RU2573310C1 - Method for extraction of vegetal raw materials, chlorophyll-containing bioactive product manufacture method, involving such extraction, and product - Google Patents

Abstract

FIELD: food industry.

SUBSTANCE: vegetal raw materials extraction method envisages usage of raw materials represented by dried milled vegetal raw materials and an extragent represented by chilled liquid freon; vegetal raw material extraction is performed repeatedly with such freon, the module being 5 - 6, during 2-3 hours. The extraction method is used in the chlorophyll-containing bioactive product manufacture method. The bioactive product has an increased content of chlorophyll in comparison with equivalent products manufactured as a result of extraction with carbohydrates or low-molecular alcohols.

EFFECT: invention allows to reduce the time of the technological process of raw materials treatment, enhance the quality of the bioactive product manufactured and enhance the process environmental safety.

11 cl, 1 dwg, 6 ex

Description

FIELD OF THE INVENTION

The invention relates to a new technology for processing plant materials, namely, the extraction of dry plant materials with Freon / Freon. Thanks to it, you can get antioxidants - chlorophyll-containing bioactive products for the food industry and other industries, for example, from woody greens (needles, leaves), grassy raw materials (alfalfa, mint, plantain, nettle, etc.) and algae. The new method improves the quality of chlorophyll-containing bioactive products. increase their output, increase the environmental and hygienic safety of the process.

State of the art

Currently, the food industry notes the need to introduce natural biologically active substances (BAS) into commercial products to increase the nutritional value of products and attract consumers by improving their quality of life. A special place among natural biologically active substances is given to chlorophyll-containing bioactive products, since the positive role of chlorophyll as an antioxidant, immunomodulator, and adaptogen is proved. Chlorophyll-containing biologically active substances (HS-BAS) are also successfully used in the cosmetic and pharmaceutical industries. The role of chlorophyll derivatives as an antimicrobial, antifungal, antimutagenic agent, the ability of chlorophyll to improve hematopoiesis, and to increase immunity is well known. Chlorophyll-containing bioactive products (BP) are usually considered such concentrates that contain at least 300 mg% (3%) of chlorophyll derivatives. The qualitative and quantitative composition of BP concentrates varies depending on the processed plant material. Therefore, to obtain BP, it is important to use only the plant raw materials that are used in the food and cosmetic industries: algae, pine and spruce needles, birch leaves, nettle, alfalfa, mint, plantain, etc. Chlorophyll-containing BPs are used in drinks, tooth elixirs, and pastes therapeutic purposes and other useful products.

Known methods for producing chlorophyll-containing products from grassy, algal raw materials or woody greens by extraction with diethyl ether or ethyl alcohol, followed by distillation of the solvent / Yagodin V.I. Fundamentals of chemistry and technology for processing green wood. L .: Leningrad State University, 1981, p. 113 /. These methods are explosive and flammable, environmentally disadvantageous, lead to large losses of toxic solvents with narcotic effects and are usually used in laboratory experiments to determine the qualitative and quantitative composition of chlorophyll-containing concentrate in plant materials.

A known method of processing brown algae by extracting from them a chlorophyll-containing bioactive product (kelp concentrate - KL) with a hydrocarbon solvent with a carbon number from 1 to 6 to obtain KL, kelp extract, mannitol and alginates. The method is described in patent RU 2132622 C1. However, this method has significant disadvantages:

- a high liquid module (LM) extraction from 10 to 20 leads to large losses of extractant, and with a low liquid module (example 1 of this patent), the entire extractant is sorbed on algae, and in practice the method with a low LM is not reproduced on an industrial scale;

- a significant yield of bioactive product is explained by a high content of ash substances and other impurities that pollute CL, reduce the purity and quality of BP.

When extracting other plant materials - woody greens (coniferous paws, birch leaves), grassy materials (nettle, plantain, peppermint) with hydrocarbon solvents, for example, gasoline, chlorophyll-containing resinous substances are released, which, in addition to chlorophyll derivatives, are a complex multicomponent mixture of resin and fatty acids, ash substances (minerals), bitterness, volatile, waxy substances with a yield of 3-4% of the feedstock with a total content of up to 7% of these components in the needles. Resinous substances are used to produce coniferous chlorophyll-carotene paste obtained by hydrolysis of resinous substances with an aqueous solution of sodium alkali with a yield of 5% of the original coniferous foot / B.I. Jagodin, Fundamentals of chemistry and technology for processing green wood. L .: Leningrad University, 1981, p. 95-113 /.

