PL228631B1 - Biopreparation on solid subsoil for cultivation of plants and method for producing the biopreparation - Google Patents

Description

(12) PATENT DESCRIPTION ₍ and ₉₎ PL ₍ u) 228631 (13) B1 (21) Filing number: 409902 (22) Filing date: October 23, 2014 (51) IntCI.

A01N 25/08 (2006.01) A01N 65/00 (2009.01) A01N 65/12 (2009.01) A01N 65/34 (2009.01) A01P 1/00 (2006.01) A01P 3/00 (2006.01)

A biopreparation on a solid substrate for plant care and a method of producing a biopreparation

(73) The right holder of the patent: INSTITUTE OF INDUSTRIAL CHEMISTRY THEM. PROF. IGNACY MOŚCICKI, Warsaw, PL (43) Application was announced: 25 April 2016 BUP 09/16 (72) Inventor (s): (45) The grant of the patent was announced: IRENA GRZYWA-NIKSIŃSKA, Warsaw, PL IZABELLA LEGOCKA, Warsaw, PL MAŁGORZATA MACHAŁOWSKA, Warsaw, PL 30/04/2018 WUP 04/18 ALICJA KOWIECZNIKOW, Hipolitów, PL (74) Representative: thing, pat. Jolanta Rosińska

what what what

CM

CM

Ω.

PL 228 631 B1

Description of the invention

The subject of the invention is a biopreparation on a solid substrate with protective and possibly nutritional properties intended for plants and a method of producing a biopreparation.

In modern agriculture, in addition to artificial and natural fertilizers, large amounts of plant protection products are also used. Currently, it is necessary to use agents that fight fungi, molds or pests in mass production of food. The currently used plant protection products are mainly produced synthetically. Unfortunately, their use, in addition to pest control, often has adverse side effects. Such agents often have a harmful effect on humans and animals, causing serious poisoning. Moreover, their continuous use pollutes the environment by the accumulation of toxic substances which degrade very slowly in the soil.

A relatively small amount of fruit and vegetables comes from the so-called organic crops that do not use synthetic plant protection products and artificial fertilizers. However, this production is of little importance in global food production.

It is known to have natural plant compounds with protective and nutritional properties for plant care, the effectiveness of which is similar to that of synthetic agents. For example, some farmers now use nettle decoction to spray tomato bushes. This allows for obtaining well-formed fruit, free from mold and fungi.

Biologically active compounds present in plants are divided into basic ones, which fulfill building, nutritional, energy or reserve functions (carbohydrates, fats, amino acids, proteins, enzymes), and secondary ones, which are products of plant metabolism (glycosides, flavonoids, anthocyanins, essential oils) , tannins found in oak bark, blueberry, walnut and sage, fenugreek seed mucilage, flax and coltsfoot, saponins, bitterness and alkaloids, and phytoncides), which are substances secreted by plants for protection. These substances have a bactericidal and fungicidal effect. The most famous plants containing such compounds include garlic, onion, yarrow, juniper, lavender, pine, mint.

Cabbage juice is known for its strong fungicidal and bactericidal properties due to the biologically active substances present in it, the most important of which are glucosinylate, and especially their decomposition products - isothiocyanates and indoles. These substances occur in various types of cabbage in various amounts, often not exceeding a dozen or so per mille. Also in other plants, such as nettle, biologically active substances are present in small amounts. Therefore, the use of directly squeezed cabbage, nettle or other plant juice or, accordingly, an extract, is ineffective.

In order to obtain preparations with an effective biocidal effect, it is recommended to use multi-concentrated products. However, the preparation of concentrated preparations from plant juice by evaporating the water is very expensive, and some of the unstable active substances also evaporate with the water vapor.

Polish patent applications PL 398858 and PL 398859 describe methods of multiple thickening of active substances from cabbage juice by the method of selective sorption and desorption. As a result of selective sorption, active substances are absorbed on the active surface of the sorbent, from which they are then desorbed with an appropriate eluent. The use of such preparations as biocides has a great advantage because they contain selectively isolated only those active substances that have a biocidal and pesticidal effect.

