RU2348168C1 - Method of processing fir tree greenery extraction wastes - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: proposed method envisages fir tree greenery extraction wastes being treated with a water-immiscible organic solvent and further extraction. The extraction process is as follows. First water is added to the wastes mass that is subsequently maintained at a temperature of 80-90°C during three hours, the heating combined with solvent residues stripping off the stratum of greenery mass with water steam. The resultant aqueous extract undergoes concentration under vacuum conditions at a temperature of 60-80°C. The final product (concentrated extract that may be in the form of either a water solution containing 50-70% of solids or a solid matter) is utilised as a fodder additive.

EFFECT: environmentally friendly method of processing fir tree greenery extraction wastes enabling production of a bioactive preparation to be utilised in the sphere of agriculture.

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Description

The invention relates to methods for processing waste from the extraction of plant materials, specifically wood fir green, to obtain biologically active substances - a concentrate of sugars, oligosaccharides, flavonoids, which can be used as a feed additive for farm animals.

Known methods for the extraction of green wood of fir with organic solvents allow the isolation of valuable biologically active compounds - triterpene acids and neutral extractives, however, wood waste is generated containing residual amounts of organic solvents - extractants, in addition, bioactive substances that are not recoverable by organic substances remain in the waste solvents - sugars, polysaccharides, flavonoids.

The known method [RU 2233868] for producing biologically active substances from woody fir green, which consists in extracting dried woody green with a mixture of isopropyl alcohol and water with distillation of the extractant, separation of the layers of the resulting concentrate and subsequent extraction of the aqueous-organic layer with a non-polar solvent, resulting in a polar fraction substances, and the amount of triterpenic acids is isolated from the upper organic layer. The disadvantage of this method is the generation of waste green wood fir with incomplete extraction of water-soluble biologically active components during extraction with aqueous isopropanol, significant amounts of solvent are contained in the mentioned waste.

A known method of processing woody green fir [RU 2199861], which allows to obtain a biologically active amount of neutral isoprenoids, as well as triterpenic acids, which consists in the fact that chopped woody fir firs are extracted with an organic solvent, the extract is separated, the latter is treated with an aqueous solution of an alkaline agent, and the aqueous-aqueous solution is separated alkaline layer, acidify the latter and isolate the amount of triterpenic acids from it with an organic solvent. From the organic layer of the extract remaining after alkaline washing, a sum of neutral isoprenoids is isolated, for which the solvent is first distilled off from the extract, and then the volatile components of fir oil are distilled off from it at a residual pressure of 0.1 mm Hg. at a temperature of 70-80 ° C.

The disadvantage of this method is the complete absence of extraction of water-soluble components from woody fir green, the formation of waste woody green fir containing residues of an organic solvent-extractant.

The closest analogue is the method of obtaining feed products from green wood conifers [RU 2032359]. The method consists in the following: the coniferous mass previously aged in piles is subjected to primary low-temperature extraction by exposure to gasoline and water vapors with the isolation and purification of a low-temperature vitamin-containing concentrate when it is heated no higher than 80-85 ° C. After that, coniferous mass and concentrates are re-extracted at more high temperature to obtain a cellulose-containing residue, which after steaming and purification from gasoline impurities in the heated state is kept, mixed with previously aged constant in clamps wood pulp. Next, heat treatment is carried out, during which an enzyme-yeast mixture is added, and then, when the temperature is reduced to 50-70 ° C, the resulting product is mixed with a low-temperature vitamin-containing concentrate and sent for further drying or granulation.

The disadvantage of this method is the inefficiency of using a mixture of gasoline and water for the extraction of a number of components, in particular acids (for fir greens, these are mainly triterpene acids containing impurities of tar and fatty acids). Removing valuable components, triterpene acids, from vapors of gasoline and water in vapors of gasoline and water is inefficient, since these compounds have low solubility in gasoline and water. As a result, the use of vapors of gasoline and water as extractants for the coniferous mass does not make it possible to isolate the valuable components of fir green wood - triterpene acids.

A disadvantage is the fact that conducting joint extraction with water and gasoline vapors does not allow efficient extraction of water-soluble components at a temperature of 80-85 ° C, since non-extractable components, in particular triterpene acids, interfere with the transport of extractants (gasoline and water) in particles of plant materials. Subsequent extraction at a higher temperature (steaming) leads to the destruction of biologically active components.