Known methods for the extraction of needles and kelp with alcohol-water solutions, including extraction with 80-85% ethyl alcohol (RU 2132622 C1). For example, a method for producing CL in a complex scheme for processing brown algae (kelp, fucus) by extraction of crushed brown algae with 85% ethanol, followed by distillation of the solvent from the water-alcohol fraction, regeneration of the solvent to obtain rectified alcohol, multi-stage crystallization of salts and mannitol, obtaining CL from one stripped off water extract as a result of multiple crystallization and further processing of algal meal to alginates. The Arkhangelsk Experimental Algae Plant (AOVK) is working on this technology.

The extraction process of plant materials with hydrocarbon solvents or low molecular weight alcohols is not effective. Solvents are toxic, harmful to health, especially in unusual situations: accidental emissions into the atmosphere, penetration into wastewater.

To improve the quality of the chlorophyll-containing bioactive product, extraction can be carried out at room temperature of 20-30 ° C. However, this leads to a sharp decrease in the yield of the bioactive product by 5–6 times, even with an extraction duration of 6–10 hours, and at elevated temperatures from 60 ° C to the boiling point of the extractant, the quality of the bioactive product inevitably decreases due to oxidation and destruction of pigments during a rather long process extraction - from 4 to 6 hours.

From SU 973602, a method for extracting oil from an oil-containing material is known. The method consists in evacuating the oil-containing material, feeding solvent vapor into the extraction volume with condensing them in the vapor of the material and then treating it with a liquid solvent, the solvent vapor being fed at a rate that provides a pressure increase of 0.1-5 atm. per minute until the pressure in the system reaches equilibrium, and when treated with a liquid solvent, the pressure differential at the outlet and entrance to the extraction volume is maintained, which is necessary to create a temperature difference of 0.1-10 ° C, while liquefied gas is used as the solvent. As a solvent, fluorine derivatives of hydrocarbons or carbon dioxide are used.

However, this method is used only for the separation of oil from oil-containing raw materials, but it has never been used for the extraction of various types of plant materials in order to obtain chlorophyll-containing BP.

Closest to the proposed product and the method used to isolate chlorophyll-containing bioactive products of various chemical compositions is a method for extracting plant materials with a hydrocarbon solvent or low molecular weight alcohol at an elevated temperature (from 60 ° C to boiling point), a liquid module 4-6, extraction time 5 -6 hours This is the previously mentioned method for producing resinous substances from the coniferous paws of pine and spruce by extraction with a low molecular weight hydrocarbon solvent gasoline / B.I. Jagodin, Fundamentals of chemistry and technology for processing green wood. L .: Leningrad University, 1981, p. 95-113 /, followed by obtaining from resinous substances coniferous chlorophyll-carotene paste (HHKP).

The disadvantages of these technologies for processing plant materials include the following. The extraction process with hydrocarbon solvents or low molecular weight alcohols is economically costly, leading to large losses of raw materials, extrahepts, effluents and air emissions. Solvents are toxic, harmful to health, especially in non-standard situations: accidental emissions into the atmosphere, into sewage.

Extraction at elevated temperatures inevitably leads to a decrease in the quality of the chlorophyll-containing bioactive product (BP) due to the oxidation of polyunsaturated fatty acids, the destruction of pigments, on the one hand, and contamination of the BP with some water-soluble components during a rather long extraction process, on the other.

When extraction with low molecular weight alcohol containing up to 15 - 25% water, there is an additional decrease in alcohol concentration due to moisture of the extracted raw materials and partial losses of ethanol during the extraction process. This, in turn, requires the inclusion of an alcohol recovery unit in the process to strengthen the alcohol to an initial concentration of 85%.

Large losses of BP occur due to incomplete extraction from raw materials with a liquid module (LM) 4-6. The increase in LM leads to inappropriate losses of extractant (alcohol or gasoline) and additional stages of the process, increased economic losses due to increased extraction time, heat load.

Similar disadvantages have all the previously described and traditionally used methods for extracting plant materials with low molecular weight hydrocarbons or alcohols.

To eliminate these disadvantages, freon, otherwise called freon, which is a mixture of ethane and methane, is used as a solvent in the proposed method for extracting plant materials.

SUMMARY OF THE INVENTION

The objective of the present invention is to reduce the time of the technological process of processing plant materials, increase the yield and quality of the resulting bioactive product, increase the environmental safety of the process.

