RU2233104C1 - Method for complex reprocessing of brown algae for producing of iodine-containing and polysaccharide products - Google Patents

Abstract

FIELD: food-processing industry, in particular, reprocessing of brown algae for obtaining of base products having biological properties.

SUBSTANCE: method involves grinding brown algae; extracting with aqueous-alcoholic solution, in particular, 65-75%-solution of ethanol, at temperature of 50-60⁰C for 1.5-2.5 hours; removing alcohol from aqueous-alcoholic extract; cooling resultant aqueous-lipid emulsion to temperature of 5-10⁰C; separating said emulsion by settling into aqueous and lipid fractions to obtain biologically active substances; obtaining iodine-containing mineral-magnetic complex from aqueous fraction and iodine-containing lipid complex from lipid fraction; extracting algae remains (1) with 1.0%-hydrochloric acid solution for 6-10 hours at room temperature; heating resultant mass to temperature of 45-55⁰C for 4-6 hours; sequentially neutralizing resultant acidic extract with potassium or sodium carbonate to pH value of 7; boiling out under vacuum at temperature of 50-55⁰C to volume making 1/4-5 of initial volume; providing double settling of fucoidane concentrate with triple volume of ethanol; extracting algae remains (II) at pH value of 8-9 for 10-15 hours at room temperature, followed by heating mass to temperature of 80-85⁰C for 1-2 hours; filtering extract until contaminants content is below 1 g/l; obtaining calcium algilose and/or sodium algilose as biologically active substances. Calcium algilose is produced by adding 10%-calcium chloride solution to filtrate at the rate of 2.0-2.5% by weight of dry substances. Sodium algilose is produced by adding sodium carbonate to alginic acid at the rate of 27-30% by weight of dry substances. Alginic acid is separated from filtrate by 10%-hydrochloric acid solution.

EFFECT: provision for simultaneously obtaining of several additives containing biologically active substances, maximal extraction of iodine-containing compounds by using soft modes of reprocessing of raw materials.

3 cl, 3 ex

Description

The invention relates to the food industry and can be used for complex processing of brown algae to produce iodine-containing and polysaccharide food additives, which can be used as a source of iodine, nutrients, deficient amino acids, polyunsaturated, fatty acids and polysaccharides with high pharmacological activity

Laminar algae are a natural source of nutrients, including iodine, in the form of mineral salts and organic compounds. The content of iodine in brown algae is on average 0.1-0.2%. The main part of iodine-containing substances is water-soluble and is easily extracted from algae. In the process of processing algae, the main amount of iodine is lost along with nutrients, fucoidan, free amino acids, mannitol. Our processing method allows you to save all biologically active substances and get them in the form of iodine-containing and polysaccharide food additives.

The iodine-containing additives include trace elements: copper, molybdenum, selenium, and others; amino acids - first of all, tyrosine, phenylalanine, methionine and unsaturated fatty acids, and only with the presence of the whole complex of these substances is it possible to synthesize thyroid hormones and assimilate iodine in the human body

Brown algae polysaccharides (alginate and fucoidan) possess valuable physicochemical properties and high pharmacological activity, in particular, antitumor, anti-inflammatory, sorption, etc.

These polysaccharides are used in the food industry, for example, sodium alginate, both as a thickener, stabilizer, and as food additives with therapeutic and prophylactic properties.

A known method of complex processing of brown algae to obtain mannitol, mineral, lipid concentrate and kelp extract (SU, AS No. 1381925, MKI C 07 C 31/26 "Method for producing mannitol from kelp algae"). The method includes grinding brown algae, extracting them with 86% alcohol solution for 1 h at a temperature of 80 ° C, distilling off the alcohol from the extract, settling the aqueous extract, separating the kelp mineral and lipid concentrate.

The disadvantage of this method is the production of mineral and lipid concentrate with a small iodine content as a result of the use of high temperature during extraction of the feedstock.

A known method of complex processing of dry algae (RU, Patent No. 2142812, MKP ⁶ A 61 K 35/80 “Method of complex processing of dry raw materials of algae”). As dry raw materials, thalli of the White Sea kelp are used. Extract dry crushed algae simultaneously with oil or fat and a water-alcohol mixture with a ratio of components: dry algae 1; oil or fat 3-40; ethyl alcohol 1.5-15; water 1-30. The extract is separated from the meal, the oil or fat phase is separated, mannitol and mineral concentrate are isolated from the water-alcohol phase, and alginate is extracted from pulp.