It has been found that highly concentrated preparations for the care of plants with biocidal and possibly additionally nutritional properties can be obtained in a much simpler way compared to the known methods. The method according to the invention makes it possible to obtain a biologically active product without the processes of desorption of active substances from the carrier surface and distillation of eluents, and avoiding the associated risk of loss of more volatile and unstable active substances. Moreover, the absorption of biologically active substances on a solid support enables their gradual release from the support as a result of varying soil or air humidity.

The biopreparation on a solid substrate for plant care, containing biologically active substances with fungicidal and / or bactericidal and / or pesticidal and possibly nutritional properties, according to the invention, contains at least 2% by weight of biologically active plant substances isolated from cabbage leaves, nettle leaves, horsetail leaves , leaves and / or root of safflower or leaves and / or root of sickle crown and up to 98% by weight of natural solid

The mineral support from the group of silicon compounds, including siliceous earth or aluminosilicate, also modified, or a mixture thereof in any proportion.

The biopreparation according to the invention preferably contains from 2 to 10% by weight of plant biologically active substances and from 90 to 98% by weight of a natural solid mineral carrier from the group of silicon compounds.

Preferably, the siliceous earth has a grain size of 0.1 to 1 mm.

The modified siliceous earth is preferably chemically modified siliceous earth. The modification of siliceous earth with chemical methods is to improve its sorption capacity.

The chemically modified siliceous earth is preferably mineral acid modified siliceous earth. Such siliceous earth can be obtained, for example, by the method described in the Polish patent application PL 274474A2.

Preferably, the aluminosilicate has a grain size of 300 to 500 nm.

Preferably, the aluminosilicate is halloysite, also modified. Haloysite (aluminosilicate with the structure Al4 [Si4O10] (OH) 8-10H2O) is a mineral characterized by high sorption capacity.

The modified halloysite is preferably physically and / or chemically modified halloysite.

Physically modified halloysite is a halloysite which is preferably thermally modified, most preferably at a temperature of 450 ° C, or by means of ultrasound, most preferably at a frequency of 250-350 kHz for 2-3 hours.

The physical modification of halloysite is aimed at improving its sorption capacity by creating defects in the crystal lattice. The biopreparation according to the invention preferably comprises halloysite with a permanently modified crystal structure as a solid support. Such halloysite is obtained, for example, by the method disclosed in the Polish patent specification PL 213655. Chemically modified halloysite is a halloysite modified with urea. The modification of halloysite with urea enhances the nutritional effect of the preparation. Such halloysite is obtained, for example, by the method described in the Polish patent application P-409737.

The biopreparation according to the invention may have both biocidal and nutritional properties, if the carrier of biologically active substances is a mineral sorbent - it has nutritional functions. Moreover, the source of the nutritional properties of the biopreparation can be plant active substances, if plant juice or extract were used to obtain it. On the other hand, the preparation has only biocidal properties, if plant biologically active substances derived from the eluate were used to obtain it, after the process of selective sorption and desorption on non-ionic sorbents.

The invention also relates to a method of producing the above-described biopreparation containing biologically active substances with fungicidal and / or bactericidal and / or pesticidal and possibly nutritional properties, which consists in the fact that biologically active plant substances are separated from cabbage leaves, nettle leaves, horsetail leaves, the leaves and / or the root of the safflower or the leaves and / or the root of the crescent crown in the form of an aqueous or organo-aqueous solution are brought into contact with a bed of natural solid mineral support from the group of silicon compounds including siliceous earth or aluminosilicate, also modified, or their mixture in any proportion, then, after filtering, the product obtained is dried.

Preferably, in the aqueous-organic solution of plant biologically active substances, the aqueous-organic solvent is a mixture of water and a highly polar water-miscible solvent with a carbon number in the molecule from C1 to C3.

The highly polar water-miscible solvent is one selected from the group consisting of methanol, ethanol or acetone.

Preferably, the volume ratio of water to the water miscible organic solvent is at least 70:30.