The problem is solved in that the dried shredded plant material is extracted with freon. Freon provides hygienic and environmental safety of the method, as it is a non-toxic solvent. Freon or freon is a mixture of ethane and methane, soluble in organic solvents, insoluble in water, used in the form of a liquid or gas, colorless and odorless, with a low boiling point. During evaporation, it absorbs heat, and then releases it during condensation. Extraction with freon is carried out at minus temperature, and condensation at positive temperature is 10-25 ° С. The entire extraction process is carried out for 2-3 hours, at a pressure of 3 to 10 atm (kg / cm ² ).

The first object of the invention is a method for extracting plant materials, which involves the use of dried crushed plant materials as plant materials, and liquid refrigerated freon as an extractant. The extraction of the dried crushed plant material is carried out by liquid chilled freon repeatedly with a module from 5 to 6, for 2-3 hours. The extraction temperature is from minus 10 to minus 20 ° C, and the pressure is from 3 to 10 atm.

The second object of the invention is a method for producing a chlorophyll-containing bioactive product, which includes the above extraction of dried crushed plant material with liquid chilled freon with a liquid module from 2 to 5, after which the temperature is raised to 10-25 ° C to condense the freon and evaporate the extractant residues, and then separate extract for liquid BP and dry meal. According to this method, a third object of the present invention is obtained - a chlorophyll-containing bioactive product, which can be further used in the food, cosmetic and pharmaceutical industries as a source of biologically active substances, and in particular chlorophyll.

In a particular case, liquid BP also contains polyunsaturated fatty acids and ash. In this case, the preferred plant material is woody greens - needles or algae.

Plant raw materials can also be grassy raw materials or any terrestrial part of plants for food, cosmetic or medicinal purposes, for example, birch leaves, nettle, mint, plantain, alfalfa, etc.

BP from pine needles in addition to ash and fatty acid components contains resin acids, volatile, bitterness, and other bioactive substances (vitamins, squalene, prenols).

BP from kelp or fucus algae also contains iodine and other minerals, omega-3 polyunsaturated fatty acids, mannitol.

Disclosure of invention

To increase the yield, improve quality, reduce the time of the technological process, increase its environmental and hygienic safety, the extraction of dried crushed vegetable raw materials is carried out not with an ordinary organic solvent, but with freon at a negative temperature.

When using any brands of freon, the extraction time is necessary and sufficient is 2-3 hours. The extraction temperature is minus 10-25 ° C, and the yield of BP is almost the same and is at least 95% of the content of BP in the initial plant material in terms of dry weight.

The extraction is carried out with liquid refrigerated freon, namely at negative temperatures from minus 10 to minus 25 ° C, in contrast to the known methods of extraction with various organic solvents at elevated temperatures. Extraction with freon allows one to obtain chlorophyll-containing BP at lower temperatures of higher quality, to preserve biologically active substances, even such labile components as chlorophyll, and, therefore, to increase the quantity and quality of useful biologically active substances in the resulting BPs. This is an advantage and one of the technical results of the present invention.

When woody greens are extracted with freon, a multicomponent BP is obtained, in which, in addition to chlorophyll derivatives, other useful biologically active substances are contained: resin acids, polyunsaturated fatty acids, ash substances, alcohols, including phytosterols, aliphatic compounds, vitamins and provitamins, squalene, prenols, volatile, bitterness, which significantly increases the value of BP.

Freon is usually used as a refrigerant in various refrigeration units. The authors of the present invention unexpectedly found that it can be used for extraction of oil-free raw materials in order to obtain a chlorophyll-containing concentrate - BP. The use of freon makes it possible to isolate high-quality BP with a yield of more than 95% to the content in the initial plant material in terms of absolutely dry mass (asm), whereas when a BP is obtained at AOBK, the yield is not more than 80%. Thus, there is a clear increase in the yield of the target PSU.

At the same time, the technology for processing plant materials is simplified: the process time, the extraction time — almost 2 times, the heat consumption for extraction decreases, and the quality of the final product increases. Moreover, the process according to the present invention is hygienic and environmentally friendly, has no wastewater and air emissions. Depending on the brand of freon used, the extraction parameters also change somewhat. When using Freon brand 12 as an extractant, extraction is carried out at a pressure of 4-5 atm .; Freon brand 22 - at 8-10 atm; Freon brand 410 (a mixture of methane and ethane) - pressure 4-5 atm.

The use of freon also provides increased environmental safety, fire and explosion safety of the process. Unlike other known extractants, freon is chemically inert, with a low level of toxicity (Grade 4), fire and explosion safe even in direct contact with fire, harmless to humans and animals.

In this case, a completely new principle of extraction of plant materials is used. Extraction by freon is carried out at a negative temperature (-10) - (-25 °) C, which allows you to keep unchanged state of the bioactive components and improve the quality of the final bioactive product. This is also a technical result of the present invention.