The disadvantage of this method is:

- incomplete extraction of biologically active substances of algae - fucoidan;

- high extraction temperature, at which loss of algae iodine compounds occurs, as well as a decrease in the quality of alginates;

- the operation of thermal alkaline extraction with sodium carbonate after alcohol treatment for 0.5-1.5 hours is insufficient for algae swelling and maximum extraction of alginic acid into the extract, resulting in a small yield of sodium alginate.

The known method (RU, patent No. 2005485, IPC C1, A 61 K 35/80. Bull. No. 1 “A method of obtaining funds for the treatment of skin diseases in animals”). Air-dried ground algae of the genus Laminaria are twice extracted with 96% ethanol at a temperature of 65-75 ° C, the extracts are combined and kept at ambient temperature for at least 16 hours, the precipitated mannitol precipitate is filtered off and recrystallized from aqueous ethanol, the filtrate is evaporated to dryness, the residue extracted with 96% ethanol, the resulting extract was evaporated to dryness to obtain a biologically active product of lipid nature (“Algolipin”).

The disadvantage of this method is:

- receiving only two products (mannitol, “Algolipin”);

- production wastes are valuable biologically active substances - minerals, fucoidan, alginate-containing products.

A known method of producing a lipid concentrate from brown algae (RU, application No. 93002017, IPC A 61 K 35/80 “Method for producing a lipid concentrate from algae”), according to which air-dried raw materials and crushed are twice extracted with 86-89% ethanol solution at 65 - 75 ° С, mannitol and lipids are extracted from the extract, which are then purified from water-soluble impurities.

The disadvantage of this method is:

- the irrational use of raw materials, in which only two products from algae (mannitol and lipids) are obtained, while a large number of biogenic macro- and microelements are lost;

- algae pulp containing alginates and fucoidan is not used.

A known method for the complex production of water-soluble polysaccharides from brown algae - laminarans and fucoidans (RU, patent No. 2135518, IPC 08 V 37/00 “Method for producing water-soluble polysaccharides from brown algae”). The method involves the processing of fresh, or fresh-frozen, or dry algae with solvents in order to remove low molecular weight substances, the extraction of polysaccharides with 0.1 N hydrochloric acid at room temperature and water at 50-60 ° C. The separation of laminarans and fucoidans and their subsequent fractionation is carried out with using hydrophobic chromatography The disadvantage of this method is that:

- receive only three products - alcohol-water extract, laminaran and fucoidan;

- alcohol-water extract is not divided into fractions;

- production wastes are valuable biologically active substances - alginate-containing products.

The closest in technical solution is the method of complex processing of a mixture of White Sea brown algae (L. saccharina and L. digitata) (RU, patent No. 2028153 C1, IPC ⁶ A 61 K 35/80. Bull. No. 4 “A method of obtaining biologically active substances from kelp ”) in order to obtain mannitol and polysaccharides (water-soluble polysaccharide complex, laminar, fucoidan and sodium alginate) by extracting crushed dried raw materials with 90-96% ethanol in a ratio of raw materials: ethanol 1: 6 at a boiling point of the extractant for 3 hours, evaporation of the filter Nogo alcoholic extract, mannitol crystallization, its purification by recrystallization.

