proportion of polar lipids in the meat is not reported in quantitative lipid determination (total or crude fat). Therefore, to date, it did not appear to be promising to develop methods for selectively obtaining this class of meat from meat. Such processes are linked to two main conditions;

1. Separation of the massive excess of nautral fats (triglycerides) and

2. the physical separation of the protein-lipid complex by a digestion process to allow complete extraction of the polar lipids.

Technological measures, which fulfill the requirement in principle, are the onzymatischo hydrolysis of meat for the production of peptide mixtures (Poptonen), the z. B. in culture media of Baktorienkulturon vorzug findon.

Meat hydrolysis to obtain peptones is done with preference to oine separation of fats (trigylcorido).

Furthermore, enzymatic hydrolysis is carried out with an enzyme mixture of oankreatic origin, so that rust activities of pancreatic lipasone and phospholipases can be effective. Thus triglycorido can be cleaved into mono- and diglycerides and phospholipids into lysopliosphatides and phosphatidone. These decomposition products are dissolved in the form of an aqueous solution of incubation in the form of a megaroid, so that they disassociate themselves with a simple solution.

As to the industrial extraction of waste from vegetable raw materials, dioxin is usually carried out by pressing and / or extraction with organic solvents, preferably Hoxan or Bonzin, from tiorischon raw materials by smelting, preferably with superheated steam, and dio of microwave biomassone Extraction with aqueous / non-aqueous solvents, preferably azeotropone Gomischon from Hoxan, Mothanol and Wassor. Thus, the ancestors described in the following patents for the separation of lipids from Futtorhefon WP 160231, 207127, 53984, 54655, 64018, 70856, 108114 and 139650 are particularly noteworthy.

In fats thus obtained from animal or vegetable raw materials, os is lipid mixtures; in donon non-interfacially active neutral lipids, in particular triglycorido, are dominant. In contrast, lipids from microwave biomass contain depending on the microorganism species, the Nährsu'ostrai and the incubation conditions more or less large proportions of surface-active compounds, in particular phosphatides, which, however, for the food industry due to various Bedonkon no größoro significance.

Accordingly, the production of surface-active phosphatides for the application areas mentioned above is still mainly carried out by deposition from vegetable crude oils (decoupling) or egg yolks (extraction). The industrial production of glycorido surfactants, especially mono- and diglycerides, is carried out primarily by re-esterification of glycerides with glycerol, esterification of glycerol with fatty acids or lipolytic cleavage of triglycoridone.

In many cases, there is a reasonable interest in oinor cost-effective production of surface-active compounds based on glycerides and phospholipids with utilization of available and complete utilization of domestic raw materials; in woitoron, this also refers to those precursors which are characterized by a high HLB word and a related hohos limit-flared voltage-lowering potential gogonübor partial glyceride and phospholipidone.

Object of the invention

The aim of the invention is therefore to develop resulting raw materials, in particular waste products, for the production of surface-active compounds, especially with phosphatides or partial glycerides enriched lipid mixtures, for industrial applications, preferably in the food industry. The invention is thus based on the object aufzeigun a selection of raw materials and the targeted Verfahrensbodingungon for the production of surface-active lipids with differentiated composition and properties.

Explanation of the nature of the invention

The essence of the present invention resides in obtaining the proportions of polar lipids present in the meat or in the offals of sheep of farmed animals by enriching them, optionally also modifying them, when added or in connection with oinor meat hydrolysis preparation, and of all other constituents of the meat are removed by extraction

 The essential steps of enzymatic meat hydrolysis exist here

- in the separation of neutral fats (triglyceride) from the zorkloinerton Floisch after thermal treatment in an aqueous medium,

- in the application of nonspecific (in the cleavage mechanism) proteinases, dio freely voi. '' oolytic activity and are the

Possibility of targeted limited and / or stereospecific lipolysis by the additional use of appropriate lipolytic enzymes (eg pancreatic enzyme mixtures).

Under these conditions, complete solubilization of the cellular membranes containing the dio polar lipids is eliminated. These membranes remain after hydrolysis rather than fragments in the incubation. They represent particulate components that do not soak up under the influence of gravity, but frame them. In accordance with the invention, these particles were separated from the aqueous peptide solution by simple method of substitution, the lipid separation being quantitative. This means that during incubation no simple or miscellular solution of polar lipids in the aqueous medium has taken place.

Preferred proteinases for such meat hydrolyses are animal, vegetable and microbial enzymes, preferably theimitase, subtilisin, pronase, papain, ficin, bromine, pancreatic proto-inasegomic and / or pepsin. An example of this is the microbial proteinase thermitase from Thermoactinomycos vulgaris, which is also used to obtain special peptide mixtures as part of chemically defined diets.

After complete proteolytic cleavage of the flesh while remaining in lnkubatio ^r omedium residues which can be deposited as a brown homogeneous pasty mass by filtration or separation.

