COMPOSITONS AND METHODS COMPRISING NITRIFICATION INHIBITORS CONTAINING A MIXTURE OF PROTIC AND APROTIC SOLVENT SYSTEMS

• US 20150299062A1
• Filed: 04/17/2015
• Published: 10/22/2015
• Est. Priority Date: 04/17/2014
• Status: Active Grant

• Current Assignee: Soilgenic Technologies LLC
• Original Assignee: David Parker, Gary David Mcknight, Randall Linwood Rayborn, Raymond Patrick Perkins, Wei Xu, Zehui Yang
• Inventors: McKnight, Gary David, Rayborn, Randall Linwood, Xu, Wei, Perkins, Raymond Patrick, Yang, Zehui, Parker, David
• Granted Patent: US 9,650,306 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C05C 9/00 Fertilisers containing urea or urea compounds
• CPC Class Codes: C05G 3/90 for affecting the nitrification of ammonium compounds or urea in the soil
• CPC Class Codes: C09K 15/18 containing an amine or imine moiety
• CPC Class Codes: C09K 15/22 containing an amide or imide moiety
• CPC Class Codes: C09K 15/28 containing nitrogen, oxygen and sulfur
• CPC Class Codes: C09K 15/30 containing heterocyclic ring with at least one nitrogen atom as ring member
• CPC Class Codes: Y02P 60/21 Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Abstract

The present invention relates to increasing longevity of the nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors. The liquid formulation can also be comprised of nitrification inhibitors and optionally urease inhibitors that are blended solutions of each. The nitrification inhibitors are present in a mixture that comprises both a protic and an aprotic solvent system. The novel formulations are designed to be applied to fertilizers, especially urea and manure based fertilizers. The delivery formulations provide an environmentally sound and inherently safe solvating system that improves the storage stability of the urease inhibitors by utilizing liquid organic non-water containing solvents, maintains the nitrification inhibitors in solution to storage temperatures of at least 10° C., and provides improved application to fertilizer of nitrification inhibitors. These delivery formulations enable safe storage, transport and subsequent application or blending with urea-based or manure-based fertilizers that can be applied to soil in either a liquid or granular form to provide improved nitrogen retention in the soil for uptake for plant life.

Claims

1. A composition comprising one or more nitrification inhibitors in an organic liquid solvating system comprising a mixture of aprotic solvents and protic solvents

wherein a first aprotic solvent is dimethyl sulfoxide, dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having the formula

R₁—

S(O)—

R₂,

wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and R₂ is ethyl, n-propyl, phenyl or benzyl,

and a protic solvent is one or more of

a) an alcohol or polyol from the family of alkylene and poly(alkylene) glycols

b) an alkylene glycol selected from the group consisting of ethylene, propylene, and butylene glycol,

c) glycerin,

d) an alkylene glycol alkyl ether selected from the group comprising of dipropylene glycol methyl ether, tripropylene glycol methyl ether, and tripropylene glycol butyl ether

e) an alkanolamine selected from the group comprising of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and/or

f) ethyl, propyl, or butyl lactate

wherein the organic liquid solvating system meets the following criteria;

a. environmentally safe

b. has a flashpoint above 145°

F.

c. inherently rated safe for contact with humans and animals

d. able to provide improved and even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules

e. results in a composition comprising at least one of nitrification inhibitor at levels of 1-50% with a Chill Point <

40°

F.

2. The composition of claim 1, wherein the nitrification inhibitor comprises one or more of the following 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, 7) 3,4-dimethylpyrazole phosphate.

3. The composition of claim 1, wherein one of the aprotic solvents in the mixture is dimethyl sulfoxide.

4. The composition of claim 3, wherein dimethyl sulfoxide comprises between about 10 and 90% of the composition.

5. The composition of claim 1 wherein the one or more nitrification inhibitors comprises one or more of the following:

1) dicyandiamide,

     2) 2-chloro-6 trichloromethyl)pyridine,

     3) 4-amino-1,2,4-6-triazole-HCl,

     4) 2,4-diamino-6-trichloromethyltriazine,

     5) thiourea,

     6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, or

     7) 3,4 dimethylpyrazole phosphate;

in a formulation wherein nitrification inhibitor(s) is/are present in an amount that is between about 5-45% of a total formulation amount and the composition also contains a mixture of DMSO and one or more protic solvents in ratios that are between about 20/80 to 80/20.

