WO1990001271A1

WO1990001271A1 - Process for producing antioxidant, biologically active extracts and oily, greasy compositions rich in vitamins and their use as an active ingredient of industrial, therapeutic and cosmetic preparations, as well as an active ingredient added to nutrients and to fodder

Info

Publication number: WO1990001271A1
Application number: PCT/HU1989/000042
Authority: WO
Inventors: Valéria TÓTHNÉ PÁPAY; Valéria Katalin TÓTH; Tünde TÓTH
Original assignee: Tothne Papay Valeria; Toth Valeria Katalin; Toth Tuende
Priority date: 1988-08-11
Filing date: 1989-08-11
Publication date: 1990-02-22

Abstract

Process for the production of antioxidant, biologically active extracts and oily, greasy compositions rich in vitamins and their use as active ingredients of industrial, therapeutic and cosmetic preparations and as active ingredients added to nutrients and to fodder, by extracting and/or heat treating together or separately one or more substances which are part of plant and/or animal origin and/or fat or oil containing ballast material, fat and protein containing animal or plant material with at least 5 % of unsaturated fatty acids and vitamins A, D, E and K, the extraction and/or heat treatment is carried out, optionally in a CO2, nitrogen oxide or ethane atmosphere, in carbonic acid, acetic acid, formic acid or formic acid-hydrogen peroxide vapour space cold and/or warm, for one minute to several days, at a temperature of -70°C to +300°C, with one or more organic solvents and/or water, glycerine, 1,2-propylene glycol and/or with the mixture of these and/or with or without the aqueous solution of salts, acids and bases, optionally in the presence of aromae, flavouring, colouring and sweetening substances, enzymes and/or preservatives, until the oily material precipitates, then optionally the oil or greasy material is separated from the solid phase or aqueous or organic solvent containing phase, it is cleaned and dehydrated and optionally the oily, greasy compositions or extract or fat obtained are adsorbed together or separately onto carbohydrate material or onto salts or alkaline-earth metals and are dried.

Description

PROCESS FOR PRODUCING ANTIOXIDANT, BIOLOGICALLY ACTIVE EXTRACTS AND OILY, GREASY COMPOSITIONS RICH IN VITAMINS AND THEIR USE AS AN ACTIVE INGREDIENT OF INDUSTRIAL, THERAPEUTIC AND COSMETIC PREPARATIONS, AS WELL AS AN ACTIVE INGREDIENT ADDED TO NUTRIENTS AND TO FODDER

The invention relates to a process for producing antioxidant, biologically active extracts and oily greasy compositions rich in vitamins and their use as an active ingredient of industrial, therapeutic and cosmetic preparations, as well as an active ingredient added to nutrients and to fodder.

For the existence, growth and multiplication of the living organisms nutriments of proper composition are required.

The energy requirement of human and animal organism is covered by fats, carbohydrates and proteins, while vitamins and trace elements maintain and regulate the metabolism.

In addition to foods of vegetable origin people consume foods of animal origin too. To produce animal protein fodder of proper composition and good quality is needed, the production cost of fodder amounts to 50-80% of the total cost of meat production.

For protecting the health selection of the composition of food or fodder is of utmost importance, as even the slightest change in metabolism may be injurious to health.

Microorganisms living in the human being or in its environment attack the organism in case of diseases or weakened health, upon the effect of stress, of physical or nervous overstrain, in case of change in the weather. The microorganisms penetrate through the intact or damaged tissues, are parasitic on the organism, produce toxines and enzymes, by this the normal metabolism is unbalanced the natural protective barriers of the organism are loosened, the tissues are dissolved, the structure of cells is injured, the microorganisms disturb the vital functions, decrease the oxidative phosphorylation , less energy is delivered, the prophylactics are neutralized the organism is poisoned and thereby can cause death. Oils and fats contain unsaturated fatty acids, lecithin, phospholipoids, choline and vitamins being soluble in fat, vitamin E of antioxidant property, which substances prevent the decomposition of foodstuffs and their becoming rancid and preserve vitamins and fat. Oils and fats rich in unsaturated fatty acids, lecithin and vitamins protect the organism, they are taking part in the maintenance of ability of protection, they protect and preserve the wholeness of the blood- -vessels and epidermis, protect the skin against iπfec- tioπs, have an antiphlogistic effect and have an important role in the haematogenesis.