Preferably, plant juice, possibly after removal of sediments therefrom, is used as an aqueous or aqueous-organic solution of plant biologically active substances, an extract or a solution of plant biologically active substances obtained by selective sorption and desorption on a non-ionic sorbent. Removal of sediments from plant juices is carried out by known methods, e.g. filtration, centrifugation.

The contact of the solution of plant biologically active substances with the bed of natural solid support from the group of silicon compounds can be carried out in various ways.

It is preferable to mix the solution of the plant active substances with the carrier bed for at least 15 minutes.

PL 228 631 B1

The solution of plant active substances is also preferably passed through a column or serially connected columns packed with a bed of support, most preferably through two columns connected in series.

The biopreparation according to the invention is obtained by drying and optionally grinding the final product into a powder. The result is a product with a color determined by the color of the carrier used. The preparation can be applied to plants in a dry form or as an aqueous suspension.

The kinetics of the release of plant active substances from the carrier over time was investigated during the storage of the biopreparation in the air. A sample of the carrier with 9.8% by weight of plant active substances (separated from cabbage in the process of selective sorption and desorption on a non-ionic sorbent) was subjected to thermogravimetric analysis (TGA). It was found that the content of active substances loaded onto the support (here: haloizite) varied from 9.8 wt% to 0.05 wt% after 2 weeks. It has been shown that the biopreparation according to the invention shows a prolonged effect compared to the same amount of active substances in the thickened solution.

The biopreparations according to the invention can be widely used as plant care products harmless to humans and animals.

The invention is illustrated in the examples.

P r z k ł a d 1

The example uses white cabbage juice obtained by squeezing shredded cabbage on a fruit press. This juice, when squeezed directly, was very cloudy. For clarification, the juice was acidified with lactic acid to pH 5.2, and then centrifuged in a sedimentation centrifuge at 6000 rpm. After centrifugation, a completely clear liquid was obtained with a pH of 5.0, transmittance 67.5 (color in% transmittance at wavelength λ = 600, measured on a spectrophotometer), dry matter content at the temperature of 120 ° C was 5.39% by weight, ash content 0.50 wt.% The obtained liquid was passed through a set of two glass columns operating in series. Each column was filled with a mineral sorbent - halloysite with a particle size of 370-390 nm, thermally modified at 450 ° C. The clear liquid was passed through two glass columns operating in series, filled with 200 cm ^{3 of} sorbent each. The clear liquid was dispensed onto the first column. The leak from the first column was directed to the second column. The course of the sorption process was controlled by examining the effluents from the first and second columns for the content of isothiocyanates. The liquid was passed through until active substances were detected in the second column effluent. Then the sorption cycle was interrupted. The liquid from the first column was drained and the loaded carrier was discharged. The second column was used as the first for the next sorption cycle. A total of 540 volumes of liquid were passed through the columns based on the volume of sorbent in one column. Then, the remnants of the liquid were filtered off from the loaded carrier using a vacuum cleaner, and then it was dried at a temperature of about 60 ° C. After drying, the product was obtained in the form of a fine powder, light brown in color, containing 6.97% by weight of sorbed bioactive substances. They are mainly isothiocyanates and indoles.

The obtained product can be used as a plant care preparation that fights mold, fungi, bacteria and pests. The preparation can be used in dry form or as an aqueous suspension.

P r z k ł a d 2

The example used was squeezed cabbage juice, the same as in example 1. The example was carried out as described in example 1, except that siliceous earth (from Merck Sp. Z oo, 0.1 grain size) was used as the column filler. mm), in the amount of 200 cm ³ . 480 volumes of juice (96 liters) were passed through the columns. The procedure was followed in the same way as in Example 1. After drying, the biopreparation for plants was obtained in the form of a light beige powder with similar properties as in Example 1, containing 4.86% by weight of absorbed active substances, mainly isothiocyanates and indoles.