The resulting Biomar.se is humid or dried either directly or after an additional lipolytic treatment with known enzymes with such enzyme activity, dio selective lipid cleavage, preferably of phospholipids allow, an extraction with non-aqueous and / or aqueous solvents unterorfon, where Llpldgemlsche with different fraction distribution and different interfacial tension Erniчreinigung potential incurred, which are predestined for various applications.

Lipolytic modification of the lipids, as well as solvent fractionation, is always advantageous in the context of the invention when it is desired to obtain relatively high HLB liposomes and limit cell stress-relieving potentials with preferential use as emulsifiers for O / W emulsions otherwise emulsifiers with relatively low HLB and interfacial tension lowering potential with preferential use in W / O emulsions will result.

For the lipid extraction orelf in accordance with the invention in a conventional manner for a binary azootrope mixtures of polar and nonpolar solvents, preferably of chlorinated hydrocarbons, alcohols or ketones with hydrocarbons, foror ternary azetrope mixtures nichtwäßrigor and aqueous solution, preferably hydrocarbons, ketones and water, optionally adding acids and bases to cleave protein / lipid linkages sir d.

The use of the first-mentioned solvents requires drying of the biomasses to be extracted, whereas the latter solvents can be used for direct extraction in conjunction with a mechanical phase separation preceding the disintegrable distillation.

In certain cases, a lipid fractionation according to the invention by successive extraction also turns out using polar, water-miscible solvents, preferably alcohols and ketones, in combination with nonpolar, water-immiscible solvents, preferably hexane or gasoline, on the other hand by means of supercritical gases, preferably carbon dioxide and mixtures thereof with propane or trifluoromethane, as advantageous; Solcho procedures allow namely the separate recovery of phospholipids and partial glycerides.

The general advantage of the method according to the invention is therefore not only in the utilization of waste products of the above-mentioned raw materials with regard to the production of surface-active lipids, but also in a targeted change in their interfacial activity by modification and / or fractionation during dor recovery. The invention will be explained in more detail by the following exemplary embodiments.

Auslührungsbelsplele

example 1

10kg of beef is minced in a mincer and taken up in 10 μl of water. This mixture is heated to 100 ° C. with stirring for 10 minutes. The sedimented cooked meat is separated from both the liquid fat and the aqueous phase. It is suspendiort 250I in fresh water with potassium carbonate (about 350 g) adjusted to pH 8.0 and heated to a temperature of 6O ⁰ C. At this temperature, thormitase is added with a total activity of 1-10 ^{e of} TE. The protein cleavage takes place with constant stirring at 60 ° C within 4 hours. Subsequently, the incubation mixture is adjusted with phosphoric acid to pH 6.5 and heated to inactivate the enzyme 5 min to 100 ⁰ C. The coarse particulate connective remnants (about 200 g) are separated by a sieve. The flocculated components of the incubation mixture are recovered by filtration of the still hot peptide solution. Dio Mengo's dunkol brown filtration residue is 11 kg at a solids content of 22%.

The mainly consisting of water-insoluble cell particles and membrane-bound intact Lipiclon filtration residue is subjected to gentle drying in a fluidized bed with a mixture of trichlorethylene and ethanol (28:72 vol .-%) at 6O ⁰ C a percolation. The filtered Miszolla is distilled in a vacuum rotary evaporator, resulting in a lipid mixture.

Yield and interfacial tension lowering potential of the'oid mixture is shown in Table 1. The final product is predestined for the production of emulsions of the W / O type.

Example 2

100 kg of pork are comminuted as in Example I, boiled in water and separated from the liquid fat and the aqueous phase. The cooked meat is suspended in 250 l of water and adjusted to a pH of 7.5 with sodium hydroxide solution. At a temperature of 50 ° C, an enzyme mixture consisting of O, 5 x 10e TEThermitasu ^and 0.5 x 10 ⁶ TE pancreatin is added.

After incubation for 4 hours boi 50 ⁰ C is heated for inactivation of the enzyme for 5 min at 100 ⁰ C.

The particulate and flocculated components are separated from the peptide solution by a separator. The amount of separated residue is 20kg at a solids content of 12%.

The predominantly water-insoluble cell particles and membrane-bound lipolytic cleavage products of Lipiclon best'iende separation residue is subjected without prior drying with a mixture of hexane, ethanol and water (76: 23: 2 vol .-%) at HO ⁰ C immersion immersion. The centrifuged and filtered Miszella is distilled in a vacuum rotary evaporator, resulting in a lipid mixture.

Yield and characteristic value of the lipid mixture are reproduced in Table 1. The final product is predestined for the production of emulsions of a W / O type.

Example 3

After gentle drying in the fluidized bed, a filtration residue resulting according to example 1 is successively mixed with mixtures of ethylisoic acid ester, acetone and glacial acetic acid (2: 97: 1.5% by volume) and also methanol and ethylonyl chloride (65.5: 34.5%) Vol .-%) at 3O ⁰ C extracted by the Perkolationsprinzip. the filtered Miszellen be distilled in a vacuum rotary evaporator to give a mixture of phosphatides and a solchos the remaining lipid classes arise.

Yield and characteristic value of the phosphatide fraction are reproduced in Table 1. The final product is predestined for the production of emulsions of a W / O type.