Then, the algae are extracted twice with water in a ratio of 1:10 at a temperature of 80 ° C for 30 min, the aqueous extracts are combined, filtered, evaporated in vacuo, from the cooled extract 96% ethanol in the ratio extract: ethanol 1: 2 precipitates a water-soluble polysaccharide complex, and is filtered off , purified three times with 96% ethanol, dried. The alcohol mother liquor remaining after precipitation of the water-soluble polysaccharide complex is evaporated to 1/10 of the initial volume, after which the condensed extract is treated with 80% ethanol in the ratio of extract: ethanol 1: 3. The resulting precipitate (laminaran and fucoidan) is centrifuged, separated by treatment with a 0.4% hydrochloric acid solution at a precipitate: hydrochloric acid ratio of 1: 5 at room temperature for 2.0 hours; then, a 0.5 M solution of cetavlon is added to the resulting solution to convert the acid polysaccharides to a precipitate. The precipitate was separated, and the supernatant was treated with 80% ethanol (to precipitate laminaran) in the ratio of supernatant: ethanol 1: 3. The resulting laminaran is filtered, purified with 96% ethanol, and dried. The precipitate formed after the addition of cetavlon is dissolved in a 0.4% hydrochloric acid solution in the ratio of precipitate: hydrochloric acid solution 1:10 and treated with 70% ethanol in a solution: ethanol ratio of 1: 3, a precipitate of fucoidan precipitates, which is filtered, purified, dried . After that, the algae pulp was extracted with a 1.5% sodium carbonate solution in a ratio of 1:20 at a temperature of 50 ° C for 1 h, the aqueous-alkaline extract was filtered, the filtrate was treated with concentrated sulfuric acid, the precipitate formed was separated, treated with 1.5% sodium carbonate solution and get sodium alginate precipitation of 96% ethanol in the ratio of solution: ethanol 1: 5. Sodium alginate is filtered, dried.

The disadvantage of this method are:

- a small yield of sodium alginate;

- the use of alcoholic extraction at the boiling point of the extractant to extract mannitol from brown algae, which leads to the loss of iodine-containing compounds and the destruction of polysaccharide chains;

- the complexity and energy intensity of the process associated with the need for evaporation of a large amount of ethanol solution;

- production wastes are valuable biologically active substances of brown algae - lipid fraction, a large number of minerals.

The objective of this technical solution is the integrated processing of brown algae with the simultaneous production of several food additives containing biologically active substances, the maximum extraction of iodine-containing compounds through the use of soft processing modes of raw materials, expanding the range of products.

The problem is solved by grinding the raw material, extracting it with an aqueous-alcoholic solution, separating the aqueous-alcoholic extract from the algal residue (I) by filtration and obtaining biologically active substances from it; extraction of the algal residue (I), separation of the extract from the algal residue (II) by filtration, obtaining from it a polysaccharide; extraction of the algal residue (II) with sodium carbonate solution, separating the filtrate from the algal residue treated with sodium carbonate by filtration, isolating alginic acid from the filtrate, treating it with a salt to obtain a biologically active substance, while the grinding of the raw materials is carried out with a 65-75% ethanol solution at a temperature 50-60 ° C for 1.5-2.5 hours, the water-alcohol extract is freed from alcohol, the resulting water-lipid emulsion is cooled to a temperature of 5-10 ° C, and it is separated by settling into the aqueous and lipid and make biologically active substances from them, moreover, iodine-containing mannitol complex is obtained from the aqueous fraction, and iodine-containing lipid complex is obtained from the lipid fraction; the algal residue (I) is extracted with a 1.0% hydrochloric acid solution for 6-10 hours at room temperature, followed by heating the mass to a temperature of 45-55 ° C for 4-6 hours, and then the acid extract is successively neutralized with potassium or sodium carbonate to pH 7 and evaporated in vacuo at a temperature of 50-55 ° C to 1 / 4-5 of the original volume of the extract, fucoidan concentrate was precipitated twice with a three-fold volume of ethanol; the algal residue (II) is extracted at pH 8-9 for 10-15 hours at room temperature, followed by heating the mass to a temperature of 80-85 ° C for 1-2 hours and insisting it for 3-4 hours, filtering the extract to an impurity content of not more than 1 g / l, calcium algylose and / or sodium algylose are obtained as a biologically active substance, while calcium algylose is obtained by adding calcium chloride to the filtrate in the calculation of 2.0-2.5% by weight of dry substances, and sodium algylose - by adding sodium carbonate to alginic acid calculation of 27-30% by weight solids, wherein the alginic acid is recovered 10% solution of hydrochloric acid and calcium chloride is used as a 10% solution.

The proposed technical solution meets the criteria of “novelty”, “inventive step” and “industrial application”.

The proposed method of complex processing of algae allows you to simultaneously get several food additives containing biologically active substances: two iodine-containing products - iodine-containing mineral-mannitol and iodine-containing lipid complexes - with an iodine content exceeding its content in the feedstock in 3.2-4.5 and 1 , 6-2.0 times, respectively, sodium algylose and calcium algylose, as well as fucoidan concentrate. The resulting nutritional supplements have a wide range of pharmacological properties.