The principle of operation of the devices used in the claimed method is based on the operation of a domestic refrigerator. Freon for extraction is fed chilled in a condenser-refrigerator to minus temperature (minus 15 - minus 20 ° C) and therefore in a liquid state. Liquid freon is passed through the plant raw material, which together with the extracted biologically active substances in the form of an extract enters the evaporator tank, where at a temperature of plus 10-25 ° С the extract is separated into gaseous freon entering the compressor and liquid condensate containing BP. Freon liquefies upon cooling in a compressor-refrigerator and is again fed to extraction repeatedly and continuously for 2-3 hours. At the end of the extraction, the temperature in the extractor is raised to 10-25 ° C to condense and evaporate the remainder of the freon, then the meal is discharged, from which gaseous freon has already been driven off into the compressor refrigerator. The container with freon extract is also heated to a temperature of 10-25 ° C, at which gaseous freon also enters the compressor refrigerator.

The moisture content of the raw materials recommended for the technological process is not more than 11-15%. At higher humidity, Freon mixes with water, the extraction time increases, the raw materials can freeze, so the yield of BP decreases.

When the extraction temperature is increased to 60 ° C, the quality of BP decreases, chlorophyll derivatives and other pigments, as well as thermally unstable biologically active substances, for example, polyunsaturated fatty acids, are destroyed.

As a result of Freon extraction, two products are obtained: chlorophyll-containing BP and meal. The latter is a by-product of the intermediate and is further processed: alginates are obtained from algal meal, and sorbents are obtained from meal of other plant materials.

Chlorophyll-containing bioactive product is used as a biologically active substance in food, cosmetic, medical and pharmaceutical compositions.

To date, the authors were not aware of the possibility of obtaining chlorophyll-containing BP, which is not an oil concentrate, from plant materials using freon instead of the known and commonly used for the extraction of low molecular weight alcohols and hydrocarbon solvents. Thus, it was not obvious that Freon can be used to extract dried plant materials to produce chlorophyll-containing bioactive products (BP) for various purposes.

Brief Description of the Figures

The figure 1 shows a schematic diagram of the production of chlorophyll-containing BP on the example of processing algae kelp using freon as an extractant. Wood greens - needles or leaves and other plant materials are similarly processed to produce chlorophyll-containing BP.

The implementation of the invention

The following are examples of obtaining BP according to the present invention. In the examples, Freon brand 12 is used, working pressure 4-5 atm; brand 22 freon - working pressure 8-10 atm, brand 410 freon (this is a mixture of 20 and 22), working pressure 4-5 atm. The output when using any brand of freon is the same.

Example 1. Laminaria weighing 12 kg with a moisture content of 12% was dried in a shelf dryer to a moisture content of 5%, crushed in a hammer mill to particles about 1 mm in size. The crushed kelp was loaded into the extractor to the full volume, then air was removed from the feed using a vacuum pump to 0.8-1.0 atm. The extractor was filled with gaseous Freon brand 12 with a pressure increase of 4-5 atm. Liquid freon was pumped into the extractor in a five-fold volume from the loaded raw materials (ЖМ - 5) from the compressor-cooler through the lower valve. Liquid freon repeatedly for 2 hours. pumped through plant material in the extractor, extracting the raw material at a temperature of minus 10 - minus 20 ° C. Further, freon exited through the upper valve into the container for the extract, where it was heated to 10-25 ° C, expanding and passing into a gaseous state, and then again into the compressor-refrigerator for cooling and liquefaction. In this case, the liquid part of the extract accumulated in the tank. After 2 hours after the extraction was completed, freon was evacuated in a gaseous state from the container with the extract when heated to 25 ° C, and it entered the compressor cooler. At the end of the extractor, the remaining meal was also heated to 25 ° C to separate freon gas (enters the refrigerator compressor), the hatch was opened and the meal was poured out of the extractor in the form of dry flour.

The yield of chlorophyll-containing BP was 0.24 kg or 2% of the initial dry kelp (when the content in the kelp in terms of ASM is 2.04%, which is 98%). The content of chlorophyll derivatives in BP was 820 mg%, which is 300 mg% higher than when extracted with 85% ethyl alcohol according to conventional technology.

The yield of meal was 97%. Meal can be further directed to obtaining alginates. In addition to chlorophyll — 8.2%, BP included mannitol — 5%, polyunsaturated fatty acids — 30%, iodine — 1.2%, other macro- and microelements — 16%, fiber — 4%, and other components — alginates. (up to 100%).