Example 4

A separation residue resulting according to Example 2 is extracted without prior drying with a mixture of benzene, propanol and dilute sodium hydroxide solution, pH 9.0 (82.5: 9.0: 8.5% by volume) at 4O ⁰ C according to the immersion principle , The centrifuged and filtered Miszeiia is distilled in a vacuum rotary evaporator resulting in a lipid mixture. Yield and characteristic cIop Lipidgemischos are shown in Tab. 1. The final product is predestined for the production of emulsions of an O / W type.

Example 5

A Miszeiia obtained according to Example 1 is mixed with 5% water and heated at 90 ° C, wherein dissolved phosphatides deposit in the hydrate form, and the remaining lipid fractions remain in solution. The separatively abgesonnton phosphatides were dried in a thin film evaporator, won the golösten lipid fractions by distillation. Yield and characteristic value of the phosphatide fraction are given in Table 1. The final product is predestined for the production of emulsions of a W / O type.

Example 6

A Lipidgomisch obtained according to Example 1 is extracted with Acoton, wherein phosphatides remain as insoluble lipids, and remaining lipid fractions are selectively dissolved out. The filtered phosphatides were docolventisiert under nitrogen atmosphere, the dissolved lipid fractions recovered by distillation.

Yield and password of the phosphatide fraction are given in Tab. The final product is predestined for the preparation of W / O type emulsions.

Example 7

An accumulating in Example 2 lipid mixture is subjected to 4-hour Druckoxtraktion with liquefied carbon dioxide at P ₁ == 300 bar, T) = 4O ⁰ C and P ₂ = 40 bar and T ₂ = 20 ° C, wherein phosphatides as ungolöste fraction bac 'remain The other lipids go into solution.

Yield and characteristic value of the phosphatide fraction are reproduced in Table 1. The final product is predestined to produce emulsions of the O / W type.

Tab .: Yields and Grenzfiechenspannungs-Ernledrlgungspotentiale of accruing in accordance with the Ausführungsbeisplolen final products

Boispiol Gosamtlipide " Phosphatides u. Lipid predilution ²¹ free and Tri-u.Partial- % free fat interfaces % glycolipids esterified sterolo glycerides 43.8 acids voltage ³¹ % % 50.7 % rnNm 9.4 3.5 - 0.5 8.84 1 67.2 17.2 4.7 - 1.4 5.99 2 74.0 10.9 - - - 6.47 3 C9,5 18.0 - - - 5.69 4 75.4 8.3 - - - 10.55 5 67.2 18.7 - - 3.73 6 74.0 16.1 - _ 2.67 7 74.0

1) based on dio dry mass dos residue of meat hydrolysis.

2) based on the mass dor extracted Gesamtlipiod.

3) measured in 0.5% chloroform solution against bidistilliortos water boi 25 ⁰ C after 5 min.

Claims (5)

1. A process for the production of surface-active lipids in the form of structural lipids from membranes of animal tissue in the meat processing industry after proteolytic hydrolysis, preferably Abprodukton of enzymatic meat processing in which boned and optionally freed from depot fat by leaching animal tissue is subjected to a proteolysis, characterized in that Unspecific proteinases and peptidases, optionally in conjunction with a limited lipolysis by specific esterases, are used and after separation of the resulting soluble peptides resulting wet or dried Filtrations- or separation residues with binary or ternary, preferably azeotropic solvent mixtures, optionally with simultaneous lipid fractionation with selective Solvents, and, if desired, extract from the Miszella the dissolved surface-active lipids by vacuum distillation under nitrogen. Atmosphere to be separated. 2. The method according to claim 1, characterized in that the proteolysis by regarding the cleavage mechanism more or less unspecific proteinases and peptidases of microbial, plant or animal origin, preferably thermitase, subtilisin, pronase, papain, ficin, bromelin, pancreatic proteinase mixtures and / or pepsin is carried out under such selected conditions that ensure complete solubilization of the protein in an aqueous medium. 3. The method according to claim 1 to 2, characterized in that the lipolysis is carried out by selected Eisterasen, preferably Phoopholipasen as a component of pancreatic enzyme mixtures, during or after the protoolysis under such specified conditions that ensure complete solubilization of the lipids in alcohols. 4. The method according to claim 1 to 3, characterized in that for the extraction of the structural lipids azeotropic mixtures of solvents either binary mixtures of polar and nonpolar solvents, preferably of chlorinated hydrocarbons, alcohols or ketones with hydrocarbons, or ternary mixtures of nonaqueous and aqueous solvents, preferably from Hydrocarbons, alcohols and water or hydrocarbons, ketones and water are used, and optionally acids or bases for the purpose of cleavage of lipid-protein bonds are added. 5. The method according to claim 1 to 4, characterized in that as a selective solvent for Lipidfraktionierung either polar, water-miscible solvents, preferably alcohols and ketones, in combination with nonpolar, with Wa '. These water immiscible solvents, preferably hexane or gasoline , or supercritical gases, preferably carbon dioxide and its mixture with propane or trifluoromethane.