WO2014185794A1 - A silicon formulation with plant growth stimulating properties, a method of the preparation of a silicon formulation with plant growth stimulating properties and its use - Google Patents
A silicon formulation with plant growth stimulating properties, a method of the preparation of a silicon formulation with plant growth stimulating properties and its use Download PDFInfo
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- WO2014185794A1 WO2014185794A1 PCT/PL2013/000116 PL2013000116W WO2014185794A1 WO 2014185794 A1 WO2014185794 A1 WO 2014185794A1 PL 2013000116 W PL2013000116 W PL 2013000116W WO 2014185794 A1 WO2014185794 A1 WO 2014185794A1
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/18—Semi-solid fertilisers, e.g. foams or gels
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
Definitions
- the invention relates to a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance.
- the invention also relates to a method of the preparation of a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance and the application of a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance in agricultural and horticultural crops.
- Silicon which constitutes approximately 28% of the lithosphere, is an essential element in the life of plants and other living organisms. In plants, it accumulates mainly in cell walls, reinforcing them mechanically. Dicotyledonous plants contain much smaller quantities of it than monocotyledons.
- Silicon is present predominantly in the polymorphic Si02 compounds.
- Liquid silicon forms are represented by aqueous solutions of silicon acids or salts thereof, which are transformed into organic silicon as a result of chemical processes occurring in plants.
- the liming of acidic soils causes silicon to be transformed into forms which are poorly absorbed by plants.
- silic acid particles in colloidal solutions are characterised by a large surface, of approximately 300 m 2 per 1 ml of solution.
- active silanol Si-OH hydrophilic groups are observed on their surface, such molecules have a tendency to separate from the water and clump together to form larger agglomerates, which reduces their water solubility and hinders their uptake by plants.
- organic compounds such as polysaccharides, polyalcohols and amino acids, stabilises silicate solutions against undesired polymerisation, increasing their bioavailability.
- silicon protects them from excessive evaporation of water by transpiration, and thus contributes to improving the supply of plant nutrients.
- the presence of silicon in the structure of plant relieves stress, which is reflected inter alia in periods of drought.
- the cell walls reinforced with silicon provide a stronger natural barrier for the mushroom spores and pests, and become more resistant to enzymes produced by pathogens (fungistatic role).
- Silicon also reduces the abiotic stress (stress caused by external factors) by increasing the tolerance of plants to low temperatures, intensifying photosynthesis in low light intensity, protecting against the toxic effects of high levels of manganese and iron in the soil, and reduces the toxic effects of aluminium on root growth (as silicon compounds are a selective ligand of aluminium ions). Silicon also has an important influence on the regulation of nutrient uptake, which is most evident in the case of phosphorus uptake. Fertilisation with silicon compounds allows for much lower rate of fertilisation with phosphorus compounds wherein maintaining similar yields.
- the use of water-soluble silicon compounds in the cultivation reduces the susceptibility of plants to pests and diseases, and stress caused by adverse weather conditions, and also increases the. production of biomass and strengthens stems, and therefore reduces lodging. Thanks to providing plants with bioavailable silicon, it is possible to reduce the use of plant protection products, which translates into a reduction in the cost of cultivation and the protection of the environment.
- the patent literature also contains information on the use of silicon formulation of in plant cultivation.
- the formulation in the form of an aqueous solution containing boric acid and non-colloidal silicic acid as well as a water absorbing additive the method for its formulation and its use.
- Said solution is characterised in that the silicon content (in the form of silicic acid) is of 0.01 to 2% by weight, and the content of boron (in the form of boric acid) is of approximately 0.0001 to 4% by weight, wherein the solution has a pH of less than 2.
- the solution contains at least 30% of the water-absorbing additive, such as a polysorbate, vegetable gum, substituted cellulose, glycerol and fatty acid polyester, polyethylene glycol, polydextrose, propylene glycol, propylene glycol alginate, polyoxy ethylene glycol ester, pectin or amidated pectin, sucrose and fatty acid ester, acetylated or hydroxypropyl starch, starch phosphates, urea, sorbitol, ma!titol, vitamins, or mixtures thereof.
- the process for preparing the solution referred to above consists in hydrolysing one or more silicon and boron compounds in an acidic solution containing one or more dissolved water absorbing additives.
- Patent specification PL 193859 relates to a nitrogenous fertiliser with prolonged action, which is constituted by ammonium silicate in a crystalline form, resulting frorr he double replacement reaction of silicic acid or alkali metal (sodium or potassium) silicate with an ammonium salt of an acid selected from the following group: sulphuric, hydrochloric, nitric, phosphoric, carbonic or by aqueous ammonia, wherein the fertiliser contains 25% of nitrogen and 53.5% of silicon in the form of silicon dioxide.
- the ready product is in the form of granules for soil application.
- the JPH 0459614 patent description relates to an aqueous solution of silicic acid containing silicon in a high concentration obtained by adding a special solubilising agent to the silicate.
- a special solubilising agent selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, casein, gelatin, arginine, histidine, L-glutamic acid, soy protein hydrolysates of many amino acids and urea, is added to the aqueous silicate solution, and then pH 5-7 is adjusted with the acid.