The essence of the method is as follows: pre-crushed, to a particle size of 0.3-0.5 cm, dry algae is extracted with a 65-75% solution of ethyl alcohol with a ratio of raw materials: extractant 1: 5-10, temperature 50-60 ° C for 1.5-2.5 hours with periodic stirring. At the end of the extraction process, the treated algae is separated from the extract by filtration and sent to obtain polysaccharides, and the extract to distill off the alcohol.

After removing alcohol from the aqueous-alcoholic extract, a water-lipid mixture is obtained, which is cooled to a temperature of 5-10 ° C, and then defended for separation into lipid and aqueous fractions.

The aqueous fraction, hereinafter referred to as the “iodine-containing mineral-mannitol complex”, is drained, concentrated at a temperature of not more than 60 ° C (with or without vacuum) to a mass fraction of water of not more than 60% and evaporated or sent for drying at a temperature not exceeding 60 ° From to a mass fraction of water in a product no more than 15% and pack.

The remaining lipid fraction, hereinafter referred to as the “Iodine-containing lipid complex”, is drained and packaged.

The iodine-containing mineral complex is a granule or powder from dark to light brown in color with a characteristic odor of algae. Of the organic substances, the main part is mannitol (28.3-38.7%), amino acids (6.7-8.8%). The content of mineral substances reaches 40-50%, iodine - 0.7-1.03% (in terms of dry matter).

The iodine-containing lipid complex is a thick, oily mass of greenish-brown color with a characteristic odor of algae.

In the “lipid complex”, the main part is accounted for by organic substances: protein (4.2-5.0%) and lipids (80.9-88.0%); mineral substances (6.2-10.8%), iodine content (0.32-0.43%).

The algal residue (I) is treated with a 1% solution of hydrochloric acid, LC 1:10 for 6-10 hours at room temperature, and then the mass is heated to a temperature of 45-55 ° C for 4-6 hours with periodic stirring. The acid extract is separated from the algal residue (II) treated with hydrochloric acid by filtration, followed by centrifugation. The acid extract is first neutralized with sodium carbonate (or potassium) to pH 7, and then evaporated in vacuo at a temperature not exceeding 50-55 ° C to 1 / 4-5 of the original volume of the extract. From the solution obtained after evaporation, the fucoidan concentrate is precipitated by treating it twice with 96% ethanol in a solution: alcohol ratio of 1: 3 and dried.

Fucoidan concentrate is a powder from light cream to pale yellow odorless, soluble in water, in acids, insoluble in ethanol.

Fucoidan Concentrate contains: 33.4-40.1% fucoidan; 31.1-34.7% of minerals; 18.3-22.7% sulfate groups; 0.9-1.1% alginic acid.

The yield of fucoidan concentrate is 10.6-12.3%.

The algal residue (II) after acid treatment is used to produce sodium algylose or calcium algylose. The algal residue (II) is washed with fresh water at room temperature and treated with a solution of sodium carbonate at a liquid phase of 1: 40-50, first at room temperature at pH 8-9 for 10-15 hours, and then with stirring and maintaining the temperature at 80-85 ° С for 1-2 hours and insisting for 3-4 hours. The resulting extract is filtered in two stages: on a rotary filter with a sieve No. 6-8 and then on a rotary filter with a sieve No. 65-70. The result is a filtrate with an impurity content of not more than 1 g / l, which is cooled to a temperature of 10-20 ° C.

Two target products are obtained from the obtained filtrate.

The filtrate is divided in half and alginate-containing products are obtained from them, which are named "Sodium Algylose", "Calcium Algylose".

“Sodium algylose” is prepared as follows.

Alginic acid is isolated from the filtrate by adding a 10% hydrochloric acid solution to pH 1-2 (with periodic stirring), which is separated from the solution by filtration. The alginic acid gel is washed with hot water at a temperature of 60-70 ° C to pH 3-4.

The washed alginic acid gel is mixed with sodium carbonate at the rate of 27-30% by weight of the solids of the gel and get the target product. The mixture is kept at room temperature and periodically stirred until the reaction between the alginic acid gel and sodium carbonate is completed to a pH of 6.5-7.0.

The target product is twice precipitated with 96% ethanol and dried at a temperature not exceeding 50-55 ° C.

