Classifications

• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05C—NITROGENOUS FERTILISERS
  • C05C9/00—Fertilisers containing urea or urea compounds
  • C05C9/005—Post-treatment
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
  • C05G5/00—Fertilisers characterised by their form
  • C05G5/30—Layered or coated, e.g. dust-preventing coatings
  • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer

Definitions

• the present invention relates to a process for preparation of nano-fertilizer composition for improving the bioavailability of plant nutrients.
• Plants require certain essential nutrients for normal functioning and growth. Nutrient levels outside the amount required for normal functioning and growth may cause overall crop growth and health to decline due to either a deficiency or a toxicity. Nutrient deficiency occurs when an essential nutrient is not available in sufficient quantity to meet the requirements of a growing plant. Toxicity occurs when a nutrient is in excess of plant needs and decreases plant growth or quality.
• N nitrogen
• P phosphorous
• K potassium
• Ca calcium
• Mg magnesium
• S sulfur
• micronutrients required in small amounts for plant growth are boron (B), chlorine (Cl), manganese (Mn), iron (Fe), zinc (Zn), copper (Cu), molybdenum (Mo) and selenium (Se).
• Fertilizers particularly synthetic fertilizers have a major potential to pollute soil, water and air; in recent years, many efforts were done to minimize these problems by agricultural practices and the design of the new improved fertilizers.
• Water soluble conventional fertilizers typically result in a large amount of macronutrients being lost by leaching and evaporation.
• Conventional fertilizers are generally applied on the crops by either spraying or broadcasting.
• one of the major factors that decide the mode of application is the final concentration of the fertilizers reaching to the plant. In practical scenario, very less concentration (much below to minimum desired concentration) reaches to the targeted site due to leaching of chemicals, fixation, drift, runoff, evaporation, hydrolysis by soil moisture, and photolytic and microbial degradation. It has been estimated that around 40-70% of nitrogen, 80-90% of phosphorus, and 50-90% of potassium content of applied fertilizers are lost in the environment and could not reach the plant, which causes sustainable and economic losses.
• Nanotechnology is an enabling technology.
• Metallic, oxide and semiconductor nanoparticles have properties entirely different from their bulk. Due to their unusual optoelectronic and physico-chemical properties, they find application in electronics, sensing, catalysis, paints, solar cells, etc.
• Polymer nanoparticles are a different class of nanoparticles, which have the ability to entrap different entities.
• the objective of using polymer nanoparticles is to exploit the small size and its ability to penetrate tissue; and has been extensively used in pharma to design anti-cancer nano-drugs.
• the present invention is using this ability of polymer nanoparticles to entrap molecules as delivery vehicles inside plants.
• the primary object of the present invention herein is to provide a process of preparing the nano-fertilizer composition which is capable of slow release/controlled release of a plant nutrient inside plant system.
• Yet another object of the present invention herein is to provide a nano-fertilizer composition using a synthetic polymer Polyethylenimine (PEI).
• PEI Polyethylenimine
• Yet another objective of the present invention is to provide a nano-fertilizer composition encapsulating nitrogen, phosphorous and potassium or NPK fertilizer compounds, secondary nutrients; and micronutrients to provide an economical and readily available source imminently suitable for correcting macronutrient and micronutrient deficiencies in plant life growing at such sites.
• the present invention provides a process for preparing nanofertilizer composition providing important plant nutrients for agricultural application without causing or limiting environmental hazard.
• the nano-fertilizer composition of the present invention is capable of slow release/controlled release of a plant nutrient inside plant system.
• the synthetic polymer is polyethyleneimine (PEI) having molecular weight in the range of 5000 Da to 25000 Da.
• the ratio of plant nutrient: synthetic polymer (PEI) by weight is in the range from 1 to 2750 and the synthetic polymer concentration is varied from 0.02% to 1% wt./v.
• the cross-linking agent is selected from the group comprising of carboxylic acid polymer preferably polyacrylic acid or a copolymer of acrylic and maleic acid or a conventional molecule such as sodium triphosphate (STPP).
• carboxylic acid polymer preferably polyacrylic acid or a copolymer of acrylic and maleic acid or a conventional molecule such as sodium triphosphate (STPP).
• STPP sodium triphosphate
• the carboxylic acid cross linker is in the molecular weight range of 5000 Da to 70000 Da.
• nano-fertilizer can optionally be formed in PEI system without the presence of a cross-linking agent.
• the present invention provides a nano-fertilizer composition preferably in form of an aqueous solution comprising plant nutrient trapped inside synthetic polymer nanoparticle, wherein the synthetic polymer nanoparticle is made by cross-linking of polyethyleneimine and acrylic acid polymer.
• the fertilizer is present in an amount 1% to 55% of the total weight of the nano-fertilizer composition and the size of the nanoparticle is in the range of 1-1000 nanometers.
• the plant nutrient is urea.
• Figure 1 is a schematic diagram that shows the formation of nutrient nanoparticles encapsulated inside PEI-Sokolan PA25 cross-linked nanoparticle system.
• Figure 2 is a Transmission electron micrographs for nano urea.
• the dark objects are nanoparticles.
• Figure 3 shows the Field Emission Scanning Electron Microscopy (FE-SEM) image of nano urea and corresponding particle size distribution.
• Figure 4 shows the dynamic light scattering data and zeta potential of the particles.
• nanoparticle refers to any particle having an average diameter of less than 1000 nanometers (nm).
• nanoparticles have an average diameter of less than 300 nm, less than 100 nm, less than 50 nm, less than 25 nm, less than 10 nm or less than 5 nm.
• each nanoparticle has a diameter of less than 300 nm, less than 100 nm, less than 50 nm, less than 25 nm, less than 10 nm or less than 5 nm.
• nanoparticle formulation or “nanoparticle composition” are used interchangeably with reference to any substance that contains at least one nanoparticle.
• a nanoparticle formulation is a uniform collection of nanoparticles.
• Nanoparticle formulation could contain nanoparticles having diameters in a range from 1 nm to 1000 nm, 5 nm to 500 nm, 5 nm to 300 nm, 5 nm to 100 nm, 5 nm to 50 nm or below 5 nm.
• the nanoparticle formulation could also have a bi-modal size distribution where some particles could he in a range of 5-50 nm and remaining could he in the range of 50 nm to 1000 nm.
• the term plant nutrient means mineral nutrients which include the broad class of macronutrient and micronutrient.
• the macronutrient further includes primary nutrient such as nitrogen (N), phosphorous (P) and potassium (K) and secondary nutrients such as calcium (Ca), magnesium (Mg) and sulfur (S).
• micronutrients includes boron (B), copper (Cu), iron (Fe), chloride (Cl), manganese (Mn), molybdenum (Mo) and zinc (Zn).
• a liquid formulation of nano fertilizer can be applied through spray on leaves of plants. The nanoparticles enter the plant through the stomatai openings or cuticle and get absorbed in the plant system. The nanoparticles are further transported to different regions in the plant through the known mechanisms of nutrient transport inside plant.
• Urea is widely used as a fertilizer and it is believed that more than 80% of the world's urea production is used as a fertilizer. It has the highest nitrogen content (46%) of all solid nitrogen based fertilizers used. Urea in the soil is converted to ammonia by hydrolysis. The ammonia is then oxidized to nitrates by the bacteria present in the soil. The nitrates are then absorbed by the plants for its nutrients. Urea is also used as a base for the manufacture of many other nitrogen based fertilizers.
• synthetic polymers refer to oligomers and polymers containing amino groups, consideration is given, for example, to polyamines, polymeric polyamines, nitrogen-substituted vinyl polymers, polyoxazolines, polydiallyldimehtylammonium polymers, polyallylamine polymers, polypropylenimine and its dendrimers, polyethylenimine and its dendrimers, polyamidoamine and its dendrimers, and also copolymers and derivatives and combinations of two or more of the stated substances.
• Preferred oligomers and polymers containing amino groups comprise polyamines and polymeric polyamines, polyalkylenimines such as polyethylenimines and polypropylenimine s, for example, polyvinylamines, polyalkoxylated polyamines, ethoxylated polyamines, propoxylated polyamines, alkylated and benzylated polyamines, and also combinations of two or more of the aforementioned components.
• oligomers and polymers containing amino groups are polyethylenimines, polyethylenimine dendrimers, and also their copolymers, derivatives, and mixtures of at least two of these components.
• Suitable polyethylenimines may comprise linear or branched polyethylenimine polymers or oligomers having for example 10 or more monomer units, and also their derivatives, analogs, copolymers, and mixtures of at least two of these components.
• Suitable polyethylenimines may preferably comprise branched polyethylenimine.
• Polyethylenimine is a polymer with repeating units composed of the amine group and two carbon aliphatic CH2CH2 spacers.
• Linear polyethyleneimines contain all secondary amines, in contrast to branched PEIs which contain primary, secondary and tertiary amino groups.
• Polyethylenimines may be obtained through the polymerization of ethylenimine, and are available commercially on the market, in the form, for example, of the Lupasol® and Epomin® product families and there, in particular, in the form of the products Lupasol® G20, Lupasol® FG, Lupasol® G35, Lupasol® P, and Lupasol®1595 (the Lupasol® products are available from BASF (Florham Park, N.J., USA)), and also Epomin® SP-003, Epomin® SP-006, Epomin® SP-012, Epomin® SP- 018, Epomin® SP-200, Epomin® SP-1000, and Epomin® SP-1050 (the Epomin® products are available from Nippon Shokubai (Osaka, Japan)).
• the first step in the process of the present invention is to prepare aqueous solution of plant nutrient by dissolving it in water.
• Second step involves preparation of aqueous solution of synthetic polymer polyethyleneimine (PEI) by dissolving it in water. It is followed by drop wise addition of aqueous solution of PEI to aqueous solution of plant nutrient. After complete addition of PEI solution to plant nutrient solution, the resultant mixture is stirred for sufficient time to ensure homogeneous solution.
• the homogenously mixed PEI-plant nutrient solution may optionally be added to cross-linking agent like polyacrylic acid (Sokalan PA-25) solution. After complete addition, the mixture is stirred for sufficient time.
• the resultant solution formed is colloidal dispersion of nanoparticles of urea.
• the pH of the colloidal suspension of nano-urea is in range from pH 4 to 6.
• Urea is obtained from Avra having specification of Mol. wt. 60.06 g/mol and density- 1.32 g/cm 3 .
• Lupasol WF is obtained from BASF having specification of Mol. wt. 25,000 g/mol, concentration upto 99% and density 1.10 g/cm 3 .
• Lupasol G-100 is obtained from BASF having specification of Mol. wt. 5,000 g/mol, concentration upto 50% and density 1.08 g/cm 3 .
• Sokalan PA -25 CL PN is obtained from BASF having specification Mol. wt. 4000 g/mol, concentration upto 49% and density 1.26 g/cm 3 .
• Sokalan CP 5 is obtained from BASF having specification Mol. wt. 70,000 g/mol, concentration upto 40% and density 1.30 g/cm 3 .
• Mechanism The presence of amine groups in the PEI molecule attracts nutrient molecules such as urea for example, which in water can have a delta negative (from oxygen in carbonyl) and delta positive charges on Nitrogen due to resonating structure. This leads to weak attachment of urea molecule to amine groups of PEI.
• Sokalan PA- 25 acts as a cross-linking molecule, thus leading to the formation of PEI-Sokalan PA- 25 cross linked nanoparticle, which has urea embedded inside the nanoparticle.
• polymer nanoparticle acts as a carrier of urea as illustrated in Figure 1. This process is applicable to other nutrients also and has been disclosed in examples below.
• Example 1 Process for formation of Nano-urea
• urea is taken as plant nutrient.
• urea powder 10.8 g is taken in a beaker and dissolved in 10 ml of distilled water.
• lOmL of Lupasol-WF solution is fdled in burette and then added drop-wise to urea solution.
• the resultant mixture is stirred for 15 minutes to ensure homogeneous solution.
• the dark dots in the image are nanoparticles clearly showing the ultrasmall size of nano urea (size range 1-30 nm).
• Scanning electron microscopy (SEM) image and corresponding particle size distribution are illustrated in Figure 3. SEM is carried out by using FEI Nova NanoSEM 450 instrument. Small white dots in the image of Figure 3 are nanoparticles of urea.
• Figure 4 shows the dynamic light scattering data which shows a bimodal distribution of nanoparticles. This gives the hydrodynamic diameter of the nanoparticles. Data for zeta potential is also shown. The zeta potential of the particles is -42 mV indicating that the nanoparticles are negatively charged.
• Example 2 Process for synthesis of 1000 lit (1 KL) of Nano-urea at pilot plant
• Example 3 Process for synthesis of nano urea while varying the concentration of urea in the final formulation (1% urea to 55% urea)
• l% Urea a. In a beaker, 0.24g of urea powder is dissolved in 4mL distilled water. In another beaker, 0.0022g of Lupasol WF is dissolved in 2mL distilled water. 2mL of Lupasol-WF solution is fdled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b . After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 6mL of Lupasol WF- urea solution is added dropwise to 18mL of 0. 1% Sokalan PA-25 solution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• 5 % Urea a. In a beaker, 1.2g of urea powder is dissolved in 5mL distilled water. In another beaker, 0.0022g of Lupasol WF is dissolved in 2mL distilled water. 2mL of Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b. After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 7mL of Lupasol WF- urea solution is added dropwise to 17mL of 0. 1% Sokalan PA-25 solution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• Urea 55% Urea: a. In a beaker, 13.2g of urea powder is dissolved in 15mL distilled water. In another beaker, 0.0022g of Lupasol WF is dissolved in 2mL distilled water. 2mL of Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b . After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 17mL of Lupasol WF- urea solution is added dropwise to 7mL of 0. 1% Sokalan PA-25 solution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• Example 4 Process for synthesis of nano urea while varying the initial (starting) concentration of Lupasol from 0.5% to 1%
• Lupasol 0.5%
• a In a beaker, 2.4g of urea powder is dissolved in 7mL distilled water. In another beaker, 0.0275g of Lupasol WF is dissolved in 5mL distilled water. 5mL of Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution.
• b After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• 12mL of Lupasol WF- urea solution is added dropwise to d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• 1% Lupasol a. In a beaker, 2.4g of urea powder is dissolved in 7mL distilled water. In another beaker, 0.0555g of Lupasol WF is dissolved in 5mL distilled water. 5mL of Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b. After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 12mL of Lupasol WF- urea solution is added dropwise to 12mL of 0. 1% Sokalan PA-25 solution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• Example 5 Process for synthesis of nano urea while varying the initial (starting) concentration of Sokolan PA 25: (Sokolan was varied from 0.5% to 1%) [0061] Sokolan 0.5%: a. In a beaker, 2.4g of urea powder is dissolved in 7mL distilled water. In another beaker, 0.0022g of Lupasol WF is dissolved in 2mL distilled water. 2mL of Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b. After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• Sokolan 1% a. In a beaker, 2.4g of urea powder is dissolved in 7mL distilled water. In another beaker, 0.0022g of Lupasol WF is dissolved in 2mL distilled water. 2mL of Lupasol-WF solution is fdled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b. After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 9mL of Lupasol WF- urea solution is added dropwise to 15mL of 1% Sokalan PA-25 solution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• Example 6 Process for synthesis of nano urea by varying polymer molecular weights (PEI molecular weight is varied from 5000 to 25000 Da; and Sokolan molecular weight is varied from 5000 to 70,000 Da)
• Lupasol WF Molecular weight 25000 Da; Sokolan CP5 (a co-polymer of acrylic acid and maleic acid): Molecular weight: 70,000 Da.
• c. Lupasol solution is added dropwise to urea solution and stirred for 15 minutes.
• 0.26g Sokalan CP-5 is dissolved in 80mL distilled water. e.
• a. In a beaker, 0.00432g of Lupasol G-100 is dissolved in lOmL distilled water.
• b. In another beaker, 10 grams of urea is dissolved in 10 mL of water.
• c. Lupasol solution is added drop wise to urea solution and kept for stirring for 15 minutes.
• 0.052g Sokalan CP-5 is dissolved in 80mL distilled water.
• Example 7 Process for synthesis of nano urea by using a conventional cross-linking agent such as sodium triphosphate (STPP) instead of Polyacrylic acid (Sokolan) crosslinking polymer a.
• STPP sodium triphosphate
• Sokolan Polyacrylic acid
• Example 8 Process for synthesis of nano diammonium phosphate (DAP) a.
• DAP powder is dissolved in lOmL distilled water.
• 0.011g of Lupasol WF is dissolved in lOmL distilled water.
• lOmL of Lupasol -WF solution is filled in burette and then added drop-wise to DAP solution. The solution is kept on stirring for uniform mixing and dissolution.
• b. After complete addition of Lupasol WF solution to DAP solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• 20mL of Lupasol WF- DAP solution is added dropwise to lOOmL of 0.
• Example 9 Process for synthesis of nano Monoammonium phosphate (MAP) in the absence of cross-linking agent a.
• MAP itself acts as a polymer cross-linking agent.
• b. In a beaker, 10g of MAP powder is dissolved in 20mL distilled water.
• MAP solution is added drop-wise to 80mL 0.1% Lupasol- WF solution. The solution is kept on stirring for uniform mixing and dissolution.
• d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• Example 10 Process for synthesis of nano Monopotassium phosphate (MKP) in the absence of cross-linking agent a. In this process MKP itself acts as a polymer cross-linking agent. b. In a beaker, 10g of MKP powder is dissolved in 20mL distilled water. c. Then MKP solution is added drop-wise to 80mL 0.1% Lupasol- WF solution. The solution is kept on stirring for uniform mixing and dissolution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• MKP Monopotassium phosphate
• Example 11 Process for synthesis of nano Dipotassium phosphate (DKP) in the absence of cross-linking agent a. In this process DKP itself acts as a polymer cross-linking agent. b. In a beaker, 10g of DKP powder is dissolved in 20mL distilled water. c. Then DKP solution is added drop-wise to 80mL 0.1% Lupasol - WF solution. The solution is kept on stirring for uniform mixing and dissolution. d. After complete addition, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles.
• DKP Dipotassium phosphate
• Nano NPK 5-5-5 preparation is demonstrated:
• Nano-urea nano-particles a. In a beaker, 6.6g of urea powder is dissolved in 2.5mL distilled water. 2.5mL of 0.1% Lupasol-WF solution is filled in burette and then added drop-wise to urea solution. The solution is kept on stirring for uniform mixing and dissolution. b. After complete addition of Lupasol WF solution to urea solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution. c. Finally, 5mL of Lupasol WF-Urea solution is added dropwise to 25mL of 0. 1% Sokalan PA-25 solution. d.
• Nano-DKP and Nano-MAP nano-particles a. In a beaker, 5.7g of DKP powder and 1.2g of MAP powder was dissolved in 30mL 0.1% Lupasol-WF solution. b. After complete dissolution, the mixture is stirred for 30 mins and the resultant solution formed is colloidal dispersion of nanoparticles. c. Once all nano-particles are formed individually, 30mL of nano- DKP and nano-MKP solution is added to 30mL nano-urea solution. d. The resultant solutions are stirred on for 30 mins for homogeneous mixing of the solutions.
• Example 13 Process for synthesis of nano calcium a.
• 12g of calcium nitrate powder is dissolved in lOmL distilled water.
• 0.011g of Lupasol WF is dissolved in lOmL distilled water.
• lOmL of Lupasol-WF solution is filled in burette and then added drop-wise to calcium nitrate solution. The solution is kept on stirring for uniform mixing and dissolution.
• b. After complete addition of Lupasol WF solution to calcium nitrate solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• Example 14 Process for synthesis of Nano-magnesium a.
• 12g of magnesium sulphate powder is dissolved in lOmL distilled water.
• 0.011g of Lupasol WF is dissolved in lOmL distilled water.
• lOmL of Lupasol-WF solution is fdled in burette and then added drop-wise to magnesium sulphate solution.
• the solution is kept on stirring for uniform mixing and dissolution.
• b After complete addition of Lupasol WF solution to magnesium sulphate solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• Example 15 Process for the synthesis of nano - boron a.
• 12g of borax powder is dissolved in lOmL warm distilled water.
• 0.011g of Lupasol WF is dissolved in lOmL distilled water.
• lOmL of Lupasol-WF solution is fdled in burette and then added drop-wise to borax solution. The solution is kept on stirring for uniform mixing and dissolution.
• b. After complete addition of Lupasol WF solution to borax solution, the resultant mixture is stirred for 15 mins to ensure homogeneous solution.
• 20mL of Lupasol WF- borax solution is added dropwise to 100mL of 0.1% Sokalan PA-25 solution.
• d. After 12 hrs a turbid colloidal dispersion of nanoparticles of boron can be seen.

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