- the weight ratio of silicate to the solubilising agents is preferably (1 :0.1) - (1 :1 .0). If the above-mentioned silicon solution is used as a fertiliser, preferably, potassium salt is used as the silicate, and the acid for pH adjustment is preferably phosphoric acid.
- the aim of the present invention is to provide such a formulation of silicon formulation, a method for its preparation, and its use, which would have the properties of stimulating plant growth, contain water-soluble compounds of silicon with a high concentration (the content of which is expressed by S1O2), suitable for storage in the form of stock solution or powder which is completely soluble in water, while having a reduced tendency to polymerise and containing such enhancers of the water solubility of silicon compounds that would act as a stimulant for the absorption of silicon compounds contained in the formulation by plants.
- An additional objective is to complete the said formulation with at least one macro- and/or micronutrients such as nitrogen (N), phosphorous, (P2O5), potassium (K2O), magnesium ( gO), calcium (CaO), sulphur (SO3), boron (B), copper (Cu) Iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn), and cobalt(Co), while maintaining a reduced tendency of the formulation to polymerise and the stimulating effect of the enhancers of the water solubility of silicon compounds on the bioavailability of silicon compounds by plants though using (applying) the formulation into the roots and/or outside the roots.
- macro- and/or micronutrients such as nitrogen (N), phosphorous, (P2O5), potassium (K2O), magnesium ( gO), calcium (CaO), sulphur (SO3), boron (B), copper (Cu) Iron (Fe), manganese (Mn), molybdenum (Mo), zinc (
- the silicon formulation with plant growth stimulating properties in the form of an aqueous solution or powdery water-soluble substance, containing water-soluble silicon compounds, stabilisers of the silicon compounds solution against undesired polymerisation, and pH control agents, is characterised by the fact that it contains silicon compounds in an amount of 0.5 to 60% by weight (calculated as S1O2), preferably 10 to 25 % by weight, dissolved in an aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, and further preferably contains at least one of macro- and/or micronutrient such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, wherein the pH of the formulation is 3 to 12, preferably 4 to 7.
- the source of water-soluble silicon compounds should be silicic acids, potassium silicates, sodium silicates, or mixtures thereof, wherein the pH used in the formulation of the silicon compounds is from 2 to 13. It has been found that some of the above-mentioned substances stabilising the silicon compound solution and preventing the polymerisation increase the bioavailability of silicon for the plants. Therefore, it is preferred that the formulation contain mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof in an amount of 0.1 to 10% by weight.
- the formulation shall contain said macro- and/or micronutrients in the form of salts of the citric acid and/or ethylenediaminetetraacetic acid (Versene, EDTA).
- said macro- and/or micronutrients in the form of salts of the citric acid and/or ethylenediaminetetraacetic acid (Versene, EDTA).
- the formulation according to the invention has a liquid, gel form and is fully soluble in water.
- the formulation can also be transformed into a fully water-soluble powder through processes of drying the liquid, preferably spray drying.
- the method for preparing the silicon formulation with plant growth stimulating properties wherein water-soluble compounds of silicon, stabilisers of silicon compound solution against undesired polymerisation, and pH control agents are combined in an aqueous medium, is characterised in that the soluble silicon compounds having a pH of 2 to 13, in the form of silicic acids, potassium silicate, sodium silicate or mixtures thereof in the amount of 0.5 to 60% by weight, preferably 0 to 25% by weight (calculated as S1O2), are dissolved in an aqueous medium containing stabilisers such as polyalcohols, polysaccharides, fulvic acids, amino acids or mixtures thereof and compounds of nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, and the final pH of the composition is determined in the range of 3 to 12, preferably 4 to 7, ideally with citric acid, hydroxides and/or carbonates of alkali metals, especially sodium or
- the formulation of the stock solution thus obtained has a high content of silicon, and additionally contains nutrients and additives, which in addition to the solution-stabilising properties have a positive influence on the bioavailability for plants.
- the silicon formulation can be prepared in the form of powder to be dissolved in water.
- the said stock solution is dried, preferably in spray dryers, and packed in airtight containers.
- mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof are used as substances stabilising the composition and preventing the polymerisation of the silicon compounds, in an amount of 0.1 to 10% by weight, as it increases the bioavailability of silicon in plants.
- metal complexes which constitute macro- and/or micronutrients, which allows to improve the bioavailability of silicon for the plant and additionally prevent polymerisation, improving the stability of the formulation composition.
- metal complexes in the form of citric and/or ethylenediaminetetraacetic acid salts for the implementation of the method.
- the stock solution of the preparation, or the powder form of the formulation have too high a concentration of active ingredients for the formulation to be used directly in cultivation.
- the formulation For the application of the formulation into the root or outside the root, it is necessary to dilute it with water to obtain a concentration of active ingredients which is acceptable for the plant.
- a silicon formulation with plant growth stimulating properties containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance, containing water- soluble compounds of silicon, the content of which expressed in the form of SiO 2 is of 0.5 to 60% by weight, which formulation preferably contains at least one of the macro and/or micronutrients such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, preferably complexed, and it is obtained by dissolving silicic acids and/or salts thereof having a pH of 2 to 13 in an acidic aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, is in agricultural and horticultural applications outside the root and/or into the root, after dilution with water, in the concentration range of 0.02 to 5% by mass.