“Sodium algylose” is a light cream powder, soluble in water, insoluble in acid and alcohol. The yield is 26.6-29.8%. Sodium algylose contains: minerals 22.7-25.7%; alginic acid 73.4-76.1%; fiber 0.5-0.8% (dry matter), the viscosity of a 0.2% aqueous solution of sodium algylose is 7.5-8.6 × 10 ^-3 Pa · s.

“Calcium algylose” is prepared as follows.

A 10% solution of calcium chloride (with periodic stirring) is added to the cooled filtrate and kept for 15-20 minutes. The obtained target product is separated from the solution by filtration, and then dehydrated and dried at a temperature not exceeding 50-55 ° C.

“Calcium algylose” is a powder from white to dark cream in color with a grayish tint, insoluble in water, insoluble in acid and alcohol. The yield is 22.6-25.3%. “Calcium algylose” contains: minerals 18.0-19.5%; alginic acid 76.1-78.9%; fiber 0.6-0.9%; mass fraction of calcium 9.6-10.5% (on dry matter).

When processing raw materials with a 65-75% solution of ethyl alcohol in the temperature range of 50-60 ° C for 1.5-2.5 hours, the maximum extraction of mineral and organic compounds of iodine from algae to the extract occurs.

At an alcohol concentration of less than 65%, a time of less than 1.5 hours and a temperature of less than 50 ° C, incomplete extraction of mineral and organic iodine compounds from algae occurs. At an alcohol concentration of more than 75%, a time of more than 2.5 hours and a temperature of more than 60 ° C, the mineral and organic compounds of iodine are destroyed and lost, and the yield and quality characteristics of alginates obtained from the algal residue are reduced.

When processing the algal residue (I) with 1% hydrochloric acid solution at room temperature for 6-10 hours, followed by heating to 45-55 ° С for 4-6 hours with periodic stirring, maximum extraction of fucoidan concentrate occurs, in addition, demineralization occurs alginic acid and its maximum extraction during processing with a solution of sodium carbonate.

When using a hydrochloric acid solution with a concentration of more than 1%, fucoidan concentrate is contaminated with neutralization products.

With a decrease in the concentration of hydrochloric acid less than 1% and a time of less than 6 hours and subsequent heating to 45 ° C for 4 hours, the low molecular weight fraction of alginic acid is extracted and the yield of fucoidan concentrate decreases.

With a treatment duration of more than 10 hours, followed by heating to 55 ° C for 6 hours, there were no significant changes in the direction of increasing the yield and improving the quality of the polysaccharide.

At the end of the acid treatment, the algae are washed with fresh water and sodium alginate is extracted from the algal residue.

The main factors affecting the extraction process of the target products — Sodium Algiloses and Calcium Algiloses — are the temperature of the extractant, the duration of extraction, the water module, the pH of the medium and the degree of purification of the extract from impurities.

A solution of sodium carbonate was used as the extractant, providing a pH of extraction above 7.

The extraction is carried out at pH 8-9, room temperature for 10-15 hours, LCD 1: 40-50, followed by heating to 80-85 ° C for 1-2 hours with stirring and further infused for 3-4 hours With the recommended mode, the maximum extraction of the target products and a reduction in energy costs occur due to a reduction in the heating time of the extraction mixture by 2-3 times.

Lowering the pH of the extractant to less than 8 does not ensure complete replacement of hydrogen ions of alginic acid by sodium ions in the molecule and the maximum output of the polysaccharide in the solution. An increase in the pH of the extractant above 9 leads to an increase in the ash content of the products.

As a result of extraction at room temperature for less than 10 hours, there is no complete swelling and softening of algae tissues, and after extraction for more than 15 hours, the processes of swelling and softening of algae tissues cease.

When the mixture is heated for less than 1 hour, incomplete destruction of the cell walls occurs and the yield of alginic acid in the solution decreases, and when the mixture is heated for more than 2 hours, an increase in energy consumption occurs.

Treatment of the algal residue at a pH of more than 8 and a temperature of 80-85 ° C leads to a deep destruction of algal fiber and the release of polysaccharide into the extract, lowering the temperature treatment reduces the degree of its extraction.

An increase in the extraction temperature above 85 ° C is unacceptable, since the destruction of sodium alginate begins, leading to a decrease in its yield (less than 18%) and quality.