6. The composition of claim 1, further comprising one or more of aprotic solvents present in the amount of 0.5-40%, surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed nitrification inhibitors, dispersed urease inhibitor(s), crystallization inhibitors and/or flow modifiers.

7. The composition of claim 1, wherein the one or more nitrification inhibitors comprises one or more of the following 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-Mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, 7) 3,4 dimethylpyrazole phosphate in a formulation wherein nitrification inhibitor(s) is/are present in an amount that is between about 5-45% of a total formulation amount and the formulation also comprises N-(n-butyl) thiophosphoric triamide in an amount that is between about 5-45% of the total formulation amount.

8. The composition of claim 1, wherein the composition is substantially free of water.

9. A fertilizer granule or liquid additive, which comprises one or more nitrification inhibitors in an organic liquid solvating system comprising a mixture of aprotic and protic solvents

wherein a first aprotic solvent is dimethyl sulfoxide, dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having the formula

R₁—

S(O)—

R₂,

wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and R_n is ethyl, n-propyl, phenyl or benzyl,

and a second protic solvent is one or more of

a) an alcohol or polyol from the family of alkylene and poly(alkylene) glycols

b) an alkylene glycol selected from the group consisting of ethylene, propylene, and butylene glycol,

c) glycerin,

d) an alkylene glycol alkyl ether selected from the group comprising of dipropylene glycol methyl ether, tripropylene glycol methyl ether, and tripropylene glycol butyl ether

e) an alkanolamine selected from the group comprising of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and/or

f) ethyl, propyl, or butyl lactate

wherein the organo liquid solvating system meets the following criteria;

a. environmentally safe

b. has a flashpoint above 145°

F.

c. inherently rated safe for contact with humans and animals

d. able to provide improved and even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules

e. results in a composition comprising at least one of nitrification inhibitor at levels of 1-50% with a Chill Point <

40°

F.

10. The fertilizer granule or liquid additive of claim 9, wherein the one or more nitrification inhibitors is selected from the group consisting of 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, and 7) 3,4 dimethylpyrazole phosphate.

11. The fertilizer granule or liquid additive of claim 9, further comprising 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.

12. The fertilizer granule or liquid additive of claim 11, wherein the one or more nitrification inhibitors comprises 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-Amino-4-chloro-6-methylpyrimidine, or 7) 3,4 dimethylpyrazole phosphate;

and the one or more urease inhibitors comprises phosphoramides.

13. A method of making a composition to be added to a fertilizer comprising:

heating a mixture comprising one or more nitrification inhibitors in an organic liquid solvating system comprising a mixture of aprotic and protic solvents

wherein a first aprotic solvent is dimethyl sulfoxide, dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having the formula

R₁—

S(O)—

R₂,

wherein R₁, is methyl, ethyl, n-propyl, phenyl or benzyl and R₂ is ethyl, n-propyl, phenyl or benzyl,

and a second protic solvent is one or more of

a) an alcohol or polyol from the family of alkylene and poly(alkylene) glycols

b) an alkylene glycol selected from the group consisting of ethylene, propylene, and butylene glycol,

c) glycerin,

d) an alkylene glycol alkyl ether selected from the group comprising of dipropylene glycol methyl ether, tripropylene glycol methyl ether, and tripropylene glycol butyl ether

e) an alkanolamine selected from the group comprising of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and/or

f) ethyl, propyl, or butyl lactate

wherein the organo liquid solvating system meets the following criteria;

a. environmentally safe

b. has a flashpoint above 145°

F.

c. inherently rated safe for contact with humans and animals

d. able to provide improved and even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules

e. results in a composition comprising at least one of nitrification inhibitor at levels of 1-50% with a Chill Point <

40°

F.

cooling the mixture to a temperature that optionally allows an addition of one or more of

aprotic solvents present in the amount of 0.5-40%, surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed nitrification inhibitors, dispersed urease inhibitor(s), crystallization inhibitors and/or flow modifiers.

14. The method of claim 13, further comprising adding the composition to a fertilizer granule or liquid.

15. The method of claim 13, wherein the one or more nitrification inhibitors is selected from the group consisting of 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, and 7) 3,4 dimethylpyrazole phosphate.

16. The method of claim 13, further comprising one or more urease inhibitors selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

17. The method of claim 16, wherein the one or more nitrification inhibitors comprises 1) dicyandiamide, 2) 2-chloro-6 trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, 7) 3,4 dimethylpyrazole phosphate and the one or more urease inhibitors comprises phosphoramides.

18. The method of claim 13, wherein the composition is substantially free of water.