DESC:TECHNICAL FIELD
The present disclosure relates to agricultural nano biotechnology. More particularly, the present disclosure relates to nano-nutrients for agriculture/ horticulture developed by the ionic liquid nanotechnology approach.
BACKGROUND
Micronutrients hold a critical role in both human health and global agricultural systems. Widespread micronutrient deficiencies affect over a billion people globally. Key micronutrients such as zinc (Zn), iron (Fe), manganese (Mn), copper (Cu), boron (B), and chlorine (Cl) are essential components that influence crop yield and are linked to nutritional aspects of staple foods. Astonishingly, only approximately 50% of cultivated soils worldwide exhibit adequate bioavailability of these micronutrients.
Addressing environmental concerns has become a priority in developed nations, with excessive fertilizer and pesticide usage in rural areas leading to extensive pollution. Toxic gas emissions and chemical leaching into groundwater result from these practices. While the growing demand for food and agricultural products due to population growth is evident, it also contributes to global warming and erratic climate patterns. The detrimental effects of nutrient leaching, especially of nitrogen and phosphorous, manifest as "dead zones". This influx of nutrients through fertilizer runoff, soil erosion, and waste streams fosters harmful algal blooms, disrupting ecosystems and oxygen levels, impacting the food chain.
Addressing this issue requires curbing the excessive use of chemical fertilizers through better management practices. Plant nutrients fall into two categories: macronutrients, required in larger quantities, and micronutrients, needed in smaller doses. Essential macronutrients like carbon (C), hydrogen (H), oxygen (O), phosphorous (P), potassium (K), nitrogen (N), sulphur (S), calcium (Ca), magnesium (Mg), and silicon (Si) play a central role. Meanwhile, nitrogen (N), phosphorus (P), and potassium (K) are frequently employed macronutrients, while micronutrients like iron (Fe), molybdenum (Mo), boron (B), and others are equally indispensable.
Conventional farming practices frequently involve the application of water-soluble inorganic fertilizers such as nitrogen, phosphorus, and potassium beyond plants' uptake capacity. This often leads to leaching and contamination of water bodies, posing ecological risks. Factors such as soil composition, pH levels, and uneven fertilizer application contribute to micronutrient deficiencies in Asian nations, leading to decreased crop yield, suboptimal quality, and other stress-induced impacts on plants.
Therefore, there is a need for an invention in the state of art to utilize nanotechnology to increase crop productivity and the effectiveness of both natural and artificial sources of nutrients.
SUMMARY
In one aspect of the present disclosure, a method for preparing a nano-based crop nutrient formulation is provided. The method (100) includes the steps of dissolving (101) 3- 75 g of nitrogen compound in 22-100 g of water to obtain nitrogen compound solution, protonating (103) by adding 1-50 g of organic acid to nitrogen compound solution to obtain activated nitrogenous compound by constant stirring for 30-350 minutes at a temperature of 50-200oC, complexing (105) by adding 2-80 g of nutrient rich compounds to the activated nitrogenous compound to obtain active electron-rich complex, adding (107) 1.5- 10 g of alkali to adjust the pH and add 0.05 to 10.0 g of reducing and oxidizing agents to the active electron-rich complex to obtain multifunctional ionic liquid, adding (109) 0.1 to 80 g micronutrient rich inorganic compounds to the multifunctional ionic liquid by constant stirring for 30-350 minutes at a temperature of 50-200oC to obtain micronutrient nanoparticles and adding (111) 0.25 to 25 g of surfactants, 0.1 to 15 g of dispersing agents, 0.1 to 12 g of wetting agents, 0.1 g to 16 g of stabilizing agents and 0.01 to 2.0 g of defoamers to the micronutrient nanoparticles for 30-70 minutes at a temperature of 50-200oC to obtain the nano-based crop nutrient formulation.
In some aspects of the present disclosure, the nitrogen compound is selected from the group comprising: ammonium salts, liquid ammonia, amides, diamides, thioamides, urea, thiourea, cyanamides, dicyandiamide, amines, imines, imides, nitriles, nitrogen heterocycles, triazine (triazine monoamine, triazine diamine, triazine triazine), triazole (triazole monoamine, triazole diamine, triazole triamine) and tetrazine (tetrazine monoamine, tetrazine diamine, tetrazine triamine) based compounds.
In some aspects of the present disclosure, the organic acids are selected from the group comprising formic acid, acetic acid, propionic acid, butyric acid, citric acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, nitric acid, phosphoric acid, phosphonic acid, glutamic acid, glycolic acid, boric acid, humic acid, folic acid, sulfuric acid, hydrochloric acid, silicic acid, fulvic acid and amino acids or combinations thereof.
In some aspects of the present disclosure, the nutrient rich compounds is selected from the group comprising inorganic salts of phosphates, superphosphates, single super phosphate, phosphonic acids (PBTC), (2- phosphonobutane-1,2,4-tricarboxylic acid), 1-hydroxyethylidene-1,1- diphosphonic acid (HEDP), amino-tris-methylenephosphonic acid (ATMP), 2-hydroxyethyl-amino-bis(methylenephosphonic acid (HEAMBP), ethylenediamine-tetrakis(methylene-phosphonic acid) (EDTMP), hydroxy-phosphono acetic acid (HPAA) and hexamethylene-diamine-tetrakis(methylene-phosphonic acid) (DETPMP) and phosphonates of sodium and potassium salts , potassium phosphides, potassium chloride, potassium hydroxide, potassium carbonate, potassium phosphate, potassium phosphites, potassium borates, potassium humate, potassium silicate, potassium oxide, potassium glycinate, potassium citrate, potassium gluconate, potassium oxalate, potassium sorbate, potassium stearate, potassium acrylate, potassium sulphide, potassium sulphate, and potassium nitrate or a combination of thereof.
In some aspects of the present disclosure, the micronutrients is selected from the group comprising boric acid, disodium octa borate tetrahydrate, dipotassium octa borate tetrahydrate, calcium borate, zinc borate, boron oxide, ferrous borate, copper borate, manganese borate, molybdenum borate, potassium borosilicate, nickel borate, boron humates, boron cluster, all metal borates, anhydrous borax, colemanite, boron ethanolamine, boronated single superphosphate, sodium borosilicate, potassium boron oxide, magnesium borate, sodium tetra borate, potassium borate, or a combination thereof, zinc oxide, zinc sulphate (anhydrous, mono and hepta hydrates), zinc phosphate, zinc borate, zinc ammonium phosphate, zinc dust, zinc phosphonates, zinc fluoride, zinc bromide, zinc molybdate, zinc chromate, zinc ricinoleate, zinc ascorbate, zinc orotate, zinc methionate, zinc picolinate, zinc glycinate, zinc lozenges, zinc biopolymer complexes (including zinc polymaltose, zinc starch), zinc amino acid, zinc carboxylate, zinc benzoate, zinc tartrate, zinc carbonate, zinc hydroxide, zinc sulphide, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, zinc citrate, zinc polyphosphate, zinc gluconate, zinc cyanide and zinc silicates or combination thereof, Iron oxide, Iron sulphate, Iron sulphide, Iron chloride, Iron carbonate, Iron acetate, Iron oxalate, Iron gluconate, Iron silicates, Iron phosphate, Iron hydroxide, ferrous borate, ferrous ammonium phosphate, iron phosphonates, iron fluoride, iron bromide, iron molybdate, iron chromate, iron ricinoleate, iron ascorbate, iron orotate, iron methionate, iron picolinate, iron glycinate, iron lozenges, iron biopolymer complexes (including iron polymaltose, iron starch), iron amino acid, iron carboxylate, iron benzoate, iron ascorbate, iron oxalate, iron tartrate, iron citrate, iron polyphosphate, iron cyanide Iron nitrate and Iron citrate or combination thereof, manganese oxide, manganese sulphate, manganese chloride, manganese nitrate, manganese acetate, manganese carbonate, manganese oxalate, manganese gluconate, manganese hydroxide, manganese phosphate, manganese phosphide, manganese borate, manganese ammonium phosphate, manganese phosphonates, manganese fluoride, manganese bromide, manganese molybdate, manganese chromate, manganese ricinoleate, manganese ascorbate, manganese orotate, manganese methionate, manganese picolinate, manganese glycinate, manganese lozenges, manganese biopolymer complexes (including manganese polymaltose, manganese starch), manganese amino acid, manganese carboxylate, manganese benzoate, manganese tartrate, manganese ascorbate, manganese carbonate, manganese hydroxide, manganese sulphide, manganese chloride, manganese nitrate, manganese acetate, manganese oxalate, manganese citrate, manganese polyphosphate, manganese gluconate, manganese cyanide and manganese silicates, manganese sulphide and manganese citrate or combination thereof, copper may be copper oxide, copper sulphate, copper chloride, copper nitrate, copper acetate, copper carbonate, copper oxalate, copper gluconate, copper hydroxide, copper phosphate, copper phosphide, copper borate, copper ammonium phosphate, copper ammonium sulphate, copper phosphonates, copper fluoride, copper bromide, copper molybdate, copper chromate, copper ricinoleate, copper ascorbate, copper orotate, copper methionate, copper picolinate, copper glycinate, copper ascorbate, copper lozenges, copper biopolymer complexes (including copper polymaltose, copper starch), copper amino acid, copper carboxylate, copper benzoate, copper tartrate, copper carbonate, copper hydroxide, copper nitrite, copper polyphosphate, copper cyanide, copper silicates, copper sulfide and Copper citrate or combination thereof, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, iron molybdate, copper molybdate, zinc molybdate, nickel molybdate, cobalt molybdate, molybdenum acetate, molybdenum borate, ammonium phosphor molybdate, molybdenum phosphonates, molybdenum fluoride, molybdenum bromide, molybdenum chromate, molybdenum ricinoleate, molybdenum ascorbate, molybdenum orotate, molybdenum methionate, molybdenum picolinate, molybdenum glycinate, molybdenum lozenges, molybdenum biopolymer complexes (including molybdenum polymaltose, molybdenum starch complex), molybdenum amino acid, molybdenum carboxylate, molybdenum benzoate, molybdenum tartrate, molybdenum carbonate, molybdenum hydroxide, molybdenum sulfide, molybdenum chloride, molybdenum nitrate, molybdenum oxalate, molybdenum citrate, molybdenum polyphosphate, molybdenum gluconate, molybdenum cyanide and molybdenum silicates, molybdenum trioxide and manganese molybdate or combination thereof, nickel oxide, nickel sulphate, nickel chloride, nickel formate, nickel nitrate, nickel acetate, nickel carbonate, nickel oxalate, nickel ascorbate, nickel gluconate, nickel hydroxide, nickel phosphate, nickel phosphide, nickel borate, nickel ammonium phosphate, nickel ammonium sulphate, nickel phosphonates, nickel fluoride, nickel bromide, nickel molybdate, nickel chromate, nickel ricinoleate, nickel ascorbate, nickel orotate, nickel methionate, nickel picolinate, nickel glycinate, nickel lozenges, nickel biopolymer complexes (including nickel polymaltose, nickel starch), nickel amino acid, nickel carboxylate, nickel benzoate, nickel tartrate, nickel carbonate, nickel hydroxide, nickel nitrite, nickel polyphosphate, nickel cyanide, nickel silicates, nickel sulfide and nickel citrate or combination thereof, cobalt oxide, cobalt sulphate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxalate, cobalt gluconate, cobalt hydroxide, cobalt phosphate, cobalt phosphide, cobalt borate, cobalt ammonium phosphate, cobalt ammonium sulphate, cobalt phosphonates, cobalt fluoride, cobalt bromide, cobalt molybdate, cobalt chromate, cobalt ricinoleate, cobalt ascorbate, cobalt orotate, cobalt methionate, cobalt picolinate, cobalt glycinate, cobalt lozenges, cobalt biopolymer complexes (including cobalt polymaltose, cobalt starch), cobalt amino acid, cobalt carboxylate, cobalt benzoate, cobalt tartrate, cobalt carbonate, cobalt hydroxide, cobalt nitrite, cobalt polyphosphate, cobalt cyanide, cobalt silicates, cobalt sulfide and cobalt citrate or combination thereof, selenium oxide, selenium sulphate, selenium chloride, selenium nitrate, selenium acetate, selenium carbonate, selenium oxalate, selenium gluconate, selenium hydroxide, selenium phosphate, selenium phosphide, selenium borate, selenium ammonium phosphate, selenium ammonium sulphate, selenium phosphonates, selenium fluoride, selenium bromide, selenium molybdate, selenium chromate, selenium ricinoleate, selenium ascorbate, selenium orotate, selenium methionate, selenium picolinate, selenium glycinate, selenium lozenges, selenium biopolymer complexes (including selenium polymaltose, selenium starch), selenium amino acid, selenium carboxylate, selenium benzoate, selenium tartrate, selenium carbonate, selenium hydroxide, selenium nitrite, selenium polyphosphate, selenium cyanide, selenium silicates, selenium sulfide and selenium citrate or combination thereof, titanium oxide, titanium sulphate, titanium chloride, titanium nitrate, titanium acetate, titanium carbonate, titanium oxalate, titanium gluconate, titanium hydroxide, titanium phosphate, titanium phosphide, titanium borate, titanium ammonium phosphate, titanium ammonium sulphate, titanium phosphonates, titanium fluoride, titanium bromide, titanium molybdate, titanium chromate, titanium ricinoleate, titanium ascorbate, titanium orotate, titanium methionate, titanium picolinate, titanium glycinate, titanium lozenges, titanium biopolymer complexes (including titanium polymaltose, titanium starch), titanium amino acid, titanium carboxylate, titanium benzoate, titanium tartrate, titanium carbonate, titanium hydroxide, titanium nitrite, titanium polyphosphate, titanium cyanide, titanium silicates, titanium sulfide and titanium citrate or combination thereof, silicon dioxide, nickel silicate, copper silicate, zinc silicate, sodium silicate, potassium silicate, zeolite, bentonite, aluminium silicates, ammonium silicates, molybdate silicates, borosilicates, cobalt silicates, manganese silicate, calcium silicate, magnesium silicate, silicate biopolymer complexes (including silicate polymaltose, silicate starch), silicate amino acid, ortho silicic acid, diatomite silicon, silicon hydroxide sodium pyro silicate or combination thereof.
In some aspects of the present disclosure, the stabilizer may be selected from the group comprising ethylene glycol, propylene glycol, polyethene glycol, polyvinyl alcohol, poly (Vinylpyrrolidone), carboxymethyl cellulose, long chain thiol, sodium dodecyl sulphate, carboxylic compounds, the long and branched structure of amines, cellulose and citrate or a combination thereof.
In some aspects of the present disclosure, the method (100) may further include the adding (110) drop by drop 2-8 ml of reducing agents before the step 109 wherein the reducing agents may be selected from the group comprising sodium borohydride, lithium borohydride, aluminium borohydride, lithium alluminium hydride, sodium citrate, glycol ethylene, hydroquinone, ethanol, formaldehyde, sugar pyrolysis radicals, hydroxyl radicals, N, N-dimethylformamide and hydrazine hydrate, phytochemical extractions from bio-active plants, or a combination thereof.
In some aspects of the present disclosure, the method (100) further comprises adding (112) of 4-30 g of nanofillers to obtain granules of nano-based crop nutrient formulation wherein the nanofillers may be selected from the group consisting of montmorillonite, nano-silica, nano-zeolite, graphene, graphene oxide, boron oxide, boron nitride, nano clay, nano cellulose, nano starch and combinations thereof.
In some aspects of the present disclosure, the surfactant may be selected from the group consisting of polymeric surfactants, acrylic based EO/PO, alkyl ethoxylate, non-ionic surfactants, phosphorus ester-based surfactants, epoxide surfactants, and anionic surfactants.
In another aspect of the present disclosure, a nano-based crop nutrient formulation is provided. The crop nutrient formulation includes macronutrients in the range of 3 to 75 % (w/w), micronutrients in the range of 1 to 80 % (w/w), and micronutrient trace elements in the range of 0.5 to 50 % (w/w).
In some aspects of the present disclosure, the macronutrient is selected from the group comprising nitrogen (N), phosphorous (P), potassium (K) and combinations thereof.
In some aspects of the present disclosure, the micronutrient nanoparticles may be selected from the group comprising: zinc in a concentration of 0.1 to 75 %, iron in a concentration of 0.1 to 75 % , manganese in a concentration of 0.1 to 75 %, copper in a concentration of 0.1 to 75 %, molybdenum in a concentration of 0.1 to 50 %, boron in a concentration of 0.1 to 75 % and chlorine in a concentration of 0.1 to 75 % and combinations thereof.
In some aspects of the present disclosure, the trace elements nutrients are selected from the group comprising selenium in a concentration of 0.1 to 50 %, titanium in a concentration of 0.1 to 50 %, nickel in the concentration of 0.1 to 50 %, cobalt in the concentration of 0.1 to 50 % and silicon in the concentration of 0.1 to 50 % and combinations thereof.
In some aspects of the present disclosure, the size of the nanoparticles ranges from 0.2 to 99 nanometers and 100 to 5000 nanometers.

BRIEF DESCRIPTION OF DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of this specification, show certain aspects of the subject matter disclosed herein and, together with the description, help explain some of the principles associated with the disclosed implementations. In the drawing,
Figure 1 illustrates the method for preparing a nano-based crop nutrient formulation, in accordance with an aspect of the present disclosure;
Figure 2 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 1, in accordance with an aspect of the present disclosure;
Figure 3 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 2, in accordance with an aspect of the present disclosure;
Figure 4 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 3, in accordance with an aspect of the present disclosure;
Figure 5 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 4, in accordance with an aspect of the present disclosure;
Figure 6 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 5, in accordance with an aspect of the present disclosure;
Figure 7 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 6, in accordance with an aspect of the present disclosure;
Figure 8 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 7, in accordance with an aspect of the present disclosure;
Figure 9 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 8, in accordance with an aspect of the present disclosure;
Figure 10 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 9, in accordance with an aspect of the present disclosure;
Figure 11 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 10, in accordance with an aspect of the present disclosure;
Figure 12 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 11, in accordance with an aspect of the present disclosure;
Figure 13 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 12, in accordance with an aspect of the present disclosure;
Figure 14 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 13, in accordance with an aspect of the present disclosure;
Figure 15 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 14, in accordance with an aspect of the present disclosure; and
Figure 16 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 15, in accordance with an aspect of the present disclosure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Various embodiments of the disclosure are discussed in detail below. While specific implementations are discussed, it should be understood that this is done for illustration purposes only. A person skilled in the relevant art will recognize that other components and configurations may be used without parting from the spirit and scope of the disclosure. Thus, the following description and drawings are illustrative and are not to be construed as limiting. Numerous specific details are described to provide a thorough understanding of the disclosure. However, in certain instances, known details are not described in order to avoid obscuring the description.
References to one or an embodiment in the present disclosure can be references to the same embodiment or any embodiment; and such references mean at least one of the embodiments.
Reference to "one embodiment", "an embodiment", “one aspect”, “some aspects”, “an aspect” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Moreover, various features are described which may be exhibited by some embodiments and not by others.
The terms used in this specification generally have their ordinary meanings in the art, within the context of the disclosure, and in the specific context where each term is used. Alternative language and synonyms may be used for any one or more of the terms discussed herein, and no special significance should be placed upon whether or not a term is elaborated or discussed herein. In some cases, synonyms for certain terms are provided.
A recital of one or more synonyms does not exclude the use of other synonyms.
The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only and is not intended to further limit the scope and meaning of the disclosure or of any example term. Likewise, the disclosure is not limited to various embodiments given in this specification. Without intent to limit the scope of the disclosure, examples of instruments, apparatus, methods and their related results according to the embodiments of the present disclosure are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the disclosure. Unless otherwise defined, technical and scientific terms used herein have the meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In the case of conflict, the present document, including definitions will control.
Additional features and advantages of the disclosure will be set forth in the description which follows, and in part will be obvious from the description, or can be learned by practice of the herein disclosed principles. The features and advantages of the disclosure can be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. These and other features of the disclosure will become more fully apparent from the following description and appended claims or can be learned by the practice of the principles set forth herein.
Traditional and cutting-edge fertiliser methods and products have not been up to the task of coordinating the micronutrient distribution from fertiliser as per the crop requirements during the growing season, which results in reduced micronutrients used efficiency (MUE).
Therefore, there is a need for an invention in the state of art to utilize technology to increase crop productivity and the effectiveness of both natural and artificial sources of nutrients.
The present disclosure provides a nano-based crop nutrient formulation to boost agriculture/horticulture/plantation that could be applied can be applied as a foliar spray, root dipping, seed treatment, basal application and aeroponics in precision farming, hydroponics, dairy farming, commercial farming, plantation farming, commercial grain farming, commercial mixed farming, primitive subsistence farming, intensive subsistence, glass house farming, using with irrigation water, and as a plant nutrient in tissue culture or any in vitro culture media for micropropagation and plant regeneration.
Figure 1 illustrates the method of preparing a nano-based crop nutrient formulation, in accordance with an aspect of the present disclosure.
The method may include forming the metal nanoparticles through the following steps i) Protonation, ii) complexation, iii) Ionic liquid formation, iv), Reduction or Oxidationv) Nucleation, vi) Formulation, and vii) Stabilization.
Figure 1 herein illustrates a method for preparing a nano-based crop nutrient formulation. The method (100) may include the step of dissolving (101) 3- 80 g of nitrogen compound in 22-100 g of water to obtain nitrogen compound solution.
The method (100) may further include the step of adding (103) 1-50 g of organic acid to nitrogen compound solution to obtain activated nitrogenous compound by constant stirring for 30-350 minutes at a temperature of 50-200oC. The nitrogen compound is selected from the group that includes ammonium salts, amides, thioamides, diamides, urea, thiourea, cyanamides, dicyandiamide, nitrogen heterocycles, liquid ammonia, amides, imines, imides, triazine, triazole and tetrazine based compounds or combination thereof. The organic acids are selected from the group that includes formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, oxalic acid, tartaric acid, glutamic acid, nitric acid, phosphoric acid, phosphonic acid, citric acid, succinic acid, boric acid, humic acid, folic acid, sulfuric acid, hydrochloric acid, silicic acid, fulvic acid and amino acids or combinations thereof.
The nitrogen compounds including ammonium salts, liquid ammonia, nitrites, nitrates, amines, imines, imides, amides, diamides, thioamides, cyanamides, dicyandiamides or nitrogen heterocycles including triazines, diamine triazines, triamine triazine, diamine tetrazine and aniline react with organic acids such as citric, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, oxalic acid, ascorbic acid, glycolic acid, succinic, boric, humic, folic, sulfuric, hydrochloric, silicic, fulvic, humic, nitric, phosphoric, phosphonic, boric, amino acids or combination thereof for protonation or to activate the nitrogen functional groups.
The method (100) may further include the step of adding (105) 2-80g of nutrient rich compounds to the activated nitrogenous compound to obtain active electron-rich complex.
The nutrient rich compounds is selected from the group that includes inorganic salts of phosphates, rock phosphates, superphosphates, single super phosphate, phosphonic acids (PBTC), (2- phosphonobutane-1,2,4-tricarboxylic acid), 1-hydroxyethylidene-1,1- diphosphonic acid (HEDP), amino-tris-methylenephosphonic acid (ATMP), 2-hydroxyethyl-amino-bis(methylenephosphonic acid (HEAMBP), ethylenediamine-tetrakis(methylene-phosphonic acid) (EDTMP), hydroxy-phosphono acetic acid (HPAA) and hexamethylene-diamine-tetrakis(methylene-phosphonic acid) (DETPMP) and phosphonates of sodium and potassium salts , potassium phosphides, potassium chloride, potassium hydroxide, potassium carbonate, potassium phosphate, potassium phosphites, potassium borates, potassium humate, seaweed extract, potassium silicate, potassium oxide, potassium glycinate, potassium citrate, potassium gluconate, potassium oxalate, potassium sorbate, potassium ascorbate, potassium stearate, potassium acrylate, potassium sulphide, potassium sulphate, and potassium nitrate or a combination of thereof.
The method (100) may further include the step of adding (107) 1.5- 20 g of alkali to the active electron-rich complex to obtain multifunctional ionic liquid. A mild concentrated alkaline solution may be used to neutralise excess acids. The nutrient rich compounds involve in anion exchange reaction by reacting with phosphonates, chlorides, nitrates, sulphates, sulphonates, phosphates, phosphonates, succinate, oxalate, ascorbate, acetate, formate, propionate, benzoate, gluconate, borates and silicates. The complexed multifunctional ionic liquid thus formed may be active, electron-rich and bulkier.
The method (100) may further include the step of adding (109) 0.1 to 80 g micronutrient rich inorganic compounds to the multifunctional ionic liquid by constant stirring for 30-350 minutes at a temperature of 30-200oC to obtain micronutrient nanoparticles. The inorganic compounds of micronutrients such as Zn2+, Fe2+, Mn2+, Cu2+, Mo2+ Se+2-+6, Ti+2, Si+4-+6, Ni+2 and Co+2 nucleate with the multifunctional ionic liquid to form micronutrient nanoparticles. The micronutrients is selected from the group that includes boric acid, disodium octa borate tetrahydrate, dipotassium octa borate tetrahydrate, calcium borate, sodium borosilicate, potassium boron oxide, magnesium borate, boron humate, clusters of boron, zinc borate, calcium borate, magnesium borate, manganese borate, iron borate, copper borate, sodium tetra borate, potassium borate, zinc oxide, zinc sulphate, zinc phosphate, zinc borate, zinc carbonate, zinc hydroxide, zinc sulphide, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, zinc citrate, zinc polyphosphate, zinc gluconate, zinc cyanide, zinc silicates, iron oxide, iron sulphate, iron sulphide, iron chloride, iron carbonate, iron acetate, iron oxalate, iron gluconate, iron silicates, iron phosphate, iron hydroxide, iron nitrate, iron citrate, bio-polymer complexes of iron. Manganese oxide, manganese sulphate, manganese chloride, manganese nitrate, manganese acetate, manganese carbonate, manganese oxalate, manganese gluconate, manganese hydroxide, manganese phosphate, manganese phosphide, manganese sulphide, manganese citrate, manganese bio-polymer complexes, copper oxide, copper sulphate, copper chloride, copper nitrate, copper acetate, copper carbonate, copper carbonate, copper oxalate, copper gluconate, copper oxalate, copper ascorbate, chelated copper, copper hydroxide, copper phosphate, copper phosphide, copper sulfide, copper citrate, bio-polymer complexes of copper, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, iron molybdate, copper molybdate, zinc molybdate, molybdenum acetate, molybdenum trioxide and manganese molybdate or combination thereof.
The method (100) may further include the step of adding (111) 0.25 to 25 g of surfactants, 0.1-12 g of dispersing agents, 0.1-15 g of wetting agents, 0.1 g to 16 g of stabilizing agents and 0.01-2.0 g of defoamers to the micronutrient nanoparticles for 0.5-5.0 hours at a temperature of 50-200oC to obtain the nano-based crop nutrient formulation.
The stabilizer may be selected from the group that includes ethylene glycol, propylene glycol, polyethene glycol, polyvinyl alcohol, poly (Vinylpyrrolidone), carboxymethyl cellulose, long chain thiol, sodium dodecyl sulphate, carboxylic compounds, the long and branched structure of amines, cellulose and citrate or a combination thereof.
The method (100) may further include adding (110) drop by drop 2-8 ml of reducing agents before the step 109 reducing agents may be selected from the group that includes sodium borohydride, aluminum borohydride, lithium borohydride, lithium aluminum hydride, sodium citrate, glycol ethylene, hydroquinone, ethanol, formaldehyde, sugar pyrolysis radicals, hydroxyl radicals, N, N-dimethylformamide and hydrazine hydrate or a combination thereof. And the concentrated solutions of bio-active plant extractions are also used as a reducing agent for this type of nano formulation products.
The method (100) may further include adding (112) of 4-50 g of nanofillers to obtain granules of nano-based crop nutrient formulation wherein the nanofillers are selected from the group consisting of montmorillonite, graphene, boron nitride, nano clays, nano-silica, nano-zeolite, graphene oxide, and combinations thereof.
The surfactant is selected from the group consisting of polymeric surfactants, acrylic EO/PO, non-ionic surfactants, phosphorus ester-based surfactants, epoxide surfactants, and anionic surfactants.
The present disclosure provides a nano-based crop nutrient formulation that includes macronutrients in the range of 3 to 80 % (w/w); and micronutrient in the range of 2.0 to 75 % (w/w).
The macronutrient is selected from the group comprising nitrogen (N), phosphorous (P), potassium (K) and combinations thereof.
The micronutrient nanoparticles are selected from the group comprising: zinc in the range of 2 to 75 %, iron in the range of 2 to 75 %, manganese in the range of 2 to 75 %, copper in the range of 2 to 75 %, molybdenum in the range of 2 to 50 %, boron in the range of 2 to 75 %, silicon in the range of 2 to 50 %, selenium in the range of 2 to 50 %, titanium in the range of 2 to 50 %, nickel in the range of 2 to 50 %, cobalt in the range of 2 to 50% and chlorine in the range of 2 to 50% or a combination thereof.
In some embodiments, the source of boron micronutrients for plants includes boric acid, disodium octa borate tetrahydrate, dipotassium octa borate tetrahydrate, calcium borate, zinc borate, boron oxide, ferrous borate, copper borate, manganese borate, molybdenum borate, potassium borosilicate, nickel borate, boron humates, boron cluster, all metal borates, anhydrous borax, colemanite, boron ethanolamine, boronated single superphosphate, sodium borosilicate, potassium boron oxide, magnesium borate, sodium tetra borate, potassium borate, or a combination thereof might be used.
In some embodiments, the source of plant micronutrient zinc, may be obtained from the following chemicals which are namely zinc oxide, zinc sulphate (anhydrous, mono and hepta hydrates), zinc phosphate, zinc borate, zinc ammonium phosphate, zinc dust, zinc phosphonates, zinc fluoride, zinc bromide, zinc molybdate, zinc chromate, zinc ricinoleate, zinc ascorbate, zinc orotate, zinc methionate, zinc picolinate, zinc glycinate, zinc lozenges, zinc biopolymer complexes (including zinc polymaltose, zinc starch), zinc amino acid, zinc carboxylate, zinc benzoate, zinc tartrate, zinc carbonate, zinc hydroxide, zinc sulphide, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, zinc citrate, zinc polyphosphate, zinc gluconate, zinc cyanide and zinc silicates or combination thereof.
In some embodiments, the plant micronutrient source for iron may be iron oxide, iron sulphate, iron sulphide, iron chloride, iron carbonate, iron acetate, iron oxalate, iron gluconate, iron silicates, iron phosphate, iron hydroxide, ferrous borate, ferrous ammonium phosphate, iron phosphonates, iron fluoride, iron bromide, iron molybdate, iron chromate, iron ricinoleate, iron ascorbate, iron orotate, iron methionate, iron picolinate, iron glycinate, iron lozenges, iron biopolymer complexes (including iron polymaltose, iron starch), iron amino acid, iron carboxylate, iron benzoate, iron ascorbate, iron oxalate, iron tartrate, iron citrate, iron polyphosphate, iron cyanide Iron nitrate and Iron citrate or combination thereof.
In some embodiments, the plant micronutrient source for manganese may be manganese oxide, manganese sulphate, manganese chloride, manganese nitrate, manganese acetate, manganese carbonate, manganese oxalate, manganese gluconate, manganese hydroxide, manganese phosphate, manganese phosphide, manganese borate, manganese ammonium phosphate, manganese phosphonates, manganese fluoride, manganese bromide, manganese molybdate, manganese chromate, manganese ricinoleate, manganese ascorbate, manganese orotate, manganese methionate, manganese picolinate, manganese glycinate, manganese lozenges, manganese biopolymer complexes (including manganese polymaltose, manganese starch), manganese amino acid, manganese carboxylate, manganese benzoate, manganese tartrate, manganese ascorbate, manganese carbonate, manganese hydroxide, manganese sulphide, manganese chloride, manganese nitrate, manganese acetate, manganese oxalate, manganese citrate, manganese polyphosphate, manganese gluconate, manganese cyanide and manganese silicates, manganese sulphide and manganese citrate or combination thereof.
In some embodiments, the plant micronutrient source for copper may be copper oxide, copper sulphate, copper chloride, copper nitrate, copper acetate, copper carbonate, copper oxalate, copper gluconate, copper hydroxide, copper phosphate, copper phosphide, copper borate, copper ammonium phosphate, copper ammonium sulphate, copper phosphonates, copper fluoride, copper bromide, copper molybdate, copper chromate, copper ricinoleate, copper ascorbate, copper orotate, copper methionate, copper picolinate, copper glycinate, copper ascorbate, copper lozenges, copper biopolymer complexes (including copper polymaltose, copper starch), copper amino acid, copper carboxylate, copper benzoate, copper tartrate, copper carbonate, copper hydroxide, copper nitrite, copper polyphosphate, copper cyanide, copper silicates, copper sulfide and Copper citrate or combination thereof.
In some embodiments, the plant micronutrient source for molybdenum may be ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, iron molybdate, copper molybdate, zinc molybdate, nickle molybdate, cobalt molybdate, molybdenum acetate, molybdenum borate, ammonium phosphor molybdate, molybdenum phosphonates, molybdenum fluoride, molybdenum bromide, molybdenum chromate, molybdenum ricinoleate, molybdenum ascorbate, molybdenum orotate, molybdenum methionate, molybdenum picolinate, molybdenum glycinate, molybdenum lozenges, molybdenum biopolymer complexes (including molybdenum polymaltose, molybdenum starch complex), molybdenum amino acid, molybdenum carboxylate, molybdenum benzoate, molybdenum tartrate, molybdenum carbonate, molybdenum hydroxide, molybdenum sulphide, molybdenum chloride, molybdenum nitrate, molybdenum oxalate, molybdenum citrate, molybdenum polyphosphate, molybdenum gluconate, molybdenum cyanide and molybdenum silicates, molybdenum trioxide and manganese molybdate or combination thereof.
In some embodiments, the plant micronutrient source for nickel may be nickel oxide, nickel sulphate, nickel chloride, nickel formate, nickel nitrate, nickel acetate, nickel carbonate, nickel oxalate, nickel ascorbate, nickel gluconate, nickel hydroxide, nickel phosphate, nickel phosphide, nickel borate, nickel ammonium phosphate, nickel ammonium sulphate, nickel phosphonates, nickel fluoride, nickel bromide, nickel molybdate, nickel chromate, nickel ricinoleate, nickel ascorbate, nickel orotate, nickel methionate, nickel picolinate, nickel glycinate, nickel lozenges, nickel biopolymer complexes (including nickel polymaltose, nickel starch), nickel amino acid, nickel carboxylate, nickel benzoate, nickel tartrate, nickel carbonate, nickel hydroxide, nickel nitrite, nickel polyphosphate, nickel cyanide, nickel silicates, nickel sulfide and nickel citrate or combination thereof.
In some embodiments, the plant micronutrient source for cobalt may be cobalt oxide, cobalt sulphate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxalate, cobalt gluconate, cobalt hydroxide, cobalt phosphate, cobalt phosphide, cobalt borate, cobalt ammonium phosphate, cobalt ammonium sulphate, cobalt phosphonates, cobalt fluoride, cobalt bromide, cobalt molybdate, cobalt chromate, cobalt ricinoleate, cobalt ascorbate, cobalt orotate, cobalt methionate, cobalt picolinate, cobalt glycinate, cobalt lozenges, cobalt biopolymer complexes (including cobalt polymaltose, cobalt starch), cobalt amino acid, cobalt carboxylate, cobalt benzoate, cobalt tartrate, cobalt carbonate, cobalt hydroxide, cobalt nitrite, cobalt polyphosphate, cobalt cyanide, cobalt silicates, cobalt sulfide and cobalt citrate or combination thereof.
In some embodiments, the plant micronutrient source for selenium is selenium oxide, selenium sulphate, selenium chloride, selenium nitrate, selenium acetate, selenium carbonate, selenium oxalate, selenium gluconate, selenium hydroxide, selenium phosphate, selenium phosphide, selenium borate, selenium ammonium phosphate, selenium ammonium sulphate, selenium phosphonates, selenium fluoride, selenium bromide, selenium molybdate, selenium chromate, selenium ricinoleate, selenium ascorbate, selenium orotate, selenium methionate, selenium picolinate, selenium glycinate, selenium lozenges, selenium biopolymer complexes (including selenium polymaltose, selenium starch), selenium amino acid, selenium carboxylate, selenium benzoate, selenium tartrate, selenium carbonate, selenium hydroxide, selenium nitrite, selenium polyphosphate, selenium cyanide, selenium silicates, selenium sulfide and selenium citrate or combination thereof.
In some embodiments, the plant micronutrient source for titanium is titanium oxide, titanium sulphate, ammonium titanyl sulphate, titanium chloride, titanium nitrate, titanium acetate, titanium carbonate, titanium oxalate, titanium gluconate, titanium hydroxide, titanium phosphate, titanium phosphide, titanium borate, titanium ammonium phosphate, titanium ammonium sulphate, titanium phosphonates, titanium fluoride, titanium bromide, titanium molybdate, titanium chromate, titanium ricinoleate, titanium ascorbate, titanium orotate, titanium methionate, titanium picolinate, titanium glycinate, titanium lozenges, titanium biopolymer complexes (including titanium polymaltose, titanium starch), titanium amino acid, titanium carboxylate, titanium benzoate, titanium tartrate, titanium carbonate, titanium hydroxide, titanium nitrite, titanium polyphosphate, titanium cyanide, titanium silicates, titanium sulfide and titanium citrate or combination thereof.
In some embodiments, the plant micronutrient source for silicon is silicon dioxide, nickel silicate, copper silicate, zinc silicate, sodium silicate, potassium silicate, zeolite, bentonite, aluminium silicates, ammonium silicates, molybdate silicates, borosilicate’s, cobalt silicates, manganese silicate, calcium silicate, magnesium silicate, silicate biopolymer complexes (including silicate polymaltose, silicate starch), silicate amino acid, ortho silicic acid, diatomite silicon, silicon hydroxide sodium pyro silicate or combination thereof. The size of the nanoparticles ranges from 0.1 to 99 nanometres and 100 to 5000 nanometres.
WORKING EXAMPLES:
Example 1:
In an exemplary scenario, amide nitrogen (Urea 5.43 g) was taken and dissolved in 40.81 gm of distilled water. Then, phosphoric acid (3.0 g) was added to make a homogeneous solution through constant stirring at 60oC. The required quantity of potassium hydroxide (2.5 g) was added at the same reaction condition for the next 30 minutes. The resulting solution was used as a solid ionic liquid. It was reacted with micronutrient iron in the form of ferrous sulphate heptahydrate (14.0 g) with constant stirring, and the temperature was increased from 60 to 80oC for another 45 minutes.
In this step, the minimum required quantity of sodium borohydride (1.0 M) in the amount of 3.7 ml was slowly added along the side of the wall. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles. Nanofillers of montmorillonite and nano-silica (each 10.0 g) were added to create granules with the required mesh sizes. The resulting nanoparticle granules were analysed using FTIR, XRD crystallography, particle analyser (DSL), SEM, and TEM&HRTEM to obtain appropriate physical and chemical properties in terms of functional groups present on the material, crystalline structure, particle size, zeta potential, and morphological details. Figure 2 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 1, in accordance with an aspect of the present disclosure.
Example 2:
In an exemplary scenario, ammonium sulphate (15.0 g) was taken and dissolved in 43.0 g of distilled water. Then, boric and sulfuric acid (3.0 and 1.2 g, respectively) were added to make a homogeneous solution through constant stirring at 70oC. The required quantity of potassium carbonate (5.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution was used as an ionic liquid. It was reacted with a micronutrient of zinc in the form of zinc sulphate heptahydrate (15.0 g) with constant stirring, and the temperature was increased to 80oC for another 45 minutes.
In this step, minimum required quantity of sodium borohydride (1.0 M) in the amount of 2.8 ml was slowly added along the side of the wall. Furthermore, sodium lignosulphonates (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated zinc micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to obtain appropriate physical and chemical properties, including functional groups present on the material, crystalline structure, particle size, particle surface charges, and morphological details. Figure 3 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 2, in accordance with an aspect of the present disclosure.
Example 3:
In an exemplary scenario, ethylene diamine (10.0 g) was dissolved in 31.60 g of distilled water. Subsequently, boric and phosphoric acid (8.0 and 12.0 g, respectively) were added to make a homogeneous solution through constant stirring at 90oC. The required quantity of potassium hydroxide (9.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution was used as an ionic liquid. It was reacted with a micronutrient of manganese in the form of manganese chloride (9.0 g) with constant stirring, and the temperature was increased to 90oC for another 45 minutes.
In this step, the minimum required quantity of sodium borohydride (1.0 M) in the amount of 2.8 ml was slowly added along the side of the wall. Furthermore, N, N-dimethylformamide (4.60 g), ethylene glycol (12.0 g), and stabilizer (2.50) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated manganese micronutrient nanoparticles in the form of gel. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to obtain appropriate physical and chemical properties, such as functional groups present on the material, crystalline nature, particle size, particle surface changes, and morphological details. Figure 4 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 3, in accordance with an aspect of the present disclosure.
Example 4:
In an exemplary scenario, amide nitrogen (Urea 9.0 g) was dissolved in 30.81 g of distilled water. Subsequently, boric acid and 2-hydroxyethyl-amino-bis (methylenephosphonic acid (3.0 and 5.6 gm)) were added to make a homogeneous solution through constant stirring at 60oC. Then, the required quantity of potassium hydroxide (1.6 gm) was added at the same reaction condition for the next 30 minutes. The resulting solution was acted upon as an ionic liquid, and it could be reacted with a micronutrient of copper in the form of copper sulphate heptahydrate (16.0 g) at constant stirring and increased the temperature from 80 to 180oC for another 45 minutes. The minimum required quantity of lithium borohydride (1.0 M), 4.0 ml, was added slowly along the side of the wall in this step. The reaction continued for the next 1 hour to obtain the final ionic liquid encapsulated copper micronutrient nanoparticles. To further add a nanofiller of montmorillonite (15 g) and nano-silica (15.0 g) and dry at 90oC to obtain a fine powder of the required nano fertilizer. The resulting nanoparticles granules were analyzed by FTIR, XRD crystallography, particle analyzer (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties, including functional groups present on the material, crystalline structure, particle size, particle surface charges, and morphological details. Figure 5 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 4, in accordance with an aspect of the present disclosure.
Example 5:
In an exemplary scenario, ethylene diamine (7.60 g) was dissolved in 61.90 g of distilled water. Subsequently, both hydrochloric and boric acid (1.60 and 5.0 g) were added to make a homogeneous solution through constant stirring at 150oC. Then, the required quantity of potassium hydroxide (2.30 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with a micronutrient of molybdenum in the form of sodium molybdate dihydrate (2.60 g) at constant stirring and increased the temperature to 110oC for another 45 minutes. The minimum required quantity of lithium borohydride (1.0 M), 8.0 ml, was added slowly along the side of the wall in this step. Additionally, polymeric surfactant (2.0 gm), polyethene glycol (15.0 g), and stabilizer (2.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated molybdenum micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties, including functional groups present on the material, crystalline nature, particle size, surface charges, and morphological details. Figure 6 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 5, in accordance with an aspect of the present disclosure.
Example 6:
Dicyanamide (5.30 g) was dissolved in 37.60 g of distilled water. Subsequently, boric and hydroxy ethylene diphosphonic acid (6.0 and 15 g) were added to make a homogeneous solution through constant stirring at 90oC. Then, the required quantity of potassium hydroxide (9.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrients of zinc/manganese in the form of zinc oxide (4.30 g) and manganese oxide (4.80 g) at constant stirring and increased the temperature to 120oC for another 45 minutes. The minimum required quantity of sodium borohydride (1.0 M), 7.0 ml, was added slowly along the side of the wall in this step. Additionally, sodium lignosulphonates (2.0 g), propylene glycol (10.0 gm), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated zinc/manganese micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties, including functional groups present on the material, crystalline structure, particle size, particle surface changes, and morphological details. Figure 7 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 6, in accordance with an aspect of the present disclosure;
Example 7:
In an exemplary scenario, ethylene diamine (9.0 g) was dissolved in 24.0 g of distilled water. Subsequently, boric acid and hydroxy ethylene diphosphonic acid (4.0 and 8.0 g) were added to make a homogeneous solution through constant stirring at 160oC. Then, the required quantity of potassium hydroxide (6.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrients of iron/copper in the form of ferrous sulphate heptahydrate (11.0 g) and copper sulphate heptahydrate (4.0 g) at constant stirring and increased the temperature from 60 to 80oC for another 45 minutes. The minimum required quantity of sodium borohydride (1.0 M), 4.0 ml, was added slowly along the side of the wall in this step. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron/copper micronutrient nanoparticles. To further add a nanofiller of nano titanium dioxide (15 g) and nano-silica (15.0 g), dry at 90oC to obtain a fine powder of the required nano fertilizer. The resulting nanoparticles granules were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties, including functional groups present on the material, crystalline structure, particle size, particle surface changes, and morphological details. Figure 8 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 7, in accordance with an aspect of the present disclosure.
Example 8:
In an exemplary scenario, urea (10.0 g) was dissolved in 29.20 g of distilled water. Subsequently, boric and amino trimethylene phosphonic acid (6.0 gm and 13.0 g) were added to make a homogeneous solution through constant stirring at 170oC. Then, the required quantity of dipotassium phosphate (10.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with a micronutrient of zinc/copper in the form of zinc sulphate heptahydrate (12.0 g) and copper sulphate pentahydrate (4.0 g) at constant stirring and increased the temperature to 80oC for another 145 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M), 13.8 ml, and ammonium persulfate (0.35 g) were added slowly along the side of the wall. Additionally, polymeric epoxide surfactant (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material, crystalline structure, particle size, particle’s surface charges, and morphological details. Figure 9 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 8, in accordance with an aspect of the present disclosure.
Example 9:
Heterocyclic nitrogen (Triazine Triamine 10.0 g) was dissolved in 49.1 g of distilled water. Subsequently, hydroxy ethylene diphosphonic acid (4.0 g) was added to make a homogeneous solution through constant stirring at 175oC. Then, the required quantity of potassium hydroxide (12.2 g) was added at the same reaction condition for the next 130 minutes. The resulting solution acted as an ionic liquid, and it could be reacted with micronutrients of zinc/iron/manganese in the form of zinc sulphate heptahydrate (7.50 g), ferrous sulphate heptahydrate (5.5 g), and manganese sulphate tetrahydrate (2.20 g) at constant stirring and increased the temperature to 90oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M), 7.3 ml, and potassium persulphate (1.0 M), 7.0 ml, was added slowly along the side of the wall. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated zinc/iron/manganese micronutrient nanoparticles. The minimum required quantity of lithium borohydride (1.0 M), 6.8 ml, was added slowly along the side of the wall in this step. A nanofiller of montmorillonite and nano-silica (5.0 and 7.0 g) was added to make granules with the required mesh sizes. The resulting nanoparticles granules were analysed by FTIR, XRD crystallography, particle analyser (DSL), SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties such as functional groups present on the material, crystalline structure, particle size, particle surface changes, and morphological details. Figure 10 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 9, in accordance with an aspect of the present disclosure.
Example 10:
In an exemplary scenario, urea (9.0 g) was dissolved in 31.76 g of distilled water. Subsequently, boric and hydroxy ethylene diphosphonic acid (4.50 and 14 g) were added to make a homogeneous solution through constant stirring at 117.5oC. Then, the required quantity of potassium hydroxide (8.0 g) and mono ethanol amine (4.5 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid, and it could be reacted with micronutrients of zinc/iron/copper in the form of zinc oxide (2.9 g), iron oxide (1.44 g), and copper oxide (0.60 g) at constant stirring and increased temperature to 80oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 12.8 ml and dibenzoyl sulphate (1.2 g) was added slowly along the side of the wall. In addition, sodium lauryl sulphate (5.0 g), propylene glycol (18.0 g), and stabilizer (2.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated zinc/iron/copper micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analyzed by FTIR, XRD crystallography, particle analyzer (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties such as functional groups present on the material crystalline structure, particle size, particle surface changes, and morphological details. Figure 11 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 10, in accordance with an aspect of the present disclosure.
Example 11:
In an exemplary scenario, amide nitrogen (Urea 9.0 g) was dissolved in 23.40 g of distilled water. Subsequently, hydrochloric acid, boric acid, and hydroxy-phosphono acetic acid (4.0, 6.0, and 7.0 g) were added to make a homogeneous solution through constant stirring at 60oC. Then, the required quantity of potassium hydroxide (9.6 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with a micronutrient of iron in the form of ammonium molybdate (12.0 g) at constant stirring and increased the temperature to 60 to 80oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 4.0 ml was added slowly along the side of the wall. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated molybdenum/chlorine/boron micronutrient nanoparticles. To further add a nanofiller of graphene oxide (5.0 g) and nano-silica (20.0 g), they were dried at 90oC to get the fine powder of the required nano-fertilizer. The resulting nanoparticle granules were analyzed by FTIR, XRD crystallography, particle analyzer (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material, crystalline structure, particle size, particle surface charge, and morphological details. Figure 12 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 11, in accordance with an aspect of the present disclosure.
Example 12:
In an exemplary scenario, Complexed zinc / iron /copper /manganese /molybdenum /chlorine/boron micronutrient nanoparticles were encapsulated. Initially, the desired quantity of amine nitrogen (1,3,5,7-Tetraazatricyclo [3.3.1.13,7] decane 4.0 g) was dissolved in 49.90 g of distilled water. Subsequently, boric acid (1.2 g) was added to make a homogeneous solution through constant stirring at 55oC. Then, the required quantity of potassium chloride (2.5 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrients of zinc/iron/copper/manganese/ molybdenum/chlorine /boron in the form of zinc chloride (2.90 g), ferrous sulphate heptahydrate (2.8 g), Copper sulphate pentahydrate (1.60 g), manganese sulphate tetrahydrate (3.0 g), and ammonium molybdate (0.1 g) at constant stirring and increased the temperature to 80oC for another 145 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 8.0 ml was added slowly along the side of the wall. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles. A nanofiller of montmorillonite and nano-silica (each 12.0 g) was added to make granules with the required mesh sizes. The resulting nanoparticle granules were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material, crystalline structure, particle size, particle surface charge, and morphological details. Figure 13 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 12, in accordance with an aspect of the present disclosure.
Example 13:
In an exemplary scenario, Complexed zinc/selenium micronutrient nanoparticles/nanocomposites were encapsulated. Initially, the desired quantity of urea (10.0 g) was dissolved in 29.20 g of distilled water. Subsequently, boric and amino trimethylene phosphonic acid (6.0 gm and 13.0 g) were added to make a homogeneous solution through constant stirring at 70oC. Then, the required quantity of dipotassium phosphate (10.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrient of zinc/selenium in the form of zinc sulphate heptahydrate (12.0 g) and selenium oxide (4.0 g) at constant stirring and increased the temperature to 80oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 3.8 ml and ammonium persulfate (0.35 g) were added slowly along the side of the wall. In addition, polymeric epoxide surfactant (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material, crystalline structure, particle size, particle’s surface charges, and morphological details. Figure 14 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 13, in accordance with an aspect of the present disclosure.
Example 14:
In an exemplary scenario, urea (10.0 g) was dissolved in 29.20 g of distilled water. Subsequently, boric and amino trimethylene phosphonic acid (6.0 gm and 13.0 g) were added to make a homogeneous solution through constant stirring at 70oC. Then, the required quantity of dipotassium phosphate (10.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrient of titanium/copper in the form of titanium dioxide (12.0 g) and copper sulphate pentahydrate (4.0 g) at constant stirring and increased the temperature to 80oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 3.8 ml and ammonium persulfate (0.35 g) were added slowly along the side of the wall. In addition, polymeric epoxide surfactant (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material crystalline structure, particle size, particle’s surface charges, and morphological details. Figure 15 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 14, in accordance with an aspect of the present disclosure.
Example 15:
In an exemplary scenario, urea (10.0 g) was dissolved in 29.20 g of distilled water. Subsequently, boric and amino trimethylene phosphonic acid (6.0 and 13.0 g) were added to make a homogeneous solution through constant stirring at 70oC. Then, the required quantity of dipotassium phosphate (10.0 g) was added at the same reaction condition for the next 30 minutes. The resulting solution acted as an ionic liquid. It could be reacted with micronutrient of titanium/copper in the form of titanium dioxide (12.0 g) and copper sulphate pentahydrate (4.0 g) at constant stirring and increased the temperature to 80oC for another 45 minutes. In this step, the minimum required quantity of sodium borohydride (1.0 M) 3.8 ml and ammonium persulfate (0.35 g) were added slowly along the side of the wall. In addition, polymeric epoxide surfactant (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were added one by one at the same reaction condition. The reaction was continued for the next 1 hour to obtain the final ionic liquid encapsulated iron micronutrient nanoparticles colloidal solution. The resulting nanoparticles were analysed by FTIR, XRD crystallography, particle analyser (DSL), zeta potential, SEM, and TEM&HRTEM to get the appropriate physical properties and chemical properties in terms of functional groups present on the material crystalline structure, particle size, particle’s surface charges, and morphological details. Figure 16 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 15, in accordance with an aspect of the present disclosure.
Example 16:
In an exemplary scenario, urea (10.0 g) was dissolved in 29.20 g of distilled water. Subsequently, boric and amino trimethylene phosphonic acid (6.0 and 13.0 g) were added to create a homogeneous solution through constant stirring at 170oC. Then, the required quantity of dipotassium phosphate (10.0 g) was added under the same reaction conditions for the following 30 minutes. The resulting solution was transformed into an ionic liquid. It could have been reacted with a micronutrient of silicone/titanium in the form of zinc silicates (12.0 g) and titanyl sulphates (4.0 g) with continuous stirring while increasing the temperature to 80oC for an additional 145 minutes. In this step, the minimum necessary amount of sodium borohydride (1.0 M) totaling 3.8 ml, and ammonium persulfate (0.35 g) were gradually introduced along the side of the vessel. Additionally, polymeric epoxide surfactant (2.0 g), propylene glycol (12.0 g), and stabilizer (1.0) were sequentially incorporated under the same reaction conditions. The reaction was sustained for the next 1 hour to achieve the final ionic liquid encapsulated iron micronutrient nanoparticles colloidal solution. The resultant nanoparticles were subjected to analysis via FTIR, XRD crystallography, particle analyzer (DSL), zeta potential, SEM, and TEM&HRTEM in order to obtain the relevant physical and chemical properties in terms of functional groups present in the material's crystalline structure, particle size, particle surface charges, and morphological details. Figure 17 illustrates TEM image of an exemplary nano-based crop nutrient formulation as disclosed in example 16, in accordance with an aspect of the present disclosure.
In one aspect of the present disclosure, a method for preparing a nano-based crop nutrient formulation is provided. The method (100) includes the steps of dissolving (101) 3- 75 g of nitrogen compound in 22-100 g of water to obtain nitrogen compound solution, protonating (103) by adding 1-50 g of organic acid to nitrogen compound solution to obtain activated nitrogenous compound by constant stirring for 30-350 minutes at a temperature of 50-200oC, complexing (105) by adding 2-80 g of nutrient rich compounds to the activated nitrogenous compound to obtain active electron-rich complex, adding (107) 1.5- 10 g of alkali to adjust the pH and add 0.05 to 10.0 g of reducing and oxidizing agents to the active electron-rich complex to obtain multifunctional ionic liquid, adding (109) 0.1 to 80 g micronutrient rich inorganic compounds to the multifunctional ionic liquid by constant stirring for 30-350 minutes at a temperature of 50-200oC to obtain micronutrient nanoparticles and adding (111) 0.25 to 25 g of surfactants, 0.1 to 15 g of dispersing agents, 0.1 to 12 g of wetting agents, 0.1 g to 16 g of stabilizing agents and 0.01 to 2.0 g of defoamers to the micronutrient nanoparticles for 30-70 minutes at a temperature of 50-200oC to obtain the nano-based crop nutrient formulation.
In some aspects of the present disclosure, the nitrogen compound is selected from the group comprising: ammonium salts, liquid ammonia, amides, diamides, thioamides, urea, thiourea, cyanamides, dicyandiamide, amines, imines, imides, nitriles, nitrogen heterocycles, triazine (triazine monoamine, triazine diamine, triazine triazine), triazole (triazole monoamine, triazole diamine, triazole triamine) and tetrazine (tetrazine monoamine, tetrazine diamine, tetrazine triamine) based compounds.
In some aspects of the present disclosure, the organic acids are selected from the group comprising formic acid, acetic acid, propionic acid, butyric acid, citric acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, nitric acid, phosphoric acid, phosphonic acid, glutamic acid, glycolic acid, boric acid, humic acid, folic acid, sulfuric acid, hydrochloric acid, silicic acid, fulvic acid and amino acids or combinations thereof.
In some aspects of the present disclosure, the nutrient rich compounds is selected from the group comprising inorganic salts of phosphates, superphosphates, single super phosphate, phosphonic acids (PBTC), (2- phosphonobutane-1,2,4-tricarboxylic acid), 1-hydroxyethylidene-1,1- diphosphonic acid (HEDP), amino-tris-methylenephosphonic acid (ATMP), 2-hydroxyethyl-amino-bis(methylenephosphonic acid (HEAMBP), ethylenediamine-tetrakis(methylene-phosphonic acid) (EDTMP), hydroxy-phosphono acetic acid (HPAA) and hexamethylene-diamine-tetrakis(methylene-phosphonic acid) (DETPMP) and phosphonates of sodium and potassium salts , potassium phosphides, potassium chloride, potassium hydroxide, potassium carbonate, potassium phosphate, potassium phosphites, potassium borates, potassium humate, potassium silicate, potassium oxide, potassium glycinate, potassium citrate, potassium gluconate, potassium oxalate, potassium sorbate, potassium stearate, potassium acrylate, potassium sulphide, potassium sulphate, and potassium nitrate or a combination of thereof.
In some aspects of the present disclosure, the micronutrients is selected from the group comprising boric acid, disodium octa borate tetrahydrate, dipotassium octa borate tetrahydrate, calcium borate, zinc borate, boron oxide, ferrous borate, copper borate, manganese borate, molybdenum borate, potassium borosilicate, nickel borate, boron humates, boron cluster, all metal borates, anhydrous borax, colemanite, boron ethanolamine, boronated single superphosphate, sodium borosilicate, potassium boron oxide, magnesium borate, sodium tetra borate, potassium borate, or a combination thereof, zinc oxide, zinc sulphate (anhydrous, mono and hepta hydrates), zinc phosphate, zinc borate, zinc ammonium phosphate, zinc dust, zinc phosphonates, zinc fluoride, zinc bromide, zinc molybdate, zinc chromate, zinc ricinoleate, zinc ascorbate, zinc orotate, zinc methionate, zinc picolinate, zinc glycinate, zinc lozenges, zinc biopolymer complexes (including zinc polymaltose, zinc starch), zinc amino acid, zinc carboxylate, zinc benzoate, zinc tartrate, zinc carbonate, zinc hydroxide, zinc sulphide, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, zinc citrate, zinc polyphosphate, zinc gluconate, zinc cyanide and zinc silicates or combination thereof, Iron oxide, Iron sulphate, Iron sulphide, Iron chloride, Iron carbonate, Iron acetate, Iron oxalate, Iron gluconate, Iron silicates, Iron phosphate, Iron hydroxide, ferrous borate, ferrous ammonium phosphate, iron phosphonates, iron fluoride, iron bromide, iron molybdate, iron chromate, iron ricinoleate, iron ascorbate, iron orotate, iron methionate, iron picolinate, iron glycinate, iron lozenges, iron biopolymer complexes (including iron polymaltose, iron starch), iron amino acid, iron carboxylate, iron benzoate, iron ascorbate, iron oxalate, iron tartrate, iron citrate, iron polyphosphate, iron cyanide Iron nitrate and Iron citrate or combination thereof, manganese oxide, manganese sulphate, manganese chloride, manganese nitrate, manganese acetate, manganese carbonate, manganese oxalate, manganese gluconate, manganese hydroxide, manganese phosphate, manganese phosphide, manganese borate, manganese ammonium phosphate, manganese phosphonates, manganese fluoride, manganese bromide, manganese molybdate, manganese chromate, manganese ricinoleate, manganese ascorbate, manganese orotate, manganese methionate, manganese picolinate, manganese glycinate, manganese lozenges, manganese biopolymer complexes (including manganese polymaltose, manganese starch), manganese amino acid, manganese carboxylate, manganese benzoate, manganese tartrate, manganese ascorbate, manganese carbonate, manganese hydroxide, manganese sulphide, manganese chloride, manganese nitrate, manganese acetate, manganese oxalate, manganese citrate, manganese polyphosphate, manganese gluconate, manganese cyanide and manganese silicates, manganese sulphide and manganese citrate or combination thereof, copper may be copper oxide, copper sulphate, copper chloride, copper nitrate, copper acetate, copper carbonate, copper oxalate, copper gluconate, copper hydroxide, copper phosphate, copper phosphide, copper borate, copper ammonium phosphate, copper ammonium sulphate, copper phosphonates, copper fluoride, copper bromide, copper molybdate, copper chromate, copper ricinoleate, copper ascorbate, copper orotate, copper methionate, copper picolinate, copper glycinate, copper ascorbate, copper lozenges, copper biopolymer complexes (including copper polymaltose, copper starch), copper amino acid, copper carboxylate, copper benzoate, copper tartrate, copper carbonate, copper hydroxide, copper nitrite, copper polyphosphate, copper cyanide, copper silicates, copper sulfide and Copper citrate or combination thereof, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, iron molybdate, copper molybdate, zinc molybdate, nickel molybdate, cobalt molybdate, molybdenum acetate, molybdenum borate, ammonium phosphor molybdate, molybdenum phosphonates, molybdenum fluoride, molybdenum bromide, molybdenum chromate, molybdenum ricinoleate, molybdenum ascorbate, molybdenum orotate, molybdenum methionate, molybdenum picolinate, molybdenum glycinate, molybdenum lozenges, molybdenum biopolymer complexes (including molybdenum polymaltose, molybdenum starch complex), molybdenum amino acid, molybdenum carboxylate, molybdenum benzoate, molybdenum tartrate, molybdenum carbonate, molybdenum hydroxide, molybdenum sulfide, molybdenum chloride, molybdenum nitrate, molybdenum oxalate, molybdenum citrate, molybdenum polyphosphate, molybdenum gluconate, molybdenum cyanide and molybdenum silicates, molybdenum trioxide and manganese molybdate or combination thereof, nickel oxide, nickel sulphate, nickel chloride, nickel formate, nickel nitrate, nickel acetate, nickel carbonate, nickel oxalate, nickel ascorbate, nickel gluconate, nickel hydroxide, nickel phosphate, nickel phosphide, nickel borate, nickel ammonium phosphate, nickel ammonium sulphate, nickel phosphonates, nickel fluoride, nickel bromide, nickel molybdate, nickel chromate, nickel ricinoleate, nickel ascorbate, nickel orotate, nickel methionate, nickel picolinate, nickel glycinate, nickel lozenges, nickel biopolymer complexes (including nickel polymaltose, nickel starch), nickel amino acid, nickel carboxylate, nickel benzoate, nickel tartrate, nickel carbonate, nickel hydroxide, nickel nitrite, nickel polyphosphate, nickel cyanide, nickel silicates, nickel sulfide and nickel citrate or combination thereof, cobalt oxide, cobalt sulphate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxalate, cobalt gluconate, cobalt hydroxide, cobalt phosphate, cobalt phosphide, cobalt borate, cobalt ammonium phosphate, cobalt ammonium sulphate, cobalt phosphonates, cobalt fluoride, cobalt bromide, cobalt molybdate, cobalt chromate, cobalt ricinoleate, cobalt ascorbate, cobalt orotate, cobalt methionate, cobalt picolinate, cobalt glycinate, cobalt lozenges, cobalt biopolymer complexes (including cobalt polymaltose, cobalt starch), cobalt amino acid, cobalt carboxylate, cobalt benzoate, cobalt tartrate, cobalt carbonate, cobalt hydroxide, cobalt nitrite, cobalt polyphosphate, cobalt cyanide, cobalt silicates, cobalt sulfide and cobalt citrate or combination thereof, selenium oxide, selenium sulphate, selenium chloride, selenium nitrate, selenium acetate, selenium carbonate, selenium oxalate, selenium gluconate, selenium hydroxide, selenium phosphate, selenium phosphide, selenium borate, selenium ammonium phosphate, selenium ammonium sulphate, selenium phosphonates, selenium fluoride, selenium bromide, selenium molybdate, selenium chromate, selenium ricinoleate, selenium ascorbate, selenium orotate, selenium methionate, selenium picolinate, selenium glycinate, selenium lozenges, selenium biopolymer complexes (including selenium polymaltose, selenium starch), selenium amino acid, selenium carboxylate, selenium benzoate, selenium tartrate, selenium carbonate, selenium hydroxide, selenium nitrite, selenium polyphosphate, selenium cyanide, selenium silicates, selenium sulfide and selenium citrate or combination thereof, titanium oxide, titanium sulphate, titanium chloride, titanium nitrate, titanium acetate, titanium carbonate, titanium oxalate, titanium gluconate, titanium hydroxide, titanium phosphate, titanium phosphide, titanium borate, titanium ammonium phosphate, titanium ammonium sulphate, titanium phosphonates, titanium fluoride, titanium bromide, titanium molybdate, titanium chromate, titanium ricinoleate, titanium ascorbate, titanium orotate, titanium methionate, titanium picolinate, titanium glycinate, titanium lozenges, titanium biopolymer complexes (including titanium polymaltose, titanium starch), titanium amino acid, titanium carboxylate, titanium benzoate, titanium tartrate, titanium carbonate, titanium hydroxide, titanium nitrite, titanium polyphosphate, titanium cyanide, titanium silicates, titanium sulfide and titanium citrate or combination thereof, silicon dioxide, nickel silicate, copper silicate, zinc silicate, sodium silicate, potassium silicate, zeolite, bentonite, aluminium silicates, ammonium silicates, molybdate silicates, borosilicates, cobalt silicates, manganese silicate, calcium silicate, magnesium silicate, silicate biopolymer complexes (including silicate polymaltose, silicate starch and), silicate amino acid, ortho silicic acid, diatomite silicon, silicon hydroxide sodium pyro silicate or combination thereof.
In some aspects of the present disclosure, the stabilizer may be selected from the group comprising ethylene glycol, propylene glycol, polyethene glycol, polyvinyl alcohol, poly (Vinylpyrrolidone), carboxymethyl cellulose, long chain thiol, sodium dodecyl sulphate, carboxylic compounds, the long and branched structure of amines, cellulose and citrate or a combination thereof.
In some aspects of the present disclosure, the method (100) may further include the adding (110) drop by drop 2-8 ml of reducing agents before the step 109 wherein the reducing agents may be selected from the group comprising sodium borohydride, lithium borohydride, aluminium borohydride, lithium alluminium hydride, sodium citrate, glycol ethylene, hydroquinone, ethanol, formaldehyde, sugar pyrolysis radicals, hydroxyl radicals, N, N-dimethylformamide and hydrazine hydrate, phytochemical extractions from bio-active plants, or a combination thereof.
In some aspects of the present disclosure, the method (100) further comprises adding (112) of 4-30 g of nanofillers to obtain granules of nano-based crop nutrient formulation wherein the nanofillers may be selected from the group consisting of montmorillonite, nano-silica, nano-zeolite, graphene, graphene oxide, boron nitride, nano clay, nano cellulose, nano starch and combinations thereof.
In some aspects of the present disclosure, the surfactant may be selected from the group consisting of polymeric surfactants, acrylic based EO/PO, non-ionic surfactants, phosphorus ester-based surfactants, epoxide surfactants, and anionic surfactants.
In another aspect of the present disclosure, a nano-based crop nutrient formulation is provided. The crop nutrient formulation includes macronutrients in the range of macronutrients in the range of 3 to 75 % (w/w), micronutrient in the range of 1 to 80 % (w/w), and micronutrient trace elements in the range of 0.5 to 50 % (w/w).
In some aspects of the present disclosure, the macronutrient is selected from the group comprising nitrogen (N), phosphorous (P), potassium (K) and combinations thereof.
In some aspects of the present disclosure, the micronutrient nanoparticles may be selected from the group comprising: zinc in a concentration of 0.1 to 75 %, iron in a concentration of 0.1 to 75 % , manganese in a concentration of 0.1 to 75 %, copper in a concentration of 0.1 to 75 %, molybdenum in a concentration of 0.1 to 50 %, boron in a concentration of 0.1 to 75 % and chlorine in a concentration of 0.1 to 75 % and combinations thereof.
In some aspects of the present disclosure, the trace elements nutrients is selected from the group comprising selenium in a concentration of 0.1 to 50 %, titanium in a concentration of 0.1 to 50%, nickel in the concentration of 0.1 to 50 %, cobalt in the concentration of 0.1 to 50 % and silicon in the concentration of 0.1 to 50 % and combinations thereof.
In some aspects of the present disclosure, the size of the nanoparticles ranges from 0.2 to 99 nanometres and 100 to 5000 nanometres.
Advantages:
• The present disclosure offers a nano-based crop nutrient formulation aimed at enhancing the productivity of agricultural/horticultural crops. This formulation leads to increased crop yields, improved biomass, higher plant weight, greater plant height, broader leaves with increased branching, elongated roots with enhanced branching, and an earlier flowering stage. Additionally, the crop quality could be elevated, resulting in less reducing sugars and heightened starch content.
• The present disclosure provides a nano-based crop nutrient formulation that can be applied directly to the soil that could coat a root or seed.
• The present disclosure provides a nano-based crop nutrient formulation that could disperse faster to various targeted parts of the plant bio-system.
• The present disclosure provides a nano-based crop nutrient formulation that can be used for nano fertilization, which demonstrates minimal phytotoxicity and doesn’t require high doses of fertilizers.
• The present disclosure provides a nano-based crop nutrient formulation that are stable and can be combined with macronutrients to produce plant growth nano nutrients for agriculture/horticultural crops.
• The present disclosure provides a nano-based crop nutrient formulation that provides a method for producing organically complexed micronutrients that are more easily absorbed by plants, leading to increased crop yields and improved plant health.
• The present disclosure provides a nano-based crop nutrient formulation in which nano form of boron plays an essential part in many metabolic and biochemical processes in plants. Furthermore, it could be involved in critical plant metabolisms, including nucleic acid, carbohydrates, protein, and indole acetic acid. Additionally, the synthesis of a cell wall, structure of a cell, membrane integrity and function and metabolism of phenol also be effectively improved by using these complexed nano micronutrients.
The implementation set forth in the foregoing description does not represent all implementations consistent with the subject matter described herein. Instead, they are merely some examples consistent with aspects related to the described subject matter. Although a few variations have been described in detail above, other modifications or additions are possible. In particular, further features and/or variations can be provided in addition to those set forth herein. For example, the implementation described can be directed to various combinations and sub combinations of the disclosed features and/or combinations and sub combinations of the several further features disclosed above. In addition, the logic flows depicted in the accompanying figures and/or described herein do not necessarily require the particular order shown, or sequential order, to achieve desirable results. Other implementations may be within the scope of the following claims. ,CLAIMS:WE CLAIM
1. A method (100) for preparing a nano-based crop nutrient formulation comprises the steps:
a. dissolving (101) 3-75 g of nitrogen compound in 22-100 g of water to obtain nitrogen compound solution;
b. protonating (103) by adding 1-50 g of organic acid to nitrogen compound solution to obtain activated nitrogenous compound by constant stirring for 30-350 minutes at a temperature of 50-200oC;
c. complexing (105) by adding 2-80 g of nutrient rich compounds to the activated nitrogenous compound to obtain active electron-rich complex;
d. adding (107) 1.5- 10 g of alkali to the active electron-rich complex to obtain multifunctional ionic liquid;
e. adding (109) 0.1 to 80 g micronutrient rich inorganic compounds to the multifunctional ionic liquid by constant stirring for 0.5 to 5.0 hours at a temperature of 50-200oC.
f. adding (110) 0.1 to 15 g reducing or oxidizing agent to the micronutrients dissolved multifunctional ionic liquid by constant stirring for 30 to 300 minutes to obtain stable ionic liquid encapsulated nanoparticles of micronutrients.
g. adding (111) 0.25 to 25 g of surfactants, 0.1-12 g of dispersing agents, 0.1-15 g of wetting agents, 0.1 g to 16 g of stabilizing agents and 0.01-2.0 g of defoamers to the micronutrient nanoparticles for 30-350 minutes at a temperature of 50-200oC to obtain the nano-based crop nutrient formulation.

2. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein the nitrogen compound is selected from the group comprising: ammonium salts, liquid ammonia, amides, diamides, thioamides, urea, thiourea, cyanamides, dicyandiamide, amines, imines, imides, nitriles, nitrogen heterocycles, triazine (triazine monoamine, triazine diamine, triazine triazine), triazole (triazole monoamine, triazole diamine, triazole triamine) and tetrazine (tetrazine monoamine, tetrazine diamine, tetrazine triamine) based compounds.

3. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein organic acids are selected from the group comprising: formic acid, acetic acid, propionic acid, butyric acid, citric acid, succinic acid, oxalic acid, tartaric acid, benzoic acid, nitric acid, phosphoric acid, phosphonic acid, glutamic acid, glycolic acid, boric acid, humic acid, folic acid, sulfuric acid, hydrochloric acid, silicic acid, fulvic acid and amino acids or combinations thereof.

4. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein the nutrient rich complexing compounds is selected from the group comprising inorganic salts of phosphates, superphosphates, single super phosphate, phosphonic acids (PBTC), (2- phosphonobutane-1,2,4-tricarboxylic acid), 1-hydroxyethylidene-1,1- diphosphonic acid (HEDP), amino-tris-methylenephosphonic acid (ATMP), 2-hydroxyethyl-amino-bis(methylenephosphonic acid (HEAMBP), ethylenediamine-tetrakis(methylene-phosphonic acid) (EDTMP), hydroxy-phosphono acetic acid (HPAA) and hexamethylene-diamine-tetrakis(methylene-phosphonic acid) (DETPMP) and phosphonates of sodium and potassium salts , potassium phosphides, potassium chloride, potassium hydroxide, potassium carbonate, potassium phosphate, potassium phosphites, potassium borates, potassium humate, potassium silicate, potassium oxide, potassium glycinate, potassium citrate, potassium gluconate, potassium oxalate, potassium sorbate, potassium stearate, potassium acrylate, potassium sulphide, potassium sulphate, and potassium nitrate or a combination of thereof.

5. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein the micronutrients is selected from the group comprising boric acid, disodium octa borate tetrahydrate, dipotassium octa borate tetrahydrate, calcium borate, zinc borate, boron oxide, ferrous borate, copper borate, manganese borate, molybdenum borate, potassium borosilicate, nickel borate, boron humates, boron cluster, all metal borates, anhydrous borax, colemanite, boron ethanolamine, boronated single superphosphate, sodium borosilicate, potassium boron oxide, magnesium borate, sodium tetra borate, potassium borate, or a combination thereof, zinc oxide, zinc sulphate (anhydrous, mono and hepta hydrates), zinc phosphate, zinc borate, zinc ammonium phosphate, zinc dust, zinc phosphonates, zinc fluoride, zinc bromide, zinc molybdate, zinc chromate, zinc ricinoleate, zinc ascorbate, zinc orotate, zinc methionate, zinc picolinate, zinc glycinate, zinc lozenges, zinc biopolymer complexes (including zinc polymaltose, zinc starch), zinc amino acid, zinc carboxylate, zinc benzoate, zinc tartrate, zinc carbonate, zinc hydroxide, zinc sulphide, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, zinc citrate, zinc polyphosphate, zinc gluconate, zinc cyanide and zinc silicates or combination thereof, Iron oxide, Iron sulphate, Iron sulphide, Iron chloride, Iron carbonate, Iron acetate, Iron oxalate, Iron gluconate, Iron silicates, Iron phosphate, Iron hydroxide, ferrous borate, ferrous ammonium phosphate, iron phosphonates, iron fluoride, iron bromide, iron molybdate, iron chromate, iron ricinoleate, iron ascorbate, iron orotate, iron methionate, iron picolinate, iron glycinate, iron lozenges, iron biopolymer complexes (including iron polymaltose, iron starch), iron amino acid, iron carboxylate, iron benzoate, iron ascorbate, iron oxalate, iron tartrate, iron citrate, iron polyphosphate, iron cyanide Iron nitrate and Iron citrate or combination thereof, manganese oxide, manganese sulphate, manganese chloride, manganese nitrate, manganese acetate, manganese carbonate, manganese oxalate, manganese gluconate, manganese hydroxide, manganese phosphate, manganese phosphide, manganese borate, manganese ammonium phosphate, manganese phosphonates, manganese fluoride, manganese bromide, manganese molybdate, manganese chromate, manganese ricinoleate, manganese ascorbate, manganese orotate, manganese methionate, manganese picolinate, manganese glycinate, manganese lozenges, manganese biopolymer complexes (including manganese polymaltose, manganese starch), manganese amino acid, manganese carboxylate, manganese benzoate, manganese tartrate, manganese ascorbate, manganese carbonate, manganese hydroxide, manganese sulphide, manganese chloride, manganese nitrate, manganese acetate, manganese oxalate, manganese citrate, manganese polyphosphate, manganese gluconate, manganese cyanide and manganese silicates, manganese sulphide and manganese citrate or combination thereof, copper may be copper oxide, copper sulphate, copper chloride, copper nitrate, copper acetate, copper carbonate, copper oxalate, copper gluconate, copper hydroxide, copper phosphate, copper phosphide, copper borate, copper ammonium phosphate, copper ammonium sulphate, copper phosphonates, copper fluoride, copper bromide, copper molybdate, copper chromate, copper ricinoleate, copper ascorbate, copper orotate, copper methionate, copper picolinate, copper glycinate, copper ascorbate, copper lozenges, copper biopolymer complexes (including copper polymaltose, copper starch), copper amino acid, copper carboxylate, copper benzoate, copper tartrate, copper carbonate, copper hydroxide, copper nitrite, copper polyphosphate, copper cyanide, copper silicates, copper sulfide and Copper citrate or combination thereof, ammonium molybdate, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, iron molybdate, copper molybdate, zinc molybdate, nickel molybdate, cobalt molybdate, molybdenum acetate, molybdenum borate, ammonium phosphor molybdate, molybdenum phosphonates, molybdenum fluoride, molybdenum bromide, molybdenum chromate, molybdenum ricinoleate, molybdenum ascorbate, molybdenum orotate, molybdenum methionate, molybdenum picolinate, molybdenum glycinate, molybdenum lozenges, molybdenum biopolymer complexes (including molybdenum polymaltose, molybdenum starch complex) , molybdenum amino acid, molybdenum carboxylate, molybdenum benzoate, molybdenum tartrate, molybdenum carbonate, molybdenum hydroxide, molybdenum sulfide, molybdenum chloride, molybdenum nitrate, molybdenum oxalate, molybdenum citrate, molybdenum polyphosphate, molybdenum gluconate, molybdenum cyanide and molybdenum silicates, molybdenum trioxide and manganese molybdate or combination thereof, nickel oxide, nickel sulphate, nickel chloride, nickel formate, nickel nitrate, nickel acetate, nickel carbonate, nickel oxalate, nickel ascorbate, nickel gluconate, nickel hydroxide, nickel phosphate, nickel phosphide, nickel borate, nickel ammonium phosphate, nickel ammonium sulphate, nickel phosphonates, nickel fluoride, nickel bromide, nickel molybdate, nickel chromate, nickel ricinoleate, nickel ascorbate, nickel orotate, nickel methionate, nickel picolinate, nickel glycinate, nickel lozenges, nickel biopolymer complexes (including nickel polymaltose, nickel starch), nickel amino acid, nickel carboxylate, nickel benzoate, nickel tartrate, nickel carbonate, nickel hydroxide, nickel nitrite, nickel polyphosphate, nickel cyanide, nickel silicates, nickel sulfide and nickel citrate or combination thereof, cobalt oxide, cobalt sulphate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt oxalate, cobalt gluconate, cobalt hydroxide, cobalt phosphate, cobalt phosphide, cobalt borate, cobalt ammonium phosphate, cobalt ammonium sulphate, cobalt phosphonates, cobalt fluoride, cobalt bromide, cobalt molybdate, cobalt chromate, cobalt ricinoleate, cobalt ascorbate, cobalt orotate, cobalt methionate, cobalt picolinate, cobalt glycinate, cobalt lozenges, cobalt biopolymer complexes (including cobalt polymaltose, cobalt starch), cobalt amino acid, cobalt carboxylate, cobalt benzoate, cobalt tartrate, cobalt carbonate, cobalt hydroxide, cobalt nitrite, cobalt polyphosphate, cobalt cyanide, cobalt silicates, cobalt sulfide and cobalt citrate or combination thereof, selenium oxide, selenium sulphate, selenium chloride, selenium nitrate, selenium acetate, selenium carbonate, selenium oxalate, selenium gluconate, selenium hydroxide, selenium phosphate, selenium phosphide, selenium borate, selenium ammonium phosphate, selenium ammonium sulphate, selenium phosphonates, selenium fluoride, selenium bromide, selenium molybdate, selenium chromate, selenium ricinoleate, selenium ascorbate, selenium orotate, selenium methionate, selenium picolinate, selenium glycinate, selenium lozenges, selenium biopolymer complexes (including selenium polymaltose, selenium starch), selenium amino acid, selenium carboxylate, selenium benzoate, selenium tartrate, selenium carbonate, selenium hydroxide, selenium nitrite, selenium polyphosphate, selenium cyanide, selenium silicates, selenium sulfide and selenium citrate or combination thereof, titanium oxide, titanium sulphate, titanium chloride, titanium nitrate, titanium acetate, titanium carbonate, titanium oxalate, titanium gluconate, titanium hydroxide, titanium phosphate, titanium phosphide, titanium borate, titanium ammonium phosphate, titanium ammonium sulphate, titanium phosphonates, titanium fluoride, titanium bromide, titanium molybdate, titanium chromate, titanium ricinoleate, titanium ascorbate, titanium orotate, titanium methionate, titanium picolinate, titanium glycinate, titanium lozenges, titanium biopolymer complexes (including titanium polymaltose, titanium starch), titanium amino acid, titanium carboxylate, titanium benzoate, titanium tartrate, titanium carbonate, titanium hydroxide, titanium nitrite, titanium polyphosphate, titanium cyanide, titanium silicates, titanium sulfide and titanium citrate or combination thereof, silicon dioxide, nickel silicate, copper silicate, zinc silicate, sodium silicate, potassium silicate, zeolite, bentonite, aluminium silicates, ammonium silicates, molybdate silicates, borosilicates, cobalt silicates, manganese silicate, calcium silicate, magnesium silicate, silicate biopolymer complexes (including silicate polymaltose, silicate starch), silicate amino acid, ortho silicic acid, diatomite silicon, silicon hydroxide sodium pyro silicate or combination thereof.
6. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein the stabilizer may be selected from the group comprising ethylene glycol, propylene glycol, polyethene glycol, polyvinyl alcohol, poly (Vinylpyrrolidone), carboxymethyl cellulose, long chain thiol, sodium dodecyl sulphate, carboxylic compounds, the long and branched structure of amines, cellulose and citrate or a combination thereof.

7. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, further comprises adding (110) drop by drop 2-20 ml of reducing agents before the step 109 wherein the reducing agent is selected from the group comprising sodium borohydride, lithium borohydride, aluminium borohydride, lithium alluminium hydride, sodium citrate, glycol ethylene, hydroquinone, ethanol, formaldehyde, sugar pyrolysis radicals, hydroxyl radicals, N, N-dimethylformamide and hydrazine hydrate, phytochemical extractions from bio-active plants, or a combination thereof.

8. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, further comprises adding (112) of 4-80 g of nanofillers to obtain granules of nano-based crop nutrient formulation wherein the nanofillers are selected from the group consisting of montmorillonite, nano-silica, nano-zeolite, graphene, graphene oxide, boron nitride, nano clay, nano cellulose, nano starch and combinations thereof.

9. The method (100) of preparing a nano-based crop nutrient formulation as claimed in claim 1, wherein the surfactant is selected from the group consisting of polymeric surfactants, acrylic EO/PO, non-ionic surfactants, phosphorus ester-based surfactants, epoxide surfactants, and anionic surfactants.

10. A nano-based crop nutrient formulation comprising:
a. macronutrients in the range of 3 to 75%(w/w); and
b. micronutrient in the range of 1 to 80% (w/w).
c. micronutrient trace elements in the range of 0.5 to 50% (w/w)

11. The nano-based crop nutrient formulation as claimed in claim 10, wherein the macronutrient is selected from group comprising nitrogen (N), phosphorous (P), potassium (K) and combinations thereof.

12. The nano-based crop nutrient formulation as claimed in claim 10, wherein the micronutrient nanoparticles are selected from the group comprising: zinc in a concentration of 0.1 to 75 %, iron in a concentration of 0.1 to 75 %, manganese in a concentration of 0.1 to 75 %, copper in a concentration of 0.1 to 75 %, molybdenum in a concentration of 0.1 to 50 %, boron in a concentration of 0.1 to 75 % and chlorine in a concentration of 0.1 to 75 % combinations thereof.

13. The nano-based crop nutrient formulation as claimed in claim 10, wherein the micronutrient trace elements nanoparticles are selected from the group comprising: selenium in a concentration of 0.1 to 50 %, titanium in a concentration of 0.1 to 50%, nickel in the concentration of 0.1 to 50 %, cobalt in the concentration of 0.1 to 50 % and silicon in the concentration of 0.1 to 50 % and combinations thereof.

14. The nano-based crop nutrient formulation as claimed in claim 10, wherein the size of the nanoparticles ranges from 0.1 to 99 nanometres and 100 to 5000 nanometres.