The extract is filtered to a content of impurities in the filtrate of not more than 1 g / l, which allows to obtain a product enriched in fiber.

Precipitation of alginic acid is carried out with a 10% hydrochloric acid solution to a pH of 1-2. These pH values provide complete precipitation of alginic acid.

In order to seal the alginic acid gel and remove excess hydrochloric acid, it is washed with hot water at a temperature of 60-70 ° C to pH 3-4.

The washed alginic acid gel is mixed with sodium carbonate at the rate of 27-30% by weight of the solids of the gel.

When the concentration of sodium carbonate is less than 27%, incomplete conversion of alginic acid to sodium algylose occurs, and at a concentration of more than 30%, the ash content of the product increases.

For the reaction and the formation of sodium algylose, the mixture is kept at room temperature with periodic stirring to a pH of 6.5-7.0.

The resulting sodium algylose gel was twice dehydrated with 96% ethanol and sent for drying at a temperature of 50-60 ° C, while reducing energy consumption for drying.

Dried sodium algylose is ground and packaged.

To obtain calcium algylose, in the obtained filtrate with an impurity content of not more than 1 g / l, add a 10% solution of calcium chloride in the calculation of 2.0-2.5% by weight of dry substances.

When the content of calcium chloride is less than 2.0%, the sodium alginate is not completely converted to calcium algylose, and when the content is more than 2.5%, the ash content of the product increases.

Examples of specific performance.

Example 1

1.0 kg of dried thalli of Japanese kelp (Laminaria japonica) is crushed into pieces 0.3-0.5 cm in size, 7.5 l of a 70% ethanol solution is poured, the mixture is heated to a temperature of 55 ° C for 2 hours. After extraction, the mixture first filtered through a nylon sieve, then in a centrifuge TsLP-3-3.5.

Alcohol is distilled off from the obtained alcoholic extract. After distillation of the alcohol, the resulting water-lipid mixture is settled and divided into two fractions — water-soluble and lipid — and the mixture is pre-cooled to a temperature of 5 ° C.

After sedimentation, the lipid fraction is compacted into a dark green oily clot that floats to the surface. The aqueous fraction remains in the lower part of the dividing vessel.

The lipid fraction, hereinafter referred to as the “Iodine-containing lipid complex”, is poured into a container and packaged.

The iodine-containing lipid complex is a greasy greenish-brown substance with a characteristic odor of algae.

The aqueous fraction, hereinafter referred to as the “Iodine-containing mineral-mannitic complex”, is poured into a container and sent for filtration.

Filtration of a solution of iodine-containing mineral-mannitol complex is carried out in two stages: on a rotary filter and then on a centrifuge. After filtration, the solution is evaporated at a temperature of 55 ° C (with or without vacuum) in an evaporator to a mass fraction of water of not more than 60% and sent for drying at a temperature of 55 ° C to a mass fraction of water of 15%.

The iodine-containing mineral-mannitol complex is a granule or powder from dark to light brown in color, with a characteristic odor of algae.

As a result, 0.502 kg of an iodine-containing mineral-mannitol complex and 0.012 kg of an iodine-containing lipid complex were obtained, which amounted to 50.2% and 1.2%, respectively. The iodine content in the mineral mannitol complex is 1.03%, minerals 49.9%, mannitol 30.2%, amino acids 8.8%.

The iodine content in the lipid complex was 0.43%, minerals 6.2%, protein 5.0%, lipids 88.0%.

The algal residue (I) after separation of the alcoholic extract is placed in a container, filled with 10 l of a 1.0% hydrochloric acid solution and kept at room temperature for 8 hours with stirring and then at 50 ° C for 5 hours. The extract is separated from the remainder of algae (II) by sequential filtration through a nylon sieve and in a centrifuge. The extract obtained is neutralized with sodium carbonate to pH 7, evaporated in vacuo at a temperature of 52 ° C to 1/4 of the original volume, treated twice with a three-fold volume of ethanol, centrifuged to separate fucoidan concentrate and dried it in an oven at a temperature of 55 ° C.

Fucoidan concentrate contains 40.1% fucoidan, 31.1% minerals, 22.7% sulfate groups, 1% alginic acid. The yield of fucoidan concentrate was 12.3%.