Replacement of the above substances is of particular importance in case of those suffering in chronic illnesses, taking medicines in excess, in case of reconvalescent or underfed people, and in nutrition of children, elder people and sportsmen.

According to the prior arts oils and greases are gained from fresh or roasted seeds by cold-pressing, by pressing in warm state after heat-treatment or by solvent extraction. (The Merck Index, 9th edition,

Encyclopedia of Chemicals and Drugs, Merck and Co. Inc. Rahway N.J. USA, 1976, 349, 6687, 6853, 7363, 8006, 8502 pp); Jaky M., Meister 3 . , Stris M.: Ndveπyi olajok es allati zsirok gyartasismerete (Specification of production of vegetable oils and of fats of animal origin), Budapest 1952. page 209, Elelmiszeripari Konyv es Lapkiadό Vallalat (Publishers of Books and Periodicals of the Foodstuff Industry); E.W. Eckey: Vegetable Fats and Oils, Reinhold, New-York, 1954. 200-250, 291-295, 535-547, 742-777 pp.)

If cold-pressing or solvent extraction is used toxic materials or materials inhibiting nutrition can get into the product, accordingly further cleaning is necessary, which again deteriorates the quality of the fat, reduces the vitamin content of the oil, causes a change in the flavour and colour of the oil and makes it becoming easier rancid. In course of heat treatment, roasting or fermentation the colour and flavour of the fats changes, simultaneously also the protein content will suffer certain damages. In each cases a further purification is necessary, what increases the costs and reduces the biological value of the oil.

In different inventions it is aimed to increase the vitamin E content, partly by addition of vitamin E, partly by using seeds of increased vitamin E content for processing fats of vegetable origin.

According to the method described in the Hungarian Patent No. 181,040 fat containing proteins of animal and vegetable origin are treated together at a pressure of 1 to 2 atm, the seeds of vegetable origin are treated without roasting, thereafter they are hydrated, and a composition is produced by flocculation for fodders.

According to the method described in the Hungarian Patent No. 181,249 fat combinations of high phosphatid content are prepared from oily seeds and fats of animal origin at a high pressure and high temperature; then the mass is dehydrated, separated by centrifugiπg, and to the oil an oil containing vitamin E is added and it is mixed with milk, corn grits, soya flour .and protein of animal origin, is pulverized and spray-dried, then granulated.

According to the method described in the Hungarian Patent No. 181,760 materials with fat content are transformed into grains of microsize then are mixed with liophyl materials on hydrocarbon basis, milk, pulverized egg, organic acids, sugar and emulgeating agents, thereafter fat is produced by atomizing, freezing and shrinking. According to the method described in the

Hungarian Patent No. 185,149 seeds are roasted at a high temperature, compressed at a high pressure and the residue is hydrated, treated at a high temperature, thereafter additional oil can be pressed out. Drawback of the said inventions lies in that only fats for use in fodders can be obtained, and the heat treatment and other complicated and expensive operations used cause decomposition, change and declined quality. The object of the invention is to produce oily, fatty composition having a complex biological activity, being rich in vitamins and aroma substances and having an antioxidant effect.

The invention is based on the recognition that the aim set can be reached by the simultaneous processing of oil and fat containing organs or parts of animal or plant origin having biological activity.