P r z k ł a d 3

The example uses an aqueous extract of dried nettle leaves obtained by shaking them with water (a known method for extracting dried herbs). This extract contained 1.79 wt.% Dry weight (determined at 120 ° C), 0.44 wt.% Ash, and a pH of 7.82. This extract, without clarification, was passed through a set of two glass columns, as in Example 1. The columns were packed with a mineral sorbent consisting of a mixture of 50% halloysite and 50% silica earth. Halloysite with a particle size of 345-450 nm was used

Prior to the action of ultrasound at a frequency of 250-350 kHz for 2-3 hours, and siliceous earth with a grain size of 0.30-0.75 mm, previously activated with 20% sulfuric acid at the temperature of 39.8 ° C for 40 minutes. The flow of liquid through such a mixture of sorbents is facilitated because there is less resistance. 750 volumes of extract were passed through the columns, based on the volume of sorbent in one column. After this amount of extract had been passed through, a small amount of active substances was found in the effluent from column two. At that time, the first working column was disconnected and a mixture of halloysite and silica earth was poured out of it, filled with active substances. The second column was used as the first for the next sorption cycle. The mixture of mineral sorbents poured out from the first column was drained from the remaining liquid and dried as in Example 1. A dry preparation was obtained in the form of a light beige powder with a slight shade of green, with an active substance content of 3.70% by weight.

P r z k ł a d 4

The example uses an aqueous solution of active substances from white cabbage, obtained from a concentrated eluate of cabbage juice, known by the method of selective sorption and desorption consisting in passing cabbage juice, previously clarified, through a bed of non-ionic sorbent, and then desorbing biologically active substances from a bed of non-ionic sorbent. with 96% ethyl alcohol. The resulting eluate was concentrated. The concentrated eluate contained: dry weight 7.59% by weight, ash 0%, pH 7.1.

^{200 cm 3 of the} obtained concentrated eluate and 200 cm ^{3 of} water were poured into a 1-liter glass beaker equipped with a mechanical stirrer. 200 g of finely ground halloysite, chemically modified with urea, according to the known method from the Polish patent application P-409737, were poured into this solution while mixing. The mixture was stirred at room temperature for 15 minutes. After this time, the stirrer was turned off and the resulting packed sorbent was filtered using a vacuum cleaner. After drying, a biopreparation was obtained with properties similar to that obtained in Example 1. The product contained 9.7% by weight of biologically active substances.

P r z k ł a d 5

In the example, an aqueous extract of dried nettle leaves was used, previously concentrated, which contained: dry weight 3.5% by weight, ash 0.45% by weight, pH 7.9. This solution, in an amount of 200 cm ³ was poured into a glass beaker with stirring, as in Example 4 was added 100 cm ³ of water. Then, 200 g of silica earth (from Merck Sp z oo, grain size 0.22 mm) were poured into such a solution, with the agitator running,. The mixture was stirred for 25 minutes. After this time, the agitator was stopped and the silica earths loaded with active substances were filtered off. After drying, a powder formulation with a similar effect as in Example 1 was obtained, containing 4.3% by weight of biologically active substances.

P r z k ł a d 6

The example uses nettle juice obtained by squeezing fresh nettle leaves on a fruit press, similar to the cabbage juice described in Example 1. This juice contained much greater amounts of active substances than the corresponding amounts of the aqueous extract. The parameters of this juice were as follows: dry weight 3.81%, weight ash 0.83% by weight, pH 6.92. Then 500 cm ^{3 of} this juice was poured into a 1-liter glass beaker provided with a mechanical stirrer. While stirring, a mixture of 50 g of unmodified halloysite, grain size 370-390 nm, with 50 g of siliceous earth (from Merck Sp. Z oo, grain size 0.1 mm) was poured into the juice. The mixture was stirred for 20 minutes. Then the obtained sorbent was filtered off with a vacuum cleaner and dried. A biopreparation with a strong biocidal effect was obtained, containing 5.02% by weight of biologically active substances.

