Efficiency of man-made and/or natural organic based animal manure fertilizers by liberating the bound nutrients (macro and micro) through the use of organic, non-aqueous liquid delivery formulations containing organic poly (organicacids) and/or their salts

Abstract

The present invention relates to improving the efficacy of man-made and/or natural organic-based animal manure fertilizers by administration of an organic solvent formula containing polyorganic acids and/or their salts. The formulation liberates nutrient(s) that are normally bound in the soil as insoluble salts and complexes. These delivery formulations also provide an environmentally sound and inherently safe solvating system that improves diffusion of polyorganic acids to the granule fertilizer. These delivery formulations enable safe storage, transport and subsequent application or blending with solid or liquid fertilizers. The combined formulation and fertilizer can be applied to soil to provide improved efficacy of fertilizer by liberating nutrients bound in the soil for uptake by plant life.

Claims

1. A composition comprised of a) a liquid additive and b) fertilizer granules wherein: the liquid additive comprises a) polyorganic acids and/or their salts and b) an organic liquid solvating system wherein: the organic liquid solvating system comprises one or more protic solvents selected from the group consisting of 1) one or more alcohols selected from the group consisting of C.sub.1-10 alkanols 2) one or more polyols selected from the group consisting of poly(C.sub.1-10 alkylene) glycols, 3) one or more alkylene glycols selected from the group consisting of ethylene, propylene, and butylene glycol, 4) one or more members selected from the group consisting of glycerin, trimethylol propane, triethanol propane and pentaerythritol 5) one or more alkanolamines selected from the group consisting of: ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, 6) one or more alkylene glycol alkyl ethers selected from the group consisting of tripropylene glycol methyl ether, and tripropylene glycol butyl ether wherein: said polyorganic acids and/or their salts comprise one or more members selected from the group consisting of a) monomer, b) homopolymer, c) a copolymer and d) a terpolymer wherein said polyorganic acids composition comprises one or more members selected from the group consisting of aspartic acid, glutamic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and acrylic acid wherein the salts of the polyorganic acids are a result of a reaction with one or more neutralizing compounds selected from the group consisting of: NaOH, KOH, NH.sub.3, K.sub.2CO.sub.3, Na.sub.2CO.sub.3, KHCO.sub.3 and NaHCO.sub.3, wherein the polyorganic acids and/or their salts comprise 5-50% of the liquid additive and wherein the composition of the liquid additive comprises less than 1% water.

2. The composition of claim 1, wherein the composition of the liquid additive further comprises the protic solvent isopropylidene glycerol.

3. The composition of claim 1, wherein the liquid additive comprises protic solvents at 90% to 10% of the composition of the liquid additive.

4. The composition of claim 1, wherein the composition of the liquid additive further comprises the polyorganic acid citric acid.

5. The composition of claim 1, wherein the liquid additive further comprising one or more members selected from the group consisting of: surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, urease inhibitors, nitrification inhibitors and flow modifiers.

6. The composition of claim 5, wherein the composition comprises 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, thiourea, 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine.

7. The composition of claim 5, wherein the composition comprises one or more urease inhibitors selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

8. The composition of claim 6, wherein the composition further comprises the nitrification inhibitor 3,4-dimethylpyrazole phosphate.

9. The composition of claim 7, wherein the composition comprises the urease inhibitor N-(n-butyl) thiophosphoric triamide.

10. A composition comprising a) a liquid additive and b) fertilizer granules wherein: the liquid additive comprises a) polyorganic acids and/or their salts and b) an organic liquid solvating system, wherein: the organic solvating system comprises one or more aprotic solvents and one or more protic solvents, wherein the one or more aprotic solvents is selected from the group consisting of: dimethyl sulfoxide, dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having the formula
R.sub.1SOR.sub.2, wherein: R.sub.1 is methyl, ethyl, n-propyl, phenyl or benzyl and R.sub.2 is ethyl, n-propyl, phenyl or benzyl, alkyl carbonate selected from the group consisting ethylene, propylene and butylene carbonates, ethyl, propyl, or butyl lactate isophorone and/or dimethylsuccinate, dimethyl adipate, diethyl glutarate, dimethyl glutarate, wherein the one or more protic solvents is selected from the group consisting of: 1) one or more alcohols selected from the group consisting of C.sub.1-10 alkanols, 2) one or more polyols selected from the group consisting of and poly(C.sub.1-10 alkylene) glycols, 3) one or more alkylene glycol selected from the group consisting of ethylene, propylene, and butylene glycol, 4) one or more members selected from the group consisting of: glycerin, trimethylol propane, triethanol propane and pentaerythritol 5) one or more alkanolamines selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, 6) one or more alkylene glycol alkyl ethers selected from the group consisting of tripropylene glycol methyl ether, and tripropylene glycol butyl ether, wherein said polyorganic acids and/or their salts comprise one or more members selected from the group consisting of a) monomer, b) homopolymer, c) a copolymer and d) a terpolymer wherein said polyorganic acids' composition comprises one or more members selected from the group consisting aspartic acid glutamic acid maleic anhydride itaconic anhydride citraconic anhydride and acrylic acid, wherein the salts of the polyorganic acids are the result of the reaction with one or more neutralizing compounds selected from the group consisting of: NaOH, KOH, NH.sub.3, K.sub.2CO.sub.3, Na.sub.2CO.sub.3, KHCO.sub.3 and NaHCO.sub.3, wherein the polyorganic acids and/or their salts comprise 5-50% of the liquid additive, and wherein the composition of the liquid additive comprises less than 1% water.