In course of simultaneous processing of parts of vegetable and animal origin the efficiency of the recovery can be increased by performing the extraction in more steps in cold and warm state, thereafter, from the material obtained the individual fractions are separated by a solvent fractionation. Extraction is performed so, that fresh or air-dry materials together or in a frozen state are processed, without heating. The extraction is ^'performed from the fresh plant in a cold state for 5 minutes to several hours thereafter at the boiling point of the solvent, then extraction in is performed a warm state from the plant material mixed with the animal materials repeatedly for 15 minutes to several hours so, that the summarized duration of the warm extractions should amount to at least four hours.

The temperature range of the cold and warm extractions together is -70 to 360 °C. The efficiency of the extraction may be increased by using elevated or reduced pressure. Extracts and electrolytes are fractioned together with solvents.

Furtheron, the invention is based on the recognition, that the recovery and efficiency of the antioxidant and unsaturated fatty acids can be increased, if instead of shaking out with petroleum ether or petrol, the mixture of petroleum ether with ether is used or saponification is performed and the esters of fatty acids are produced. The invention is based also on the observation that the oxidizing substances of extracting agents and of auxiliary substances can be neutralized or oxida¬ tion can be prevented by using acids, salts or products of apiculture. Further, the invention is based on the recognition that the effect of the oily, fatty composi¬ tions obtained can be improved by means of substances having different pharmaceutical effect and by other active ingredients. Summing up, the invention relates to a process for producing antioxidant, biologically active extracts and oily, greasy compositions rich in vitamins and their use as an active ingredient of industrial, therapeutic and cosmetic preparations, as well as an active ingredient added to nutrients and to fodder. According to the invention one or more substances which are parts of plant and/or animal origin containing 1 to 95 % by weight of oil and/or fat and/or one or more tissue and/or secretion of plant and/or animal origin containing 3 to 95 % by weight of ballast material, which substances contain 1 to 90 % of fatty acid within this at least 5 % of unsaturated fatty acid, 0,0001 to 20 g of vitamin A or provitamin A, 0,0001 to 20 g of vitamin D, 0,0001 to 10 g of vitamin K, 0,0001 to 20 g of vitamin E and 2 to 80 % by weight of total protein related to 100 parts by weight of the starting material; the above protein contains in free and bound form alltogether 0,0001 to 10 g of glutamic acid, aspartic acid, lysine, methioπine, cysteine, arginine, proliπe, leucine, and glycine are extracted and/or heat-treated together or separately, once or more times after each other, optionally at elevated or reduced pressure or at atmospheric pressure, optionally in a C0₂, nitrogen oxide, ethane atmosphere, in a formic acid, carbonic acid, acetic acid or formic acid-hydrogen peroxide vapour space, cold and/or warm for 1 minute to several days at a temperature of -70 °C to +300 °C, preferably at -20 °C to +200 °C, more preferably at -20 °C to +160 C, with one or more organic solvent and/or water, glycerine, 1 , 2-propylene glycol and/or with the mixture of these and/or with or without the aqueous solution of salts, acids and bases, optionally in the presence of aromae, flavouring, colouring and sweeten¬ ing substances, enzymes and/or preservatives, until the oily material precipitates, then optionally the oil or greasy material is separated from the solid phase or aqueous or organic solvent containing phase, it is cleaned and dehydrated and optionally the oily, greasy compositions or extracts or fat obtained are adsorbed together or separately onto a material of 1 to 99 % by weight carbohydrate. content or onto salts or alkaline- -earth metals and are dried.

Parts, compositions, fractions gained in course of individually performed extraction and heat treatment are mixed in the required proportion.

The extraction may be performed by shaking in a shaker, by agitating, or using an U-extractor, the heat treatment may be realized on a baking tray, in microwave- -oven or in Papiπ-vessel. As starting materials fresh, frozen or dried vegetable parts, seeds, crops, cereal seeds, germinating seeds of plants, fruits, seeds of fruits, flowers, buds, bark of tree, leaves, roots, tubres, mushrooms, yiest, fresh or dried herbage, household waste, fresh or frozen fat of animal origin, tallow, bones, marrow, liver, meat, blood, fish, products of apiculture, milk and milk-products can be used.