The remainder of the algae (II), after treatment with hydrochloric acid, is washed with fresh water at room temperature and extracted with 45 l of a 0.5% sodium carbonate solution for 12 hours at pH 8.5 and room temperature, then the mixture is heated to 82 ° C for 1.5 h with periodic stirring and insist for 3.5 h without heating. The extract is separated from the algal mass in two stages: on a rotary filter with a sieve No. 6-8 and then on a rotary filter with a sieve No. 65-70 to an impurity content in the filtrate to 1 g / l and cooled to a temperature of 20 ° C.

Two target products are obtained from the obtained filtrate.

The filtrate is divided in half and from one part receive “Sodium Algylose”, and from the other part “Calcium Algylose”.

“Sodium algylose” is prepared as follows.

Alginic acid is precipitated from the obtained filtrate with a 10% hydrochloric acid solution to a pH of 1.5. The mixture was incubated for 20 minutes. The precipitate is separated in a centrifuge, washed with hot water to pH 3-4.

The washed alginic acid gel with an admixture is mixed with sodium carbonate at the rate of 28% by weight of solids.

The obtained target product, “Sodium Algylose,” was twice dehydrated with 96% ethanol and dried at a temperature of 55 ° C.

The yield of “Sodium Algylose” was 29.8%. The content in the obtained sodium algylose of mineral substances is 22.7%, alginic acid 76.1%, fiber 0.7%, the viscosity of a 0.2% aqueous solution of sodium alginate 8.6 × 10 ^-3 Pa · s.

“Calcium algylose” is prepared as follows.

In a cooled filtrate with an impurity content of not more than 1 g / l add a 10% solution of calcium chloride in an amount of 2.3% per dry matter of the filtrate.

The obtained target product, “Calcium Algylose”, is separated from the solution by centrifugation and dried at a temperature of 55 ° C.

The yield of calcium algylose was 25.3%. The content in the obtained calcium algylose of mineral substances is 18.0%, alginic acid 78.9%, fiber 0.7%.

Example 2

Example 2 is similar to example 1, however, the processing of crushed raw materials is carried out with a 65% ethanol solution at a temperature of 50 ° C for 1.5 hours

As a result, 0.40 kg of iodine-containing mineral complex and 0.006 kg of iodine-containing lipid complex were obtained, which amounted to 40.0 and 0.6%, respectively.

The iodine content in the “mineral complex” was 0.719%, minerals 45.4%, mannitol 28.3%, amino acids 7.8%.

The iodine content in the “lipid complex” was 0.32%, minerals 10.8%, protein 4.8%, lipids 80.9%.

The remainder of the algae (I) was extracted with a hydrochloric acid solution for 6 hours at room temperature and 4 hours at a temperature of 45 ° C, and the extract was evaporated in vacuo at a temperature of 50 ° C to 1/5 of the original volume.

The yield of fucoidan concentrate was 10.6%. Fucoidan concentrate contains 33.4% fucoidan, 34.7% minerals, 20.2% sulfate groups, 1.1% alginic acid.

The residue of algae (II), after treatment with hydrochloric acid, is washed with fresh water at room temperature and extracted with 40 l of 0.5% sodium carbonate solution for 10 hours at pH 8 and room temperature, then the mixture is heated to 80 ° C for 1.0 hour at stirring occasionally and insist for 3.0 hours without heating. The extract is filtered in two stages: on a rotary filter with a sieve No. 6-8 and then on a rotary filter with a sieve No. 65-70 to an impurity content in the filtrate to 1 g / l and cooled to a temperature of 20 ° C.

From the obtained filtrate, “Sodium Algylose” is obtained as follows.

First, alginic acid is precipitated from the obtained filtrate with a 10% hydrochloric acid solution to a pH of 1.5. The mixture was incubated for 20 minutes. The precipitate is separated in a centrifuge, washed with hot water to pH 3-4.

The washed alginic acid gel with an admixture is mixed with sodium carbonate at the rate of 27% by weight of solids.

The obtained target product, “Sodium Algylose,” was twice dehydrated with 96% ethanol and dried at a temperature of 55 ° C.

The yield of “Sodium Algylose” was 26.6%. The content in the obtained sodium alginate of mineral substances is 24.2%, alginic acid is 75.0%, the viscosity of a 0.2% aqueous solution of sodium alginate is 7.5 × 10 ^-3 Pa · s.