The problem to which the invention is directed, is to create an environmentally friendly method of processing waste from the extraction of green wood fir to obtain a biologically active drug for use in agriculture.

The problem is solved in a way in which the departure from the production of the amount of triterpenic acids (for example, according to the method described in the patent [RU 2108803]), which is wood green fir, extracted with a water-immiscible solvent (methyl tert-butyl ether) and containing residual amounts solvent, treated with hot water and the sum of sugars, polysaccharides and flavonoids is recovered.

Ecological purity in the processing of these wastes is to prevent the emission of organic solvent vapors into the atmosphere. This is achieved by the fact that the water extraction carried out after the organic extract is drained from the woody greens is carried out with simultaneous distillation with water vapor and condensation of the residual solvent, which also makes it possible to return a substantial proportion of the extractant to production and, accordingly, reduce production costs.

The proposed method is as follows.

The waste of green fir wood, formed after extraction of the sum of triterpenic acids (for example, according to the patent [RU 2108803) with a solvent that is not miscible with water (for example, methyl tert-butyl ether), is then treated with hot water and the water-soluble components — flavonoids, sugars, polysaccharides — are extracted. The extract is drained and concentrated to obtain a concentrate used as a biologically active feed additive for farm animals.

After draining the organic solvent and containing the residual solvent, a layer of wood green fir is loaded with water, and when heated to 80-90 ° C., the residual solvent is distilled off from the green wood with steam. The aqueous extract is drained from a layer of fir green wood and concentrated in vacuo to obtain an aqueous extract concentrate in the form of a solution with a dry matter content of 50-70% or in the form of a solid substance containing sugars, oligosaccharides, flavonoids. The target product obtained by the present method in the form of solutions with a concentration of 50-70 wt.%, Is a viscous dark brown liquid containing sugars, oligosaccharides, flavonoids; the target product obtained in the solid form according to the claimed method is a hygroscopic brown powder or dark brown flakes and is a concentrate of sugars, oligosaccharides, flavonoids.

The inventive method has the following advantages:

- preliminary extraction with methyl tert-butyl ether extracts from the woody fir green the sum of organic components, including organic acids and other substances insoluble in gasoline and water. Water extraction of waste from the extraction of green wood fir with methyl tert-butyl ether is carried out efficiently due to the absence of components in wood green that impede the transport of extractant (water) in milled plant material. This allows the extraction of water-soluble components at a temperature of 80-90 ° C;

- carrying out water extraction in mild conditions compared to the prototype (the second stage of extraction according to the prototype is treatment with hot steam) makes it possible to avoid the destruction of biologically valuable substances of woody fir green and to obtain preparations that are more active for farm birds;

- conducting water extraction of waste green wood fir after extraction with an organic solvent that is not miscible with water, allows to obtain from the waste generated by known methods, a new product - the sum of water-soluble biologically active components that can be used as biologically active feed additives;

- concentrating the extract to 50 wt.% and above or obtaining a solid extract ensures the preservation of consumer qualities of the product for a long time under simple storage conditions, as well as its transportation in concentrated form to the place of direct use;

- the target product, obtained both in the form of solutions and in the form of a solid concentrate, is easily and in any proportions mixed with water, therefore, a solution of the target product of the desired concentration can be prepared at the place of use and does not require special equipment;

- the method allows to utilize the organic solvent remaining on the green wood of fir for re-technological use, which also improves the environmental parameters of the process.

The invention is illustrated by the following examples.

Example 1

To 398 g of fir green wood waste from obtaining a biologically active amount of triterpenic acids resulting from the 2-fold extraction of 227 g of fir green wood with methyl tert-butyl ether according to [RU 2108803] and containing methyl tert-butyl ether (MTBE), add 300 g of water and gradually heated to 80-90 ° C in a water bath for 3 hours, driving off the residual MTBE with water vapor, a total of 230 ml of MTBE is collected. The aqueous extract is drained from a layer of fir green wood and concentrated in a vacuum of a water-jet pump at a temperature of 60-80 ° C, 100 g of an aqueous extract with a dry matter content of 20% is obtained.

Example 2

In the apparatus for extraction with a jacket contains 139 kg of waste from obtaining a biologically active amount of triterpene acids, a concentrate of neutral isoprenoids and fir oil according to [RU 2006138542 from 10.31.2006]. The waste is a layer of extracted woody fir greenery containing MTBE and resulting from the 2-fold extraction of 80 kg of woody green fir MTBE. 220 l of water are added to the apparatus.