- the macro and/or micronutrients such as nitrogen, phospho
- the formulation according to the invention is characterised by biological activity which translates into a favourable effect on the metabolism of plants and the reduction of the development of diseases and the adverse impact of abiotic and other biotic stress factors.
- the invention is illustrated by the following examples which present the methods of preparation the formulation, the resulting formulation and use of the formulation in plant cultivation.
- KELZAN HP xanthan gum obtained by means of the bacterial fermentation of carbohydrates
- the resulting solution of the iron chelate was added in a small stream to 666.0 kg of silicic acid sol contained in the second tank.
- the solutions were combined, with vigorous stirring to prevent the formation of difficult-to-dissolve agglomerates.
- the clear solution obtained after filtration was directed for packaging.
- the final formulation in the form of gel contains in % by weight: 16.9% S1O2, 2.0% iron, 2.5% mannitol (polyalcohol).
- Zinc and cobalt chelates were obtained in a separate tank by chelating zinc sulphate and cobalt sulphate with the sodium salt of EDTA in the presence of citric acid.
- a tank containing 0.0 I of water at 35 ° C equipped with a stirrer 2.15 kg of zinc sulphate containing 35.3% zinc, and 0.103 kg of cobalt chloride containing 23.4% of cobalt were dissolved.
- 0.2 kg of citric acid and 3.5 kg of tetrasodium salt of EDTA were added and stirred to obtain a clear transparent solution.
- a silicon formulation was obtained containing in 1 litre: 130 g of S1O2, 6.2 g of Mo, 7.6 g of Zn and 0.24 g of Co.
- the formulation After filtration, the formulation was directed for packaging .
- the formulation contains in 1 litre: 200.0 g of S1O2, 24.1 g of Fe and 30.0 g of mannitol.
- the resulting solution was added to 565.0 litres of potassium silicate at 35 ° C in a second tank.
- the solutions were combined slowly, in a small stream, to avoid the formation of large agglomerates, especially at the end of combing the solutions.
- the resulting formulation has a pH of 11.5 and contains in 1 litre: 150.0 g of S1O2, 99.5 g of K2O, 1.3 g of boron, 0.25 g of zinc and 50 g of methionine.
- the product was filtered after standing and directed to packaging.
- Tests were conducted at the Research Institute of Horticulture in Skierniewice to determine the biological efficacy of the silicon formulation in comparison to fungicide for the occurrence of verticillium wilt in strawberry plants.
- the silicon formula was applied by watering the plants with a solution 0.4% by weight concentration, and applying 0.2 litres of solution under each plant. Two treatments were performed: the first one on April 19, 2012, in the early balloon stage (BBCH 58), and a second one on May 1 , 2012, at the beginning of flowering (BBCH 60).
- the soil application resulted in three times smaller infection of plants in comparison to the control plants not treated with the formulation and almost twice smaller in comparison with plants treated with fungicide.
- the quadruple treatments increased the marketable yield by 34%.
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Abstract
The silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance contains water-soluble silicon compounds in an amount of 0.5 to 60% by weight (calculated as SiO2), dissolved in an aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, and additionally preferably contains at least one of the macro and/or micronutrients such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt. Silicic acids, potassium silicates, sodium silicates, or mixtures thereof are the source of silicon compounds, while the pH of the silicon compounds used in the formulation is from 2 to 13. Preferably the formulation contains mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof in an amount of 0.1 to 10 % by weight. The method of the preparation of the silicon formulation is also presented, and its use in agricultural and horticultural cultivation, after dilution with water in a concentration range from 0.02 to 5% by weight.
Description
A SILICON FORMULATION WITH PLANT GROWTH STIMULATING
PROPERTIES, A METHOD OF THE PREPARATION OF A SILICON
FORMULATION WITH PLANT GROWTH STIMULATING PROPERTIES
AND ITS USE
The invention relates to a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance.
The invention also relates to a method of the preparation of a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance and the application of a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form of an aqueous solution or powdery water-soluble substance in agricultural and horticultural crops.
Silicon, which constitutes approximately 28% of the lithosphere, is an essential element in the life of plants and other living organisms. In plants, it accumulates mainly in cell walls, reinforcing them mechanically. Dicotyledonous plants contain much smaller quantities of it than monocotyledons.
Silicon is present predominantly in the polymorphic Si02 compounds. Liquid silicon forms are represented by aqueous solutions of silicon acids or salts thereof, which are transformed into organic silicon as a result of chemical processes occurring in plants. The liming of acidic soils causes silicon to be transformed into forms which are poorly absorbed by plants.
Studies (for example, J. AMER. SOC. HORT. SCI. 1 17(6):906-912. 1992. "Soluble Silicon Sprays Inhibit Powdery Mildew Development on Grape Leaves"; Pat Bowen, Jim Menzies, David Ehre, Lacey Samuels, Anthony D.M. Glass) have shown positive impact of spraying with solutions containing silicon in the form of
silicates or silicic acid sols on the crop. Plants which were provided the same solutions through the soil reacted in a similar manner. An increase was observed in the root mass and the above-ground parts of plants. The comparative studies with plant protection products have shown similar efficacy for certain pathogens. This effect allows for the reduction in the use of harmful plant protection products and environmental protection.
It is known from practice and literature that appropriately treated silicon compounds become compounds which are assimilated by plants. Silicic acid particles in colloidal solutions are characterised by a large surface, of approximately 300 m2 per 1 ml of solution. As active silanol Si-OH hydrophilic groups are observed on their surface, such molecules have a tendency to separate from the water and clump together to form larger agglomerates, which reduces their water solubility and hinders their uptake by plants. The addition of organic compounds, such as polysaccharides, polyalcohols and amino acids, stabilises silicate solutions against undesired polymerisation, increasing their bioavailability.
In addition, by insulating and stiffening the plant cell wall, silicon protects them from excessive evaporation of water by transpiration, and thus contributes to improving the supply of plant nutrients. The presence of silicon in the structure of plant relieves stress, which is reflected inter alia in periods of drought. Moreover, the cell walls reinforced with silicon provide a stronger natural barrier for the mushroom spores and pests, and become more resistant to enzymes produced by pathogens (fungistatic role).
Silicon also reduces the abiotic stress (stress caused by external factors) by increasing the tolerance of plants to low temperatures, intensifying photosynthesis in low light intensity, protecting against the toxic effects of high levels of manganese and iron in the soil, and reduces the toxic effects of aluminium on root growth (as silicon compounds are a selective ligand of aluminium ions). Silicon also has an important influence on the regulation of nutrient uptake, which is most
evident in the case of phosphorus uptake. Fertilisation with silicon compounds allows for much lower rate of fertilisation with phosphorus compounds wherein maintaining similar yields.
The use of water-soluble silicon compounds in the cultivation reduces the susceptibility of plants to pests and diseases, and stress caused by adverse weather conditions, and also increases the. production of biomass and strengthens stems, and therefore reduces lodging. Thanks to providing plants with bioavailable silicon, it is possible to reduce the use of plant protection products, which translates into a reduction in the cost of cultivation and the protection of the environment.
The patent literature also contains information on the use of silicon formulation of in plant cultivation.
For example, in the PL 206314 patent description, the formulation in the form of an aqueous solution containing boric acid and non-colloidal silicic acid as well as a water absorbing additive, the method for its formulation and its use. Said solution is characterised in that the silicon content (in the form of silicic acid) is of 0.01 to 2% by weight, and the content of boron (in the form of boric acid) is of approximately 0.0001 to 4% by weight, wherein the solution has a pH of less than 2. The solution contains at least 30% of the water-absorbing additive, such as a polysorbate, vegetable gum, substituted cellulose, glycerol and fatty acid polyester, polyethylene glycol, polydextrose, propylene glycol, propylene glycol alginate, polyoxy ethylene glycol ester, pectin or amidated pectin, sucrose and fatty acid ester, acetylated or hydroxypropyl starch, starch phosphates, urea, sorbitol, ma!titol, vitamins, or mixtures thereof. The process for preparing the solution referred to above consists in hydrolysing one or more silicon and boron compounds in an acidic solution containing one or more dissolved water absorbing additives. The invention also includes the use of a solution as defined above, after dilution, for application on plants or trees.
Patent specification PL 193859 relates to a nitrogenous fertiliser with prolonged action, which is constituted by ammonium silicate in a crystalline form, resulting frorr he double replacement reaction of silicic acid or alkali metal (sodium or potassium) silicate with an ammonium salt of an acid selected from the following group: sulphuric, hydrochloric, nitric, phosphoric, carbonic or by aqueous ammonia, wherein the fertiliser contains 25% of nitrogen and 53.5% of silicon in the form of silicon dioxide. The method for producing nitrogen fertilisers with prolonged action from silicic acid or silicates and ammonium salts consists in conducting a double replacement reaction of silicic acid or alkali metal (sodium or potassium) silicate with an ammonium salt of an acid selected from the following group: sulphuric, hydrochloric, nitric, phosphoric, carbonic, or with aqueous ammonia in an aqueous medium, which is selected in the following manner: for each kilogram of distilled water, two moles of reagents are added, which are calculated with the reaction stoichiometry, basifying the reaction to pH = 6.0 - 10.0, preferably to pH 6.0 - 8.0 with an aqueous ammonia or a 0.5% potassium hydroxide solution. The ready product is in the form of granules for soil application.
The JPH 0459614 patent description relates to an aqueous solution of silicic acid containing silicon in a high concentration obtained by adding a special solubilising agent to the silicate. One or two or more solvents, selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, casein, gelatin, arginine, histidine, L-glutamic acid, soy protein hydrolysates of many amino acids and urea, is added to the aqueous silicate solution, and then pH 5-7 is adjusted with the acid. The weight ratio of silicate to the solubilising agents is preferably (1 :0.1) - (1 :1 .0). If the above-mentioned silicon solution is used as a fertiliser, preferably, potassium salt is used as the silicate, and the acid for pH adjustment is preferably phosphoric acid.
The aim of the present invention is to provide such a formulation of silicon formulation, a method for its preparation, and its use, which would have the
properties of stimulating plant growth, contain water-soluble compounds of silicon with a high concentration (the content of which is expressed by S1O2), suitable for storage in the form of stock solution or powder which is completely soluble in water, while having a reduced tendency to polymerise and containing such enhancers of the water solubility of silicon compounds that would act as a stimulant for the absorption of silicon compounds contained in the formulation by plants. An additional objective is to complete the said formulation with at least one macro- and/or micronutrients such as nitrogen (N), phosphorous, (P2O5), potassium (K2O), magnesium ( gO), calcium (CaO), sulphur (SO3), boron (B), copper (Cu) Iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn), and cobalt(Co), while maintaining a reduced tendency of the formulation to polymerise and the stimulating effect of the enhancers of the water solubility of silicon compounds on the bioavailability of silicon compounds by plants though using (applying) the formulation into the roots and/or outside the roots.
According to the invention, the silicon formulation with plant growth stimulating properties, in the form of an aqueous solution or powdery water-soluble substance, containing water-soluble silicon compounds, stabilisers of the silicon compounds solution against undesired polymerisation, and pH control agents, is characterised by the fact that it contains silicon compounds in an amount of 0.5 to 60% by weight (calculated as S1O2), preferably 10 to 25 % by weight, dissolved in an aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, and further preferably contains at least one of macro- and/or micronutrient such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, wherein the pH of the formulation is 3 to 12, preferably 4 to 7.
Preferably, the source of water-soluble silicon compounds should be silicic acids, potassium silicates, sodium silicates, or mixtures thereof, wherein the pH used in the formulation of the silicon compounds is from 2 to 13.
It has been found that some of the above-mentioned substances stabilising the silicon compound solution and preventing the polymerisation increase the bioavailability of silicon for the plants. Therefore, it is preferred that the formulation contain mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof in an amount of 0.1 to 10% by weight.
It has also been found that introducing metals forming macro- and/or micronutrients (K, Mg, Fe, Cu, Mn, Mo, Zn, Co) in the form of complex compounds into the composition of the formulation allows to improve the bioavailability of silicon by the plant and additionally prevents polymerisation, improving the stability of the composition of the formulation.
Preferably, the formulation shall contain said macro- and/or micronutrients in the form of salts of the citric acid and/or ethylenediaminetetraacetic acid (Versene, EDTA).
The formulation according to the invention has a liquid, gel form and is fully soluble in water. The formulation can also be transformed into a fully water-soluble powder through processes of drying the liquid, preferably spray drying.
According to the invention, the method for preparing the silicon formulation with plant growth stimulating properties, wherein water-soluble compounds of silicon, stabilisers of silicon compound solution against undesired polymerisation, and pH control agents are combined in an aqueous medium, is characterised in that the soluble silicon compounds having a pH of 2 to 13, in the form of silicic acids, potassium silicate, sodium silicate or mixtures thereof in the amount of 0.5 to 60% by weight, preferably 0 to 25% by weight (calculated as S1O2), are dissolved in an aqueous medium containing stabilisers such as polyalcohols, polysaccharides, fulvic acids, amino acids or mixtures thereof and compounds of nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, and the final pH of the composition is
determined in the range of 3 to 12, preferably 4 to 7, ideally with citric acid, hydroxides and/or carbonates of alkali metals, especially sodium or potassium.
The formulation of the stock solution thus obtained has a high content of silicon, and additionally contains nutrients and additives, which in addition to the solution-stabilising properties have a positive influence on the bioavailability for plants.
Alternatively, the silicon formulation can be prepared in the form of powder to be dissolved in water. For this purpose, the said stock solution is dried, preferably in spray dryers, and packed in airtight containers.
Preferably, in the method according to the invention, mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof are used as substances stabilising the composition and preventing the polymerisation of the silicon compounds, in an amount of 0.1 to 10% by weight, as it increases the bioavailability of silicon in plants.
Preferably, in the method according to the invention, in the preparation of the formulation, metal complexes are used which constitute macro- and/or micronutrients, which allows to improve the bioavailability of silicon for the plant and additionally prevent polymerisation, improving the stability of the formulation composition. In particular, it is preferred to use said metal complexes in the form of citric and/or ethylenediaminetetraacetic acid salts for the implementation of the method.
The stock solution of the preparation, or the powder form of the formulation, have too high a concentration of active ingredients for the formulation to be used directly in cultivation. For the application of the formulation into the root or outside the root, it is necessary to dilute it with water to obtain a concentration of active ingredients which is acceptable for the plant.
According to the invention, the use of a silicon formulation with plant growth stimulating properties, containing water-soluble compounds of silicon, in the form
of an aqueous solution or powdery water-soluble substance, containing water- soluble compounds of silicon, the content of which expressed in the form of SiO 2 is of 0.5 to 60% by weight, which formulation preferably contains at least one of the macro and/or micronutrients such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, preferably complexed, and it is obtained by dissolving silicic acids and/or salts thereof having a pH of 2 to 13 in an acidic aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, is in agricultural and horticultural applications outside the root and/or into the root, after dilution with water, in the concentration range of 0.02 to 5% by mass.
It was found in experimental crops that good results are obtained by using so-diluted formulation in water that is applied to plants by spraying, fumigation, watering or irrigation systems.
The formulation according to the invention is characterised by biological activity which translates into a favourable effect on the metabolism of plants and the reduction of the development of diseases and the adverse impact of abiotic and other biotic stress factors.
This is documented by the data from experimental cultivation presented below in the Examples, which point to a positive effect of the present silicon formulation on plants.
The research was conducted in specialised research centres in Poland, among others, Centralny Osrodek Badania Odmian Roslin Uprawnych (Research Centre for Cultivar Testing) in Stupia Wielka,, Instytut Ogrodnictwa (Research Institute of Horticulture) in Skierniewice, Instytut Fizjologii Roslin Polskiej Akademii Nauk (Institute of Plant Physiology of the Polish Academy of Sciences in Krakow), whose aim was to evaluate the biological efficacy of the formulations according to the invention containing silicon. The results of the tests clearly demonstrate the
effects of the formulation as a stimulant limiting the stress caused by biotic and abiotic factors.
The invention is illustrated by the following examples which present the methods of preparation the formulation, the resulting formulation and use of the formulation in plant cultivation.
Example 1
400 litres of water were poured into a tank equipped with a stirrer and heating equipment, and after heating it to 35-40°C, 30.0 kg of mannitol (polyhydric sugar alcohol) were introduced. After its complete dissolution, 15 litres of a solution containing 4.0 kg of potassium hydroxide and 2.0 kg of citric acid were introduced. After about 30 minutes of stirring and the completion of the reaction between substances added, the resulting solution was added in a thin stream with vigorous stirring to a second tank, in which 555.0 litres of a silicic acid sol solution was present.
After about 50 minutes of stirring, a clear pure silicon formulation solution was obtained having a pH of 6.2, containing in 1 litre: 200.0 g of S1O2, 30.0 g of mannitol and 2.7 g of K2 O in the form of citrate.
After standing for 24 h, the solids were separated, and the formulation was packaged.
Example 2
1.0 kg of a thickening agent with the trade name KELZAN HP (xanthan gum obtained by means of the bacterial fermentation of carbohydrates) was very slowly introduced into a tank containing 350.0 litres of water at 35-40°C, and stirred until it dissolved completely. To avoid the formation of difficult to dissolve agglomerates, KELZAN HP was added dispersed and in small amounts. After complete dissolution, 1.8 kg of citric acid was added and then 30.0 kg of mannitol. 80 litres of
a solution containing 24.0 kg of chelated iron was added to a completely clear solution. The iron chelate was obtained in a separate tank where the solution of iron (II) and iron (III) in a solution of citric acid was subjected to complexing with the EDTA acid.
The resulting solution of the iron chelate was added in a small stream to 666.0 kg of silicic acid sol contained in the second tank. The solutions were combined, with vigorous stirring to prevent the formation of difficult-to-dissolve agglomerates. The clear solution obtained after filtration was directed for packaging. The final formulation in the form of gel contains in % by weight: 16.9% S1O2, 2.0% iron, 2.5% mannitol (polyalcohol).
Example 3
In a tank equipped with a stirrer, 0.2 kg of citric acid in 35.5 litres of water was dissolved, and after dissolution, 3.0 kg of ammonium molybdate was added. The mixture was stirred at the temperature of 35°C until a completely clear solution was obtained. 0.8 kg of sodium hydroxide and 3.4 kg of potassium hydroxide were then added. 69.8 kg of potassium silicate solution containing 20.0 kg S1O2, and 0.7 I of a 39.0% solution of the sodium salt of EDTA were added to the resulting solution. When a clear solution was obtained, 14.0 I of a solution containing 0.76 kg of chelated zinc, and 0.024 kg of cobalt was added. Zinc and cobalt chelates were obtained in a separate tank by chelating zinc sulphate and cobalt sulphate with the sodium salt of EDTA in the presence of citric acid. For this purpose, in a tank containing 0.0 I of water at 35°C equipped with a stirrer, 2.15 kg of zinc sulphate containing 35.3% zinc, and 0.103 kg of cobalt chloride containing 23.4% of cobalt were dissolved. After complete dissolution, 0.2 kg of citric acid and 3.5 kg of tetrasodium salt of EDTA were added and stirred to obtain a clear transparent solution.
A silicon formulation was obtained containing in 1 litre: 130 g of S1O2, 6.2 g of Mo, 7.6 g of Zn and 0.24 g of Co.
Example 4
184.0 g of iron-EDTA chelate in which its content was 13.1 % was added to tank with a stirrer containing 360 cm3 of water at room temperature, After 15 minutes, when all of the chelate had dissolved, 560 cm3 of an aqueous technical solution of silicic acid was added with a density of 1.2 g/cm3 and a pH = 3, wherein the silicon content, calculated on the S1O2 was of 360 g/l. 30 g of technical mannitol was added in portions to so-prepared mixture, and after the addition ended, the composition was mixed for 20 minutes at room temperature. The obtained formulation has a pH of 6.4 and is transparent and dark-red in colour, with the final volume of 1 ,000 cm3
After filtration, the formulation was directed for packaging .The formulation contains in 1 litre: 200.0 g of S1O2, 24.1 g of Fe and 30.0 g of mannitol.
Example 5
In a stainless steel tank equipped with a stirrer and the possibility of regulating the temperature, 20.0 kg of potassium hydroxide (K2O) and 6.5 kg of sodium carbonate (Na2C03) were dissolved in 390 I of water at 20-25°C. After the complete dissolution of the ingredients, 50.0 kg of methionine and 5.0 kg of citric acid were alternately added in small portions. The whole was stirred vigorously, and after obtaining a clear solution, .8 kg of zinc chelate (EDTA) containing 14.0% of zinc, and 6.0 kg of polyborate (Na2B80i3x2H20) containing 21.5% of boron was added. The resulting solution was added to 565.0 litres of potassium silicate at 35°C in a second tank. The solutions were combined slowly, in a small stream, to avoid the formation of large agglomerates, especially at the end of combing the solutions. The resulting formulation has a pH of 11.5 and contains in 1 litre: 150.0 g
of S1O2, 99.5 g of K2O, 1.3 g of boron, 0.25 g of zinc and 50 g of methionine. The product was filtered after standing and directed to packaging.
Effect of the application of silicon formulation on plant cultivation.
Example 6 (rape, winter wheat)
In order to eliminate the risks associated with weather conditions, in 2011 , experiments were started in four Experimental Stations for Cultivar belonging to COBORU (Research Centre for Cultivar Testing) located in the north, east and south of the Poland. Identical methodology of the conducted experiments was of importance.
For rape plants, a silicon dose of 0.5 l/ha in 300 litres of water applied on the following dates: first treatment in the autumn in the development stage of 4-6 true leaves (BBCH 14-16), second treatment in the spring after the start of vegetation (BBCH 26-29 ), third treatment in bud formation stage (BBCH 50-53), fourth treatment in the green pod stage (BBCH 71-75).The four-fold application of the formulation to rape plants led to an increase in yield of 5% to 47% compared to plants not treated with the formulation. At the same time, much smaller yield loss due to hail was observed in one of the locations.
For winter wheat, the dose of 0.5 l/ha in 300 litres of water was applied four times at the following moments: first treatment in the autumn in the development stage of 3-6 leaves (BBCH 13-16), second treatment in the spring in the tillering stage (BBCH 22-29), third treatment in the stem elongation stage (BBCH 30-54), fourth treatment immediately after flowering (BBCH 65-71). In the case of winter wheat (yield increase in the range of 13-43% was achieved), the smallest yield increase was of 13% and the highest of 43%. Also the mass of a thousand seeds increased between 6 and 16% in comparison to control plants not treated with the formulation, which also had the effect of increasing the quality parameters of the
grain. The results clearly demonstrate the efficacy of the application of silicon formulations in foliar treatments (spraying) as stimulators in agricultural crops.
Example 7 (strawberry)
Tests were conducted at the Research Institute of Horticulture in Skierniewice to determine the biological efficacy of the silicon formulation in comparison to fungicide for the occurrence of verticillium wilt in strawberry plants. The silicon formula was applied by watering the plants with a solution 0.4% by weight concentration, and applying 0.2 litres of solution under each plant. Two treatments were performed: the first one on April 19, 2012, in the early balloon stage (BBCH 58), and a second one on May 1 , 2012, at the beginning of flowering (BBCH 60). The soil application resulted in three times smaller infection of plants in comparison to the control plants not treated with the formulation and almost twice smaller in comparison with plants treated with fungicide.
Example 8 (cucumber, cabbage)
In the cultivation of cucumber (the Research Institute of Horticulture in Skierniewice), the silicon formulation in the concentration of 0.2% by weight was used in the form of sprays. Starting from 10 July 2012, five treatments were made at 7 day intervals. Infection with downy mildew (Pseudoperenospora cubensis) was evaluated twice: a first evaluation, conducted 3 days after the second treatment, showed 100% efficacy with the infection of control plants at 1.3%; the second evaluation, conducted six days after the four treatments, showed 81 % efficacy with the infection of control plants at 32.2%. An 8% increase in the marketable yield of cucumber was obtained.
In the he cultivation of cabbage, the silicon formulation in the concentration of 0.4% by weight was used in the form of sprays and four treatments were performed on the following dates : 09.08, 23.08, 06.09, 20.09. 2012 (frequency every 10-14
days). Infection with the following diseases was assessed: black spots (Alternaria spp), grey mould (Botrytis cinerea), and rot (Sclerotinia sclerotiorum). In reducing black spots, 65% efficacy was achieved, for grey mould, 58% efficacy, and there was a limited inhibitory effect on the sclerotinia rot, at 22%.
The quadruple treatments increased the marketable yield by 34%.
Example 9 (spring wheat)
In 2012, a researcher of the Institute of Plant Physiology of the Polish Academy of Sciences conducted a study of the efficacy of the silicon formulation in reducing stress on plants caused by drought. The study under greenhouse conditions concerned plants of spring wheat, which is sensitive to drought stress. The day before the cessation of watering the plants, a silicon formulation spray was applied once at a concentration of 0.4% by weight.
After inducing a soil drought, the effect on turgor pressure was evaluated. The study showed more than a double reduction of the loss of electrolyte to the application of a formulation containing silicon. This result translated directly into a 40% increase in the fresh weight of the plants.
These examples confirm the efficacy and legitimacy of using silicon formulations according to the invention for horticultural and agricultural plants. The applications described in the examples were performed though spraying or soil application (irrigation or fertigation).
Claims
1. A silicon formulation with plant growth stimulating properties, in the form of an aqueous solution or powdery water-soluble substance, containing water-soluble compounds of silicon, stabilisers of the silicon compound solution against undesired polymerisation, and pH control agents, characterised in that it contains silicon compounds in an amount of 0.5 to 60% by weight (calculated as S1O2), preferably 10 to 25% by weight, dissolved in an aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, and preferably additionally contains at least one of the macro and/or micronutrients such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, wherein the pH of the formulation is 3 to 12, preferably 4 to 7.
2. A formulation according to claim 1 , characterised in that silicic acid, potassium silicates, sodium silicates, or mixtures thereof are the source of water-soluble silicon compounds.
3. A formulation according to claim 2 characterised in that the pH of silicon compounds used in the formulation is from 2 to 13.
4. A formulation according to claim 1 , characterised in that it contains mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof in an amount of 0.1 to 10 % by weight.
5. A formulation according to claim 1 , characterised in that it contains metal complex compounds which constitute macro and/or micronutrients.
6. A formulation according to claim 5, characterised in that it contains metal complexes which constitute macro-and/or micronutrients in the form of the salts of citric and/or ethylenediaminetetraacetic acid.
7. A method of preparing the silicon formulation stimulating plant growth, wherein water-soluble compounds of silicon, stabilisers of silicon compound against undesired polymerisation, and pH control agents are combined in an aqueous medium, characterised in that the soluble silicon compounds having a pH of 2 to 13, in the form of silicic acids, potassium silicate, sodium silicate or mixtures thereof in an amount of 0.5 to 60% by weight, preferably 10 to 25% by weight (calculated as S1O2), is dissolved in an aqueous medium containing stabilising agents such as: polyalcohols, polysaccharides, fulvic acids, amino acids or mixtures thereof, and preferably the compounds of nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, and the final pH of the composition is determined in the range of 3 to 12, and preferably 4 to 7.
8. A method of preparing the silicon formulation according to claim 6, characterised in that mannitol, sorbitol, betaine, methionine, glycine or mixtures thereof are used, in an amount of 0.1 to 10 % by weight.
9. A method of preparing the silicon formulation according to claim 6, characterised in that the metal complex compounds are used which constitute macro and/or micronutrients.
10. A method of preparing the silicon formulation according to claim 6, characterised in that the metal complex compounds which are macro-and/or micronutrients are used in the form of the salts of citric and/or ethylenediaminetetraacetic acid.
11. A method of preparing the silicon formulation according to claim 6, characterised in that the pH of the formulation is adjusted with citric acid, hydroxides and/or carbonates of alkali metals, especially sodium or potassium,
12. A method of preparing the formulation according to claim 7 or 8 or 9 or 10 or 11 , characterised in that the liquid composition of the formulation is dried, preferably spray dried, then packed in tight containers.
13. Use of the silicon formulation with plant growth stimulating properties, in the form of an aqueous solution or powdery form to be dissolved in water, containing water-soluble silicon compounds, the content of which expressed in the form of S1O2 is of 0.5 to 60% by weight, wherein the formulation preferably comprises at least one of the macro and/or micronutrients such as nitrogen, phosphorus, potassium, magnesium, calcium, sulphur, boron, copper, iron, manganese, molybdenum, zinc, cobalt, preferably complexed, and it is obtained by dissolving silicic acids and/or their salts having a pH of 2 to 13 in an aqueous medium in the presence of polysaccharides, polyalcohols, fulvic acids, amino acids or mixtures thereof, in agricultural and horticultural cultivation for application outside the root and/or into the root, after being diluted with water in a concentration range from 0.02 to 5% by weight.
14. Use of the formulation according to claim 13, characterised in that the formulation diluted in water is applied by spraying, fumigation, watering or irrigation.
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WO2017198957A1 (en) * | 2016-05-19 | 2017-11-23 | Agro Innovation International | Use of silicon as a stimulant for iron absorption in a plant |
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CN108046883A (en) * | 2017-11-02 | 2018-05-18 | 兰溪市奥而特农业科技有限公司 | For the preparation method of the sustained release foliar fertilizer of watch leaf flower |
CN107652066A (en) * | 2017-11-03 | 2018-02-02 | 金正大生态工程集团股份有限公司 | A kind of sugar alcohol siliceous fertilizer and preparation method thereof |
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AU2020260932B2 (en) * | 2019-04-24 | 2023-02-09 | Korea New Technology Co.,Ltd. | Silicon ion complex organized with carboxylic acid, preparation method for silicon ion complex, and product using the same |
GB2588213A (en) * | 2019-10-16 | 2021-04-21 | Maxstim Ltd | Improvements in, and relating to, biostimulants |
GB2588213B (en) * | 2019-10-16 | 2023-08-09 | Maxstim Ltd | Improvements in, and relating to, biostimulants |
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