Example 2. It differs from example 1 in that Freon brand 22 was used, the working pressure in the extractor was 8-10 atm, LM - 6, the extraction time was 3 hours. The yield of chlorophyll-containing BP was 98.1% of the content in dry kelp (2.041%). The content of chlorophyll derivatives in BP is 800 mg%, which is 280 mg% higher than during extraction with 85% ethyl alcohol according to standard technology.

Example 3. It differs from example 1 in that a 410 freop (a mixture of methane and ethane) was used as an extractant, and the working pressure was 4-5 atm. The yield of chlorophyll-containing BP is 0, 24 kg or 2% of the initial kelp (when the content in the kelp in terms of acm is 2.04%, which is 98%). The content of chlorophyll derivatives in BP is 798 mg%, which is 298 mg% higher than according to generally accepted technology. The yield of meal is 97%. Meal was sent for further processing to obtain alginates for medical purposes. Work with freon of this brand led to its additional losses, the separation of methane and ethane when heated.

Example 4. It differs from example 1 in that the raw materials used were woody greens - pine and spruce needles with a humidity of 45%. The needles were dried to a moisture content of 5%, ground, and then the method was carried out as in example 1. The yield of chlorophyll-containing BP was 98% of the needles in terms of asm. The content of chlorophyll derivatives in BP is 640 mg%, which is 200 mg% higher than with gasoline extraction (see V. Yagodin, p. 95, table 4.4).

Meal in the form of flour can be used as a sorbent - an absorber of odors. The composition of chlorophyll-containing BP: chlorophyll derivatives - 6.4%, fatty acids -25.5%, resin acids - 31.2%, macro- and microelements (ash) in total - 14.3%, the rest - biologically active substances, bitterness, volatile, fiber, waxy substances.

Example 5. It differs from example 4 in that the extraction with freon was carried out for 3 hours using brand 22 freon, the working pressure in the extractor was 8-10 atm. The yield of chlorophyll-containing BP is 98.1% of the content in the original needles in terms of acm. The content of chlorophyll derivatives is 650 mg%, which is 250 mg% higher than with gasoline extraction (see V. Yagodin, p. 95, table 4.4).

Example 6. It differs from example 1 in that dried nettle was used as a raw material. The yield of chlorophyll-containing BP is 98% of the content of the feedstock in terms of acm. The content of chlorophyll derivatives is 810 mg%. The composition of other BP components was not determined.

It was found that the process parameters are optimal, necessary and sufficient for the following process parameters: LM extraction with liquid freon - 5-6, extraction time 2-3 hours, temperature - minus 10-20 ° C.

It was found that with an increase in the extraction time over 3 h, there is no increase in the yield of BP or an increase in the content of chlorophyll derivatives in BP. With a decrease in LM less than 5, it was necessary to increase the extraction time.

The proposed method of low molecular weight extraction with Freon can significantly improve and simplify the process, improve the quality of BP, increase its output, eliminate runoff and air emissions, and therefore, improve the environmental safety of the process.

Claims (11)

1. A method of extracting plant materials, characterized in that the dried crushed plant materials are used as raw materials, and refrigerated liquid freon is used as extractant, the extraction of plant materials is carried out repeatedly with a module from 5 to 6, for 2-3 hours. 2. The method according to p. 1, characterized in that the extraction temperature is from minus 10 to minus 20 ° C, and the pressure is from 3 to 10 atm. 3. A method of producing a chlorophyll-containing bioactive product, characterized in that it involves the extraction of dried crushed plant material with liquid chilled freon according to claim 1 or 2 with a module of 5 to 6, after which the temperature is raised to 10-25 ° C to condense and evaporate the freon residues and the extract is separated into a liquid bioactive product containing chlorophyll and dry meal. 4. The method according to p. 3, characterized in that the liquid bioactive product also contains polyunsaturated fatty acids and ash. 5. The method according to p. 3 or 4, characterized in that the plant material is woody greens - needles or leaves. 6. The method according to p. 3 or 4, characterized in that the plant material is algae. 7. The method according to p. 3, characterized in that the plant material is herbaceous raw materials or the land part of food, cosmetic or medicinal plants. 8. The method according to p. 7, characterized in that as grassy raw materials use birch leaves, nettle, alfalfa, mint, plantain. 9. The method according to p. 5, characterized in that the bioactive product from the needles also contains resin acids, volatile, bitter. 10. The method according to p. 6, characterized in that the bioactive product from kelp kelp also contains iodine, omega-3 polyunsaturated fatty acids, mannitol. 11. Chlorophyll-containing bioactive product obtained by the method according to any one of p. 3-10.

Images