By supplying steam to the jacket, the contents of the apparatus are heated, while MTBE with steam is distilled off. The distillates are condensed in a refrigerator-condenser and collected in a receiver. A total of 80 liters of MTBE are collected. The aqueous extract is drained hot (60-65 ° C) and concentrated in vacuo at a temperature of 60-80 ° C, 34.2 kg of an aqueous extract concentrate with a dry matter content of 20% are obtained.

The flavonoid content in terms of rutin (determined spectrophotometrically with AlCl ₃ ) is 95 mg / 100 g; the mass fraction of hydrolyzable sugars in terms of sucrose is 6% (determined titrimetrically with the Feling reagent), the mass fraction of oligosaccharides (determined gravimetrically by precipitation with alcohol) is 11%.

Example 3

220 l of water is poured into the apparatus containing a layer of woody fir greenery after the discharge of MTBE infusions (the weight of the waste obtained according to [RU 2108803] is 139 kg, including spent fir green and residual MTBE). By supplying steam to the jacket, the contents of the apparatus are gradually heated to 80-90 ° C, while MTBE with steam is distilled off. The distillates are condensed in a refrigerator-condenser and collected in a receiver. A total of 80 liters of MTBE are collected.

The aqueous extract is poured hot (60-65 ° C) and concentrated in vacuo at a temperature of 60-80 ° C, 13.7 kg of concentrate with a dry matter content of 50% are obtained.

300 l of water are re-loaded into the apparatus with fir greens and heated to 80 ° C for 3 hours. The extract is poured hot and sent to concentration in vacuo, as described above. Obtain 6.0 kg of concentrate with a dry matter content of 50%.

For the third time, 300 l of water are loaded into the apparatus and the contents of the apparatus are heated to 80-90 ° C for 3 hours. The extract is poured off hot and concentrated in vacuo. Obtain 2.1 kg of concentrate with a dry matter content of 50%. The concentrate fractions obtained from the three extractions are combined to give 21.7 kg of an aqueous extract concentrate with a dry matter content of 50%.

The flavonoid content in terms of rutin (determined spectrophotometrically with AlCl ₃ ) is 235 mg / 100 g; the mass fraction of hydrolyzable sugars in terms of sucrose is 14% (determined titrimetrically with the Feling reagent), the mass fraction of oligosaccharides (determined gravimetrically by precipitation with alcohol) is 27%.

Example 4

220 l of water are poured into the apparatus containing a layer of fir green wood after draining MTBE infusions (the weight of the waste obtained according to [RU 2108803] is 139 kg, including spent fir green and residual MTBE). By supplying steam to the jacket, the contents of the apparatus are gradually heated to 80-90 ° C, while MTBE with steam is distilled off. The distillates are condensed in a refrigerator-condenser and collected in a receiver. A total of 80 liters of MTBE are collected.

The aqueous extract is poured hot (60-65 ° C) and concentrated in vacuo at a temperature of 60-80 ° C, 13.7 kg of concentrate with a dry matter content of 50% are obtained.

300 l of water are re-loaded into the apparatus with fir greens and heated to 80 ° C for 3 hours. The extract is poured hot and sent to concentration in vacuo, as described above. Obtain 6.0 kg of concentrate with a dry matter content of 50%.

For the third time, 300 l of water are loaded into the apparatus and the contents of the apparatus are gradually heated to 80-90 ° C for 3 hours. The extract is poured off hot and concentrated in vacuo. Obtain 2.1 kg of concentrate with a dry matter content of 50%. The concentrate fractions obtained from the three extractions are combined to give 21.7 kg of concentrate with a dry matter content of 50%.

The combined aqueous extract concentrate, obtained as a result of 3 extractions in an amount of 21.7 kg and containing 50% dry matter, is loaded into a vacuum oven and dried in a vacuum of 0.1-0.2 ata at 50-60 ° C until a glassy mass forms dark brown color. The resulting mass of 10.9 kg is crushed and packaged in sealed plastic bags.

The flavonoid content in terms of rutin (determined spectrophotometrically with AlCl ₃ ) is 450 mg / 100 g; the mass fraction of hydrolyzable sugars in terms of sucrose is 30% (determined titrimetrically with the Feling reagent), the mass fraction of oligosaccharides (determined gravimetrically by precipitation with alcohol) is 52%.

Example 5. Storage of aqueous extract concentrates.