Example 3

Example 3 is similar to example 1, however, the processing of crushed raw materials is carried out with a 75% solution of ethanol at a temperature of 60 ° C for 2.5 hours

The result was 0.498 kg of “Iodine-containing mineral complex” and 0.0118 g of “Iodine-containing lipid complex”, which amounted to 49.8% and 1.18%, respectively.

The iodine content in the “mineral complex” was 0.9%, minerals 40.2%, mannitol 38.7%, amino acids 6.7%.

The iodine content in the “lipid complex” was 0.36%, minerals 7.0%, protein 4.2%, lipids 87.0%.

The residue of algae (I) after alcohol treatment was extracted for 10 hours at room temperature and 6 hours at 55 ° C, and the extract after neutralization was evaporated under vacuum at 55 ° C to 1/4 of the original volume.

The yield of fucoidan concentrate was 11.5%. Fucoidan concentrate contains 36.8% fucoidan, 33.6% minerals, 18.3% sulfate groups, 0.9% alginic acid.

The residue of algae (II) after separation of the fucoidan concentrate is extracted with a solution of sodium carbonate at room temperature for 15 hours at pH 9, and then with stirring and maintaining a temperature of 85 ° C for 2 hours and then infused for 4 hours without heating.

The extract is filtered in two stages: on a rotary filter with a sieve No. 6-8 and then on a rotary filter with a sieve No. 65-70 to an impurity content in the filtrate to 1 g / l and cooled to a temperature of 20 ° C.

In a cooled filtrate with an impurity content of not more than 1 g / l add a 10% solution of calcium chloride in an amount of 2.5% per dry matter of the filtrate.

The obtained target product, “Calcium Algylose”, is separated from the solution by centrifugation and dried at a temperature of 55 ° C.

The yield of Calcium Algylose was 25.0%. The content in the obtained calcium alhylosis of mineral substances is 19.5%, alginic acid 76.1%, fiber 0.9%.

Claims (3)

1. A method of complex processing of brown algae, including grinding the raw material, extracting it with an aqueous-alcoholic solution, separating the aqueous-alcoholic extract from the algal residue (I) by filtration and obtaining biologically active substances from it, extracting the algal residue (I), separating the extract from the algal residue (II) by filtration, obtaining a polysaccharide from it, extracting the algal residue (II) with sodium carbonate solution, separating the filtrate from the algal residue treated with sodium carbonate filter lowering, isolating alginic acid from the filtrate, treating it with a salt to obtain a biologically active substance, characterized in that the extraction of the crushed raw material is carried out with a 65-75% ethanol solution at a temperature of 50-60 ° C for 1.5-2.5 hours, the water-alcohol extract is freed from alcohol, the resulting water-lipid emulsion is cooled to a temperature of 5-10 ° C, separated by settling it into the aqueous and lipid fractions and biologically active substances are obtained from them, moreover, an iodine-containing mannitol complex is obtained from the aqueous fraction, and iodine-containing lipid complex from the lipid fraction, the algal residue (1) is extracted with 1.0% hydrochloric acid solution for 6-10 hours at room temperature, followed by heating the mass to a temperature of 45-55 ° C for 4-6 hours, and then the acid extract is successively neutralized with potassium or sodium carbonate to pH 7 and evaporated in vacuo at a temperature of 50-55 ° С to 1 / 4-5 of the initial volume of the extract, the fucoidan concentrate is precipitated twice with a three-fold volume of ethanol, the algal residue (II) is extracted at pH 8-9 for 10- 15 hours at room temperature, followed by heating the mass to a temperature of 80-85 ° C for 1-2 hours, the filtration of the extract is carried out to an impurity content of not more than 1 g / l, calcium algylose and / or sodium algylose are obtained as a biologically active substance, in this case, calcium algylose is obtained by adding calcium chloride to the filtrate in the calculation of 2.0-2.5% by weight of solids, and sodium algylose by adding sodium carbonate to alginic acid at the rate of 27-30% by weight of solids. 2. The method according to claim 1, characterized in that alginic acid is isolated with a 10% hydrochloric acid solution. 3. The method according to claim 1, characterized in that the calcium chloride is used in the form of a 10% solution.