11. The composition of claim 10, wherein the composition of the liquid additive further comprises the protic solvent isopropylidene glycerol.

12. The composition of claim 10, wherein the composition of the liquid additive further comprises the polyorganic acid citric acid.

13. The composition of claim 10, wherein the composition of the liquid additive comprises a ratio of protic solvent to aprotic solvent of 90/10 to 10/90% and wherein the organic liquid solvating system comprises 10 to 90% of the liquid additive composition.

14. A composition comprising a) a liquid additive and b) fertilizer granules wherein the liquid additive comprises a) polyorganic acids and/or their salts and b) dimethyl sulfoxide wherein said polyorganic acids and/or their salts comprise one or more members selected from the group consisting of a) monomer, b) homopolymer, c) a copolymer and d) a terpolymer wherein said polyorganic acids' composition comprises one or more polyorganic acids selected from the group consisting of aspartic acid glutamic acid maleic anhydride itaconic anhydride citraconic anhydride and acrylic acid, wherein the salts of the polyorganic acids are the result of the reaction with one or more neutralizing compounds selected from the group consisting of: NaOH, KOH, NH.sub.3, K.sub.2CO.sub.3, Na.sub.2CO.sub.3, KHCO.sub.3 and NaHCO.sub.3, wherein the polyorganic acids and/or their salts comprise 5-50% of the liquid additive, and wherein the composition of the liquid additive comprises less than 1% water.

15. The composition of claim 14, wherein the fertilizer granule comprises one or more members selected from the group consisting of a. Urea b. monoammonium phosphate c. diammonium phosphate, and d. animal manure.

16. The composition of claim 14, wherein the composition of the liquid additive further comprises the polyorganic acid citric acid.

17. The composition of claim 14, wherein the liquid additive further comprising one or more members selected from the group consisting of: surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, urease inhibitor(s), nitrification inhibitor(s) and flow modifiers.

18. The composition of claim 17, wherein the composition comprises one or more 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, thiourea, 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine.

19. The composition of claim 17, wherein the composition comprises one or more urease inhibitors selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

20. The composition of claim 18, wherein the composition further comprises the nitrification inhibitor 3,4-dimethylpyrazole phosphate.

21. The composition of claim 19, wherein the composition comprises the urease inhibitor N-(n-butyl) thiophosphoric triamide.

Description

EXAMPLE 1

(1) 400 grams of ethylene glycol was charged to a vessel, placed under strong agitation and then heated to 60 C. 222.2 grams of polyaspartate-potassium salt/90% NVS was then slowly charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. After one hour the vessel was sealed and a vacuum of 200 mm or less was pulled to remove water. The mixture was cooled to <30 C. and then packaged off in an appropriate container.

EXAMPLE 2

(2) 120 grams of Example 1 was heated to 60 C., placed under agitation and then 80 grams of propylene glycol was charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 3

(3) 120 grams of Example 1 were heated to 60 C., placed under agitation and then 80 grams of glycerin were charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 4

(4) 120 grams of Example 1 were heated to 60 C., placed under agitation and then 40 grams of ethylene glycol and 40 grams of tripropylene glycol monomethyl ether were charged to the vessel. The combination was mixed for 30 minutes and then cooled to <40 C. and packaged off.

EXAMPLE 5

(5) 450 grams of ethylene glycol was charged to a vessel, placed under strong agitation and then heated to 60 C. 300 grams of a polysuccinimide (5000 average molecular weight) was then slowly charged to the vessel and mixed until completely dispersed. The mixture was then heated to 140 C. and held until all particles dissolved (1.5 hrs). The mix was then cooled to 50 C. 147 grams of KOH flakes were slowly charged to the mix at a rate to maintain temperature of 60-80 C. The formulation was mixed until all KOH flakes (100%) were dissolved. The mix was then cooled to 40 C. and then placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. The mixture was cooled to <30 C. and then packaged off in an appropriate container.

EXAMPLE 6

(6) 58.54 grams of Example 5 were charged to a vessel and then placed under strong agitation and then heated to 60 C. 65.4 grams of ethylene glycol were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 7

(7) 58.54 grams of Example 5 were charged to a vessel and then placed under strong agitation and then heated to 60 C. 35.4 grams of ethylene glycol and 30 grams of dimethyl glutarate were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 8

(8) 58.54 grams of Example 5 were charged to a vessel and then placed under strong agitation and then heated to 60 C. 65.4 grams of glycerin were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 9

(9) 104.3 grams of Example 5 were charged to a vessel and then placed under strong agitation and then heated to 60 C. 45.7 grams of ethylene glycol were then charged to the vessel and mixed for 30 minutes. After 30 minutes, the mixture was cooled to 38 C. and then packaged off in an appropriate container.