1. The extract obtained according to example 1 (20% dry. In-va) is stored in a refrigerator at + 5 ° C for a long time without changing the appearance and properties. When stored in an open non-sterile container at a temperature of 20 ° C for 3 days, the appearance of a colony of molds was noted on the surface of the extract.

2. The extract obtained according to example 2 (50% dry. In-va), is well preserved without changing the appearance and properties at room temperature for six months.

The influence of feed additives on the development and zootechnical indicators of poultry

Example 6

The studies were carried out jointly with the Institute of Animal Husbandry SB RAHN on young chickens.

The experiments were conducted in laboratory conditions on the young of the cross-country "IZA-F-15". The extract was set in the form of an aqueous solution at the rate of 5, 10, 25, 50 and 100 μg of dry matter per 1 kg of live weight. The extract was given once from the 1st to the 20th day of life. Giving the extract was carried out by feeding animals to the experimental group. In control, the extract was not given to animals. The number of goals in the experimental and control variants is 100-200. The repetition of the experiment is 4 times.

In experiments, it was shown that the Siberian fir extract positively affects the development of chickens, increases their safety and productivity (Table 1). At the same time, it was noted that the extract has the greatest efficiency in doses of 25 and higher μg per kg of live weight.

Table 1 The effect of the aqueous extract of Siberian fir on zootechnical indicators of young chickens Indicators Experience Options The control Experience, dose of the extract, mcg / kg 5 10 25 fifty one hundred Preservation,% 88.0 ± 5.7 90.1 ± 2.3 * 92.4 ± 2.2 * 95.4 ± 2.8 ** 97.6 ± 2.6 ** 99.0 ± 1.7 ** Homogeneity,% 80.0 ± 4.3 84.6 ± 3.1 * 88.2 ± 2.9 * 90.1 ± 2.3 ** 91.0 ± 2.0 ** 92.0 ± 1.2 ** Productivity in 140 days,% 48.0 ± 3.5 55.7 ± 3.9 * 58.1 ± 2.9 61.7 ± 3.2 62.4 ± 3.0 65.2 ± 3.1 Notch in 140 days,% 0.4 ± 0.05 0.2 ± 0.02 * 0.025 ± 0.01 ** 0 ** 0 ** 0 ** * and ** - experimental variants were noted, significantly differing by 0.5% and 0.1% significance level from control variants, respectively.

Example 7

In production conditions, we studied the effect of Siberian fir extract on the safety and development of broiler chickens of ROSS 308 cross. The extract was given to chickens according to the following scheme: from 1 to 10 days of life at the rate of 50 μg per kg of live weight, from 15 to 20 days - 25 μg per kg of live weight, from 25 to 30 days - 10 micrograms per kg of live weight and from 35 to 40 days - 5 micrograms per kg of live weight. Giving the extract was carried out by adding to the feed. In control variants, the extract was not given to animals. The number of livestock in the experimental and control variants is 25,000 - 30,000. The repetition of the experiment is 3 times.

As a result of the work, it was found that giving the extract leads to increased preservation, stimulates development and increases the productivity of chickens while increasing feed conversion (Table 2).

table 2 The effect of Siberian fir extract on zootechnical indicators of broiler chickens Indicators Experience Options The control Extract Preservation,% 92.1 ± 3.2 96.7 ± 2.0 ** The average weight of 1 head at the beginning of the growing period, g 42.2 ± 4.3 40.3 ± 3.7 The average weight of 1 head at the end of the growing period, g 1689.7 ± 134.7 1986.1 ± 78.9 ** The average daily gain,% 41.2 ± 2.5 48.6 ± 1.9 ** The output of carcasses 1 category,% 81.3 ± 5.1 92.3 ± 2.9 ** Feed conversion 1.71 ± 0.7 1.51 ± 0.6 Productivity index 221.9 ± 9.2 311.2 ± 2.6

Claims (1)

A method of processing waste from the extraction of green wood of fir with an organic solvent immiscible with water, involving extraction, characterized in that the extraction is carried out by adding water to the waste and heating to a temperature of 80-90 ° C for 3 hours while distilling off the residual solvent on the fir layer with water vapor, the resulting aqueous extract is concentrated in vacuo at a temperature of 60-80 ° C to obtain an aqueous extract concentrate in the form of a solution with a dry matter content of 50-70% or in the form of a solid Wow substance as an additive for farm animals.