Improved solvent system for dicyandiamide and / or alkylthiophosphoric triamide and use in agricultural applications

Abstract

The present disclosure relates to an improved solvent system for dicyandiamide and / or alkylthiophosphoric triamide and use in agricultural applications. More specifically, the present disclosure relates to an inhibitor composition containing dicyandiamide as a nitrification inhibitor, alkylthiophosphoric triamide as a urease inhibitor, or a combination thereof, dissolved in a liquid medium comprising an organic solvent, the organic solvent is selected, among other things, from the group consisting of one or more polar aprotic solvents, including one or more organophosphorus esters, amine solvents, heterocyclic alcohol solvents, and mixtures thereof, which compositions are useful in the manufacture of fertilizer compositions and in methods of fertilizing target plants.

Description

This application is a divisional application of the following application: Application date: October 21, 2015; Application number: 201580070005.4; Invention name: "Improved solvent system for dicyandiamide and / or alkylthiophosphoric triamide and use in agricultural applications". CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 066,513, filed on October 21, 2014, which is incorporated by reference in its entirety into this application. Technical Field

[0002] The present invention relates to liquid compositions comprising dicyandