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US-12623979-B2 - Nitrification inhibitors to improve fertilizer efficiency

US12623979B2US 12623979 B2US12623979 B2US 12623979B2US-12623979-B2

Abstract

A fertilizer composition including a) one or more solid nitrogen sources, and b) a liquid fertilizer additive composition.

Inventors

  • Gary David McKnight
  • Randall Linwood Rayborn

Assignees

  • SOILGENIC TECHNOLOGIES, LLC

Dates

Publication Date
20260512
Application Date
20240509

Claims (20)

  1. 1 . An inhibited aqueous fertilizer composition comprising, a) one or more aqueous nitrogen sources, and b) a liquid nitrification inhibitor solution, wherein the liquid nitrification inhibitor solution comprises: i) a nitrification inhibiting reaction composition, and ii) a Non-aqueous Organic Solvent Delivery System (NOSDS), wherein the nitrification inhibiting reaction composition comprises (1) one or more biodegradable polymers and/or oligomers, and (2) a non-aqueous reaction medium, wherein the one or more biodegradable polymers and/or oligomers comprise a one or more dicyandiamide-formaldehyde reaction products, wherein the one or more dicyandiamide-formaldehyde reaction products are formed in the non-aqueous reaction medium, wherein the non-aqueous reaction medium comprises a non-aqueous polar, aprotic solvent (NAPAOL), wherein the reaction parameters are set to maintain a non aqueous state to prevent the degradation of the dicyandiamide's cyano-functionality, wherein the loss of cyano functionality negatively impact the one or more biodegradable polymers and/or oligomers’ nitrification inhibition, wherein the NOSDS comprises the (1) NAPAOL and optionally, (2) one or more non-aqueous members selected from the group consisting of a) one or more additional polar, aprotic solvents, b) one or more aprotic solvents, c) one or more protic solvent, and d) combinations thereof, wherein the NOSDS's properties are: a) environmentally safe, b) flashpoint above 145° F., c) safe for contact with humans and animals, d) able to maintain the one or more dicyandiamide-formaldehyde reaction products at levels of 1-50% in down to at least 10° C., and e) able to provide solubility of the one or more dicyandiamide-formaldehyde reaction products in the one or more aqueous nitrogen sources, wherein the inhibited aqueous fertilizer composition is made by dissolving the liquid nitrification inhibitor solution-into the one or more aqueous nitrogen sources, and wherein said liquid nitrification inhibitor solution comprises 0.05-10% of the inhibited aqueous fertilizer composition.
  2. 2 . The inhibited aqueous fertilizer composition of claim 1 , wherein the one or more aprotic solvents are selected from the group consisting of: a one or more polyols capped with acetate or formate wherein a polyol portion is selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose and glycerin, b) one or more alkylene glycol alkyl ether acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and tripropylene glycol butyl ether acetate, c) isophorone, d) one or more diesters selected from the group consisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethyl glutarate, e) dimethylacetamide, f) dimethylformamide, g) dimethyl-2-imidazolidinone, and h) limonene.
  3. 3 . The inhibited aqueous fertilizer composition of claim 2 , wherein the one or more urease inhibitor comprises one or more phosphoramides.
  4. 4 . The inhibited aqueous fertilizer composition of claim 3 , wherein the one or more phosphoramides comprises one or more members selected from the group consisting of a) one or more aliphatic phosphoric triamide, b) one or more N-alkyl thiophosphoric triamides and c) combination thereof.
  5. 5 . The inhibited aqueous fertilizer composition of claim 4 , wherein one or more N-alkyl thiophosphoric triamides comprises N-(n-butyl) thiophosphoric triamide.
  6. 6 . The inhibited aqueous fertilizer composition of claim 1 , wherein the fertilizer composition further comprises one or more members selected from the group consisting of: a) surfactants, buffers, fragrance/odor masking agents, colorants, flow modifiers, silicas, and hydrophobized silicas, and b) one or more non-aqueous organic liquids selected from the group consisting of one or more polar aprotic solvents, one or more aprotic solvents, and one or more protic solvents, c) one or more biologics selected from the group consisting of: i) Bacillus biologics, ii) Azospirillum biologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria, vi) Cyanobacteria, vii) Herbaspirillum , viii) Burkholderia , ix) Pseudomonas, x ) Gluconacetobacter , xi) Enterobacter , xii) Klebsiella , xiii) Burkholderia , xiv) Bradyrhiwbium species, xv) Bradyrhiwbium japonicum , xvi) Rhizobium meliloti , xvii) Laccaria bicolor , xviii) Glomus imraradices timanita, xix) Actinomyces , xx) Penicillium , xxi) Mesorhizobiwn cicero , xxii) one or more insecticidal or insect repellent microbial species and strains are selected from the group consisting of: Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticillium lecanii, Isarfofumosarosea Lecanicillium muscarium, Streptomyces microflavus , and Muscodor albus, xxiii) one or more nematodal microbial species and strains are selected from the group consisting of: Myrothecium verrucaria, Pasteuria species, Pasteuria Metarhizium species, and Flavobacteriwn species xxiv) Reynoutria sachalinensis and xxv) one or more antifungal, antimicrobial and/or plant growth promoting microbial species and strains are selected from the group consisting of: Gliocladium species, and one or more Pseudomonas species are selected from the group consisting of: Pseudomonas fluorescens, Pseudomonas fluorescens, Putida and P. chlororaphis , Pseudomonasfluorescens VP5, Pseudomonas diazotrophicus, Enterobacter cloacae, Trichodema species, Trichoderma virens, Trichoderma atroviride strains, Coniothyrium minitans, Gliocladium species, Gliacladium virens, Gliacladium roseum , and Trichodemw harzianum species, d) and one or more biologically active agents selected from the group consisting of: i) one or more additional nitrification inhibitors, ii) one or more members selected from the group consisting of (1) one or more pesticides, (2) one or more herbicides, (3) one or more fungicides, (4) one or more insecticides and (5) combinations thereof, and iii) one or more urease inhibitors.
  7. 7 . The inhibited aqueous fertilizer composition of claim 6 , wherein the one or more additional nitrification inhibitors are selected from the group consisting of: 2-chloro-6-trichloromethyl) pyridine, 4-amino-1,2,4,6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate, dimethylpyrazole organic and inorganic salts, and 2-amino-4-chloro-6-methylpyrimidine.
  8. 8 . The inhibited aqueous fertilizer composition of claim 7 , wherein the one or more additional nitrification inhibitors comprise dicyandiamide.
  9. 9 . The inhibited aqueous fertilizer composition of claim 6 , wherein the one or more urease inhibitor comprises one or more phosphoramides.
  10. 10 . The inhibited aqueous fertilizer composition of claim 6 , wherein the one or more phosphoramides comprises one or more members selected from the group consisting of a) one or more aliphatic phosphoric triamide, b) one or more N-alkyl thiophosphoric triamides and c) combination thereof.
  11. 11 . The inhibited aqueous fertilizer composition of claim 6 , wherein one or more N-alkyl thiophosphoric triamides comprises N-(n-butyl) thiophosphoric triamide.
  12. 12 . The inhibited aqueous fertilizer composition of claim 1 , wherein the liquid nitrification inhibitor solution further comprises one or more members selected from the group consisting of: a) one or more members selected from the group consisting of surfactants, buffers, fragrance/odor masking agents, and colorant, b) one or more biologics selected from the group consisting of: i) Bacillus biologics, ii) Azospirillum biologics, iii) Azobacter biologics iv) Gluconacetobacter biologics, v) Phosphobacteria, vi) Cyanobacteria, vii) Herbaspirillum , viii) Burkholderia , ix) Pseudomonas, x ) Gluconacetobacter , xi) Enterobacter , xii) Klebsiella , xiii) Burkholderia , xiv) Bradyrhiwbium species, xv) Bradyrhiwbium japonicum , xvi) Rhizobium meliloti , xvii) Laccaria bicolor , xviii) Glomus imraradices timanita, xix) Actinomyces , xx) Penicillium , xxi) Mesorhizobiwn cicero , xxii) one or more insecticidal or insect repellent microbial species and strains are selected from the group consisting of: Telenomus podisi, Baculovirus anticarsia; Trichogramma pretiosum, Trichogramma gallai, Chromobacterium subtsugae, Trichoderma fertile, Beauveria bassiana, Beauveria bassiana, Beauveria bassiana, Paecilomyces jknwsoroseu, Trichoderma harzianum, Verticillium lecanii, Isarfofumosarosea Lecanicillium muscarium, Streptomyces microflavus , and Muscodor albus, xxiii) one or more nematodal microbial species and strains are selected from the group consisting of: Myrothecium verrucaria, Pasteuria species, Pasteuria Metarhizium species, and Flavobacteriwn species xxiv) Reynoutria sachalinensis and xxv) one or more antifungal, antimicrobial and/or plant growth promoting microbial species and strains are selected from the group consisting of: Gliocladium species, and one or more Pseudomonas species selected from the group consisting of: Pseudomonas fluorescens, Pseudomonas fluorescens, Putida and P. chlororaphis , Pseudomonasfluorescens VP5, Pseudomonas diazotrophicus, Enterobacter cloacae, Trichodema species, Trichoderma virens, Trichoderma atroviride strains, Coniothyrium minitans, Gliocladium species, Gliacladium virens, Gliacladium roseum , and Trichodemw harzianum species, and c) and one or more biologically active agents selected from the group consisting of: i) one or more additional nitrification inhibitors, ii) one or more members selected from the group consisting of (1) one or more pesticides, (2) one or more herbicides, (3) one or more fungicides, (4) one or more insecticides and (5) combinations thereof, and iii) one or more urease inhibitors.
  13. 13 . The inhibited aqueous fertilizer composition of claim 12 , wherein the one or more additional nitrification inhibitors comprise one or more nitrification inhibitors selected from the group consisting of 2-chloro-6-(trichloromethyl) pyridine, 4-amino-1,2,4,6-triazole-HCl, 2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide (DCD), thiourea, 1-mercapto-1,2,4-triazole, ammonium thiosulfate, dimethylpyrazole organic and inorganic salts, and 2-amino-4-chloro-6-methylpyrimidine.
  14. 14 . The inhibited aqueous fertilizer composition of claim 13 , wherein the one or more additional nitrification inhibitors comprises dicyandiamide.
  15. 15 . The inhibited aqueous fertilizer composition of claim 1 , wherein the one or more aqueous nitrogen sources comprise one or more members selected from the group consisting of a) urea, b) urea formaldehyde reaction products, c) ammonia, d) urea formaldehyde and ammonia reaction products, e) ammonium nitrate, f) ammonium sulfate, e) manure, f) compost liquid and g) combinations thereof.
  16. 16 . The inhibited aqueous fertilizer composition of claim 15 , wherein the one or more aqueous nitrogen sources comprise one or more members selected from the group consisting of a) urea, b) ammonium nitrate, and c) combinations thereof.
  17. 17 . The inhibited aqueous fertilizer composition of claim 1 , wherein the nitrification inhibiting reaction composition comprises the following one or more structures: a) wherein R 43 , R 44 , R 45 and R 46 are one or more members independently selected from the group consisting of: H and —CH 2 OH wherein at least one of R 43 , R 44 , R 45 and R 46 is —CH 2 OH, b) wherein R 47 , R 48 , R 49 , R 50 , R 51 and R 52 are one or more members independently selected from the group consisting of: H, and —CH 2 OH, c) wherein R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 are one or more members independently selected from the group consisting of: H and —CH 2 OH, and d) wherein R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 are one or more members independently selected from the group consisting of: H and —CH 2 OH, wherein x is 2-20, and wherein said one or more dicyandiamide-formaldehyde reaction products are made by using non-aqueous reaction conditions, and wherein said nonaqueous liquid nitrification inhibiting reaction composition comprises more than 10% by weight of said one or more structures.
  18. 18 . The inhibited aqueous fertilizer composition of claim 1 , wherein the NAPAOL comprises one or more polar, aprotic solvents selected from the group consisting of: (1) dimethyl sulfoxide, (2) a one or more sulfoxides selected from the group consisting of (a) dialkylsulfoxide, (b) diarylsulfoxide, and (c) alkylarylsulfoxide having the formula: R 9 S(O) x R 10 wherein R 9 and R 10 are each independently a C 1-6 alkylene group, an aryl group, or C 1-3 alkylenearyl group or R 9 and R 10 together with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 9 and R 10 together are a C 1-6 alkylene group which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N, and P in the ring and x is 1 or 2, (3) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, (4) 1-Methyl-2-pyrrolidone, (5) one or more organo phosphorous liquids selected from the group consisting of hexamethylphosphoramide and one or more trialkylphosphates selected from the group represented by the formula: wherein: R 22 is alkyl radical —C 1 H 3 to —C 6 H 13 R 23 is alkyl radical —C 1 H 3 to —C 6 H 13 R 24 is alkyl radical —C 1 H 3 to —C 6 H 13 (6) 1,2-dimethyloxyethane, (7) 2-methoxyethyl ether, and (8) cyclohexylpyrrolidone.
  19. 19 . The inhibited aqueous fertilizer composition of claim 1 , wherein the one or more protic solvents are selected from the group consisting of: a) an alcohol from the family of C1-10 alkanols, b) one or more polyols selected from the group consisting of trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol, sorbitan, glucose, fructose, galactose, and glycerin, c) one or more poly(C1-10 alkylene) glycols represented by the structure: H(CtHu)vOH, wherein t is an integer: 1-10 u is an integer: 2-20 and v is an integer: 1-20, d) one or more alkylene glycols selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, and butylene glycol, e) isopropylidene glycerol, f) one or more alkylene glycol alkyl ethers selected from the group represented by the structure: wherein R 1 is: CH 3 , C 2 H 5 , C 3 H 7 or C 4 H 9 wherein R 2 is: H or the structure wherein R 3 is: H or CH 3 wherein R 4 is H or CH 3 and f is an integer between 1 and 15, g) one or more alkyl lactates selected from the group consisting of ethyl lactate, propyl lactate and butyl lactate, h) one or more alkanolamines selected from the group represented by the structure: wherein R 5 is: C 2 H 4 OR 8 or C 3 H 6 OH wherein R6 is: H, C2H4OR8 or C3H6OH wherein R 7 is: H, C 2 H 4 OR 8 or C 3 H 6 OH wherein R 8 is: (C 2 H 4 O) g H and g is an integer between 1-10, and i) glycerol carbonate.
  20. 20 . The inhibited aqueous fertilizer composition of claim 1 , wherein the NAPAOL comprises dimethyl sulfoxide.

Description

The present invention claims priority under 35 USC 120 and is a continuation of Ser. No. 16/154,640 filed Oct. 8, 2018, which in turn is a continuation in part of U.S. application Ser. No. 15/985,656 filed May 21, 2018, which is a continuation in part of U.S. application Ser. No. 15/967,575 filed Apr. 30, 2018, which is a continuation in part of U.S. application Ser. No. 15/854,319 filed Dec. 26, 2017, which in turn claims priority under 35 USC 120 to U.S. application Ser. No. 15/641,264 filed Jul. 4, 2017, which in turn claims priority under 35 USC 119 to U.S. Provisional Application No. 62/358,116 filed Jul. 4, 2016, the entire contents of all of which are incorporated by reference in their entireties. FIELD OF THE INVENTION In embodiments, the present invention relates to liquid formulations comprising nitrification inhibitors chemically bound within a polymer/oligomer, dispersed within a Non-aqueous Organic Solvent Delivery System (abbreviated as NOSDS) for application to nitrogen sources. The method of making these polymeric and/or oligomeric nitrification inhibitors comprise a non-aqueous polar, aprotic organo liquid (abbreviated as NAPAOL) that is utilized as the reaction medium for the reaction of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups selected from the group consisting of a) primary amines, b) secondary amines, c) amides, d) thiols, e) hydroxyls and f) phenols and wherein the process parameters are optimized for conserving the cyano group. A non-aqueous solvent delivery system (NOSDS) can be utilized to improve the physical properties of the liquid formulation wherein the NOSDS comprises the reaction medium, NAPAOL, aprotic solvents and protic solvents which are environmentally friendly, have flashpoints above 145° F. and are inherently rated safe for contact with humans and animals. In embodiments, the present invention relates to liquid formulations containing hydrophobic, biodegradable polymers dispersed within a Non-aqueous Organic Solvent Delivery System (NOSDS) and is designed to coat fertilizer granules with a hydrophobic film utilizing simple application equipment such as mixers, blenders and tumblers. This film can impede the dissolution of fertilizer components by water improving fertilizer efficiency. The NOSDS can be aprotic solvents, protic solvents and mixtures of protic and aproic solvents which are environmentally friendly, have flashpoints above 145° F., and are inherently rated safe for contact with humans and animals. The hydrophobic polymers are the reaction product of aldehyde(s) and nitrogen containing compounds. BACKGROUND OF THE INVENTION Fertilizer efficiency has become a major issue in the world. The major element of fertilizer is nitrogen (N). In one study, using data from over 800 experiments, it was estimated that only 51% of the N applied was recovered by cereals plant (Dobermann and Cassman 2005). In another study, it was reported that average N recovery in cereals in China was 30-35% (Fan 2004). Phosphorous is the second largest element in fertilizer compositions and its efficiency is even lower. It was estimated to be around 10-25% (Unsay 1979). Potassium is the third largest fertilizer composition and its efficiency is around 40% (Baligar VC 1986). One of the main factors for the low efficiency of fertilizers is due to the excellent water solubility of many of its components. In practice, fertilizers are often just applied once at the beginning of the growing season. After the application, nutrients from fertilizers are dissolved in water and released to soil in amounts that are too much for plants to absorb. The unabsorbed nutrients can be leached to the environment, and find their way to surface water such as ponds, lakes and rivers or continue to leach into the sub-surface water table contaminating many of the rural community water supplies. Low efficiency of fertilizer not only increases the cost of fertilization, but also contributes significantly to environmental pollution. In the case of nitrogen based fertilizers, one of the major mechanisms for its poor efficiency is the impact of biologically driven processes on water solubilized sources of nitrogen. Urea is the main component of most nitrogen fertilizers. In the presence of soil moisture, natural or synthetic ureas are dissolved and are converted to ammonium ion by bacterial activity, making the nitrogen available for plant uptake. Ammonium can be further converted by bacteria in soil to nitrate through a process called nitrification. Nitrate is also available for plant uptake. Excess ammonia not absorbed by plants can leach into water which can be toxic to water creatures (US EPA822-R-13-001). Excess nitrates can also leach into water, causing the increasing of nitrate concentration in the ground water. Consumption of nitrate contaminated water by human can cause methemoglobinemia (blue baby syndrome)(Kross, Hallberg et al. 1993). Moreov