The effectiveness of the biopreparation according to the invention has been confirmed experimentally. Four identical unrooted pelargonium legs were planted in four identical containers, without a drain. Two of them (1, 2) were fed with commercially available fungicide and fertilizers. The remaining two (3, 4) were sprinkled with the biopreparation according to the invention (obtained as described in example 1). Accelerated flowering and rooting of plants fed with the new biopreparation were observed (3, 4). After two weeks, white mold was observed on the ground in containers 1 and 2, which was not observed in containers 3 and 4.

PL 228 631 B1

Claims (18)

Patent claims 1. Biopreparation on a solid substrate for plant care, containing biologically active substances with fungicidal and / or bactericidal and / or pesticidal and possibly nutritional properties, characterized by the fact that it contains at least 2% by weight of biologically active plant substances isolated from cabbage leaves, nettle leaves , horsetail leaves, leaves and / or safflower root or leaves and / or crescent root, and up to 98% by weight of a natural solid mineral support from the group of silicon compounds including siliceous earth or aluminosilicate, also modified, or a mixture thereof in any proportion. 2. Biopreparation, according to claim The method of claim 1, characterized in that it contains from 2 to 10% by weight of plant biologically active substances and from 90 to 98% by weight of a natural solid mineral carrier from the group of silicon compounds. 3. Biopreparation, according to claim The process of claim 1, wherein the siliceous earth has a grain size of 0.1 to 1 mm. 4. The biopreparation, according to claim The process of claim 1, wherein the modified siliceous earth is chemically modified silica earth. 5. The biopreparation according to claim 4. The process of claim 4, wherein the chemically modified silica earth is mineral acid modified silica earth. 6. The biopreparation, according to claim The process of claim 1, wherein the aluminosilicate has a grain size of 300 to 500 nm. 7. The biopreparation, according to claim The process of claim 1, wherein the aluminosilicate is halloysite, also modified. 8. The biopreparation, according to claim The process of claim 7, wherein the modified halloysite is a physically and / or chemically modified halloysite. 9. The biopreparation, according to claim 8. The process of claim 8, characterized in that the physically modified halloysite is a thermally modified halloysite, most preferably at a temperature of 450 ° C. 10. Biopreparation, according to claim 8. The method of claim 8, wherein the physically modified halloysite is ultrasonically modified halloysite, most preferably at a frequency of 250-350 kHz for 2-3 hours. 11. The biopreparation, according to claim The process of claim 8, wherein the chemically modified halloysite is urea-modified halloysite. 12. A method of producing a biopreparation on a solid plant care substrate, according to claim 1, A method according to any of the preceding claims, characterized in that the biologically active plant substances isolated from cabbage leaves, nettle leaves, horsetail leaves, leaves and / or safflower root or leaves and / or crescent root in the form of an aqueous or aqueous-organic solution are contacted with with a bed of a natural solid mineral support from the group of silicon compounds including siliceous earth or aluminosilicate, also modified, or with a mixture thereof in any proportion, and then, after filtering, the obtained product is dried. 13. The method according to p. 12. The method according to claim 12, characterized in that in the aqueous-organic solution of plant biologically active substances, the aqueous-organic solvent is a mixture of water and a highly polar water-miscible solvent with a number of carbon atoms in the molecule from C1 to C3. 14. The method according to p. The process of claim 13, wherein the strongly polar water-miscible solvent is selected from the group consisting of methanol, ethanol or acetone. 15. The method according to p. A process as claimed in any of the claims 12 to 14, characterized in that the volume ratio of water to water-miscible organic solvent is at least 70:30. 16. The method according to p. A method according to claim 12, characterized in that the plant juice, optionally after removing sediments from it, is used as the aqueous or water-organic solution of plant biologically active substances, an extract or a solution of plant biologically active substances obtained in the process of selective sorption and desorption on a non-ionic sorbent. 17. The method according to p. The process of claim 12, characterized in that the solution of plant active substances is mixed with the carrier bed for at least 15 minutes. 18. The method according to p. A process as claimed in claim 12, characterized in that the solution of plant active substances is passed through a column or serially connected columns packed with a bed of support, most preferably through two columns connected in series.