EXAMPLE 10

(10) 183.12 grams of dimethyl sulfoxide was charged to a vessel, placed under strong agitation and then heated to 60 C. 78.48 grams of a polysuccinimide (5000 average molecular weight) was then slowly charged to the vessel and mixed until completely dispersed. 72.74 grams of DI water was charged to the vessel and then 49.07 grams of NH4OH/28% were slowly charged holding the mixture's temperature at 60-80 C. It was mixed for one hour and then placed under a vacuum of 50 mm with a slight N.sub.2 sparge until distillation ceases. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 11

(11) 282.52 grams of dimethyl sulfoxide was charged to a vessel, placed under strong agitation and then heated to 60 C. 146.23 grams of a partial sodium hydroxide neutralized polyacrylic acid (Kemira 5847) was then charged to the vessel and mixed for 15 minutes. A vacuum of 38 mm was applied until distillation ceases. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 12

(12) 250 grams of ethylene glycol, 250 grams of L-aspartic acid and 2.94 grams of phosphoric acid/85% were charged to a vessel, then placed under strong agitation and then heated to 175 C. After 5 hrs. 64.3 grams of distillate were collected and the batch was cooled to 60 C. 97.44 grams KOH flake (100%) was then slowly charged to the vessel at a rate that allowed the batch temperature to be 60-80 C. and mixed until completely dissolved. It was then placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. After one hour, an FTIR scan was run to determine if the presence of ester had been eliminated. The mixture was sampled every 30 minutes until traces of esters had been eliminated. After the ester peak was eliminated, 281.08 grams of ethylene glycol were charged and the resulting mixture was mixed for 30 minutes. The mix was then cooled to 40 C. and then packaged off in an appropriate container.

EXAMPLE 13

(13) 71.58 grams of acetone was charged to a vessel and then 12.48 grams of maleic anhydride and 16.49 grams itaconic anhydride and 0.98 grams of benzoyl peroxide were charged to the vessel. Very slow agitation was used until the maleic briquettes were dissolved. The vessel was then sealed and inerted with N.sub.2 and the batch was heated to 60 C. and held at 55-65 C. for five hours. After five hours, the batch was cooled to 35 C. and 43.45 grams of ethylene glycol was charged. A vacuum was then pulled on the vessel slowly decreasing the pressure based on the distillation rate while heating the batch back to 55-65 C. When distillation ceases, the vacuum was broken with N.sub.2 and then 15.39 grams of KOH flake (100%) were slowly charged in order to hold temperature at 60-80 C. When KOH flakes were completely dissolved, the mix was placed under high shear agitation by using an overhead mixer equipped with a cowles blade while maintaining the batch temperature at 60-80 C. for 1 hour. Thereafter the mix was checked using an FTIR scan. The FTIR scan was run and checked every 30 minutes for the disappearance of the ester peak. After the ester peak disappeared, 89.63 grams of ethylene glycol were charged, and the batch was then mixed 30 minutes and cooled to <40 C. and then off-loaded into the appropriate container.

EXAMPLE 14

(14) 45 grams of Example 12 were mixed with 10 grams of N-Yield (an urease inhibitor in an organic liquid), 40 grams of N-Bound (a nitrification inhibitor in an organic liquid) and 5 grams of glycerin. The resulting fluid product was then off-loaded into the appropriate container.

(15) The following references are incorporated by reference in their entireties.

(16) TABLE-US-00001 4,839,461 Boehmke 4,172,072 Ashmead 4,799,953 Danzig 4,813,997 Kinnersley 4,863,506 Young 5,059,241 Young 5,047,078 Gill 5,350,735 Kinnersley 5,593,947 Kinnersley 5,783,523 Koskan 5,814,582 Koskan 6,753,395 Sanders 6,756,461 Sanders 6,818,039 Sanders 8,043,995 Sanders 8,016,907 Sanders 8,025,709 Sanders

(17) It is contemplated and therefore within the scope of the present invention that any feature that is described above can be combined with any other feature that is described above. When mixtures, formulations and/or compositions are discussed, it should be understood that those mixtures, formulations and/or compositions are contemplated as being parts of bigger mixtures, formulations and/or compositions. Further, if a composition is enumerated, methods using and methods of making that composition are contemplated and within the scope of the present invention. When a range is discussed, it is contemplated and therefore within the scope of the invention that any number that falls within that range is contemplated as an end point generating a plurality of sub-ranges within that range. For example if a range of 1-10 is given, 2, 3, 4, 5, 6, 7, 8, and 9 are contemplated as end points to generate a sub-range that fit within the scope of the enumerated range. Moreover, it should be understood that the present invention contemplates minor modifications that can be made to the compositions and methods of the present invention. In any event, the present invention is defined by the below claims.