Oil and fats are separated from solid parts, from aqueous extracts or from ballast materials by salting out, freezing or using alcoholic water or organic solvent. As solvents alcohols, aliphatic hydrocarbons, ethers, chlorinated hydrocarbons, ketones, esters, glycerines, glycols, salts, acids and bases can be used. After having separated the fat, the solid matter and the aqueous or organic solvent containing extract can also be utilized. By means of salts and heat treatment from the aqueous and organic solvent containing part the proteins and carbohydrates can be precipitated and by fractionation different biologically active substances can be obtained.

Both fats, extracts or compositions may be recovered together with the solid ballast material, or separately, in a pulverized form, dried on a material of carbohydrate basis, on salts or on alkaline earth metals. The efficiency of the oily fatty composition, oil, fat, extracts or mixture gained according to the process of the invention may be further increased by adding extracts of herbs and active ingredients of therapeutic effect, so e.g. volatile oils, aroma materials, vitamins and salts.

The main advantages of the process according to the invention are as follows:

The process can be realized on large-scale industrial level quickly, easily and in an energy saving manner, it is cheap, easily available fresh, frozen or dried parts of vegetable and animal origin can be processed together or separately, and simultaneously with the solid and oily, liquid materials a sterile composition, oil, greasy substance or extract of high active ingredient content, having an antioxidant effect can be obtained with a low energy consumption and without decomposition or change.

The product obtained is free of histamine, no substances inhibiting nourishment are contained and is sterile .

The product can be easily pulverized and can be used for therapeutical, cosmetic and industrial purposes or as a fodder. It is resistent to heat, light and oxida- tion, and has a stable composition which can be maintained permanently.

The process according to the invention will be detailed by means of examples:

Example 1

Production of an oily composition:

350 g of egg-yolk, 20 g of wheat-germs, 50 g of corn-germs, 50 g of soya-bean flour, 40 g of royal jelly, 20 g of cod-liver oil and 200 g of sunflower seed flour - Sⁱ -

are mixed with the same volume of water containing 5% of lemon juice, 20 g of 1 , 2-propylene glycol and 20 g of glycerine; the mixture obtained is cooked in a Papin-vessel at a reduced pressure for 30 minutes; then is filtered, pressed, and the residue is mixed with 200 g of sunflower oil and with water in a quantity equal to the sum of all the previous components, and is baked in a microwave oven in carbon dioxide atmosphere up to the segregation of oil, thereafter the oil is frozen out from the aqueous part; is purified with a solution containing 0,25% of sodium chloride, washed with water and dehydrated in vacuum.

The oil obtained is suitable for application in therapeutics, cosmetics, in the foodstuff and confectionery industry, and for preparing dyestoffs. The product has high vitamin content and anti¬ oxidant character, it is suitable for increasing lime and phosphorus supply, it improves haemotogenesis, reduces haemophilia, it can be used for treating disturbances of vision, impairing of sight and treating cataract, increasing epithelisation, protection of skin and skarfskin, for '.treatment of burned wounds ' and for the preparation of cosmetics and medicines . In food processing the product can be used as salad-dressing, in mayonnaise, admixed to butter, in dietetic foodstuffs, cakes, confectioneries and for improving chocolate basis.

The extract per se and also together with oil is suitable for preparing medicines, foodstuffs and cosmetics. The residue obtained after the recovery of the oil can be used in dietetic meals, foodstuffs, and as additives given to fodder.

By unifying the aqueous extracts valuable protein, polysaccharide mixture can be produced by means of alcoholic precipitation.

The egg-white can be admixed to foodstuffs, or to fodder additives or valuable lyzozime enzym may be obtained from it using am onium-sulfate precipitation and purified with ultracentrifuging.

The egg-shell can be admixed to the fodder or can be formed to a valuable calcium substituting material, and from the pellicle by cleaning, washing, sterilizing, crushing and pressing ^' a semipermeable filter can be prepared for filtering gases and salt solutions.

Example 2

250 g of egg, 100 g of beef-tallow, 100 g of soya-bean fluor, 40 g of pollens, 50 g of honey, 300 g of sweet cream, 50 g of ground hazel-nuts, 50 g of coco- -scrapings, 50 g .of cacao butter, 50 g of sesame seeds, 20 g of ground walnuts, 20 g of almonds and 50 g of comminuted raisins are mixed and baked until oil segregation, thereafter it is boiled with water of the same quantity containing 5% lemon juice, thereafter it is centrifuged with 40.000 r.p. .; the oil is purified with sodium chloride solution of 0,25%, washed with water and dehydrated in vacuum. The oil and the residue can be used together for preparing foodstuffs and confectioneries.

Purified oil respectively fat can be used - with or without being hydrogeπated - in therapeutical, cosmetical or other industrial products in foodstuffs and confectioneries, further as additives to fodder or feed.

Example 3

Antibacterial - and fungicidal, wound-healing oil and preparation 200 g of egg-yolk, 100 g of glands of duck-rump, 100 g of leaf-lard, 50 g of pollens, 150 of poplar buds or the extract thereof, 50 g of propolis and 50 g of beeswax are cooked in a microwave oven with 1000 g of water containing 1% of citric acid and 0,9 g of sodium chloride, then it is baked until oil formation. Water of 0 C° is added in identical quantity, oil and fat are allowed to freeze, the aqueous part is shaken out once with a chloroform-izopropanol mixture, thereafter, together with the oily part it is concentrated and mixed with 250 g of cyclodextriπe , 50 g of glucose, 50 g of amylopectine , 10 g of ascorbic acid, 30 g of cod-liver oil, 10 g of lactic acid and 200 g of water, then the mixture is dried in a microwave oven to a powder, and the powder is applied for pharmaceutical and cos etical purposes in the form of toilet-powder and ointment.

The product has antibacterial, fungicidal and antiinflammatory effect, heals wounds, increases capillary resistance and has a drying effect. The residue can be used for fodder.

Example 4

Feed and fodder additive of a roborant effect and curing anaemia

2000 g of frozen harslet of animal origin (liver and blood), the dried pulver prepared from 1000 g of fruits, 1000 g of vegetables (carrots, red beets, cabbage-leaves, kohlrabies, onions, tomatoes, pumpkins), 1000 g of seeds (beans, peas, soya-beans, caraway-seeds, coriander seeds, lentils, mustard-seeds), the dried pulver prepared from 1000 g of fresh-vegetables (nettles, elder-blossoms, clovers, mulleins, birch-leaves, birch barks, thyme), 500 g of milk-powder, 500 g of roasted grape-stones, as well as water of the same quantity as the above components together and containing 5% lactic acid are cooked then baked in a microwave oven up to segregation of oil, thereafter water of the same quantity is added, thereafter separated from the ballast material and shaken out with petroleum-ether then with a chloroform-iso-propyl alcohol mixture three-times. The aqueous part and the parts containing organic solvent are concentrated and dried onto a substance of carbohydrate basis or on alkaline earth metals. Fat contained in the petroleum ether is saponified with ethanol containing 5% of sodium hydroxide then is shaken out and esterified in the presence of sulphuric acid and ethanol, then it is purified with ether and aqueous sodium chloride, is shaken out, the organic solvent is removed and the residue is used in medicines and cosmetics.

The oil-containing ballast material is dried onto corngrits of identical quantity, 100 g of salt- -mixture and 150 g of egg-shell is added to it, and the product is used as fodder additive for feeding anemic animals.

The oil or oil-containing composition has a roborating effect, improves appetite, substitutes salts, is effective against anemie, and protects the organism against infections.

The product is well suitable for feeding calves, pigs, sheep, chicken, poultry, domestic animals, dogs, cats, deers and wild animals.

Claims

We claim:

1. Process for the production of antioxidant, biologically active extracts and oily, greasy composi¬ tions rich in vitamins and their use as active ingredients of industrial, therapeutic and cosmetic preparations and as active ingredients added to nutrients and to fodder, c h a r a c t e r i z ed i n extracting and/or heat treating together or separately one or more substances which are parts of plant and/or animal origin and/or fat or oil containing ballast material, tissue or secretion of animal or plant origin containing 1 to 95 % by weight of oil and/or fat which substances contain 1 to 90 % by weight of fatty acids within this at least 5 % of unsaturated fatty acids, 0,0001-20 g of vitamin A or provitamin A, 0,0001 to 20 g of vitamin D, 0,0001 to 10 g of vitamin K, 0,0001 to 20 g of vitamin E and 2 to 80 % of total protein, which protein contains in free or bound form 0,0001-10 g of glutamic acid, aspartic acid, lysine, methionine, cysteine, argiπiπe, proliπe, leucine and glyciπe, the extraction and/or heat treatment is carried out optionally at an elevated or reduced pressure, optionally in a C0₂, nitrogene oxide or ethane atmosphere, in carbonic acid, acetic acid, formic acid or formic acid-hydrogen peroxide vapour space cold and/or warm, for one minute to several days, at a temperature of -70 °C to +300 °C, preferably at

-20 C to +200 C more preferably at ■20 °C to +160 °C with one or more organic solvent and/or water, glycerine 1 , 2-propyleπe glycol and/or with the mixture of these and/or with or without the aqueous solution of salts, acids and bases, optionally in the presence of aromae, flavouring, colouring and sweetening substances, enzymes and/or preservatives until the oily material PCI7HU89/000 /01271

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precipitates, then optionally the oil or greasy material is separated from the solid phase or aqueous or organic solvent containing phase, it is cleaned and dehydrated and optionally the oily, greasy compositions or extract or fat obtained are adsorbed together or separately onto a material of 1 to 99 % by weight carbohydrate content or onto salts or alkaline-earth metals and are dried, and in that case if the extracts were gained by separate extraction and powdering, the extracts and powders are mixed in the required proportion.

2. Process for producing pharmaceutical composi¬ tions for human and veterinary use, characterized in that the extracts, oils, fats, compositions or powders prepared according to claim 1 are mixed with one another and/or with pharmaceutically acceptable carriers and/or other adjuvants and are formulated into different medicines (solutions, syrups, powders, emulsions, suppositories, ointments, toilet- -powders, injections, tablets etc.)

3. Process for producing cosmetics, characterized in that extracts, oils, fats and compositons prepared according to claim 1 are mixed with each other and/or with carriers usually applied for preparing cosmetics and are formulated into cosmetics.

4. Process as claimed in claim 1, characterized in that the extracts, oils and fats are mixed with each other or used separately, in a mixed or unmixed form in foodstuffs or in foodstuff- -concentrates in accordance with the demands and like this finished or semi-finished products, dried, pulverized foodstuffs are prepared.

5. Process as claimed in claim 1, characterized in that extracts, oils, fats, compositions or powders are mixed with each other or mixed with carriers and or other adjuvants usually applied in confectionery and in distilling industry, producing like this products of these industries.

6. Process as claimed in claim 1, ch a r a c t er i z ed in that extracts, oils, fats, compositions and powders having been gained in the process of the invention are used with or without ballast material for producing active ingredients or as ingredient of fodder.

7. Process as claimed in claim 1, ch a r a c t e r i z e d i n that the oils gained in the process of the invention can be used as starting material for preparing varnish, laque and dyestuff.

8. Process as claimed in claim 1, c h a r a c t e r i z e d i n that the whole raw material, the products and all the by-products are utilized together or separately in the canning industry, food- -iπdustry, in preparing starting materials, as nutrient substances, fodder, heating material or compost.

9. Process as claimed in claim 1, c h a r a c t er i z e d i n that the parts of animal or vegetable origin serving as starting material are processed fresh, dried or frozen, together or separately, and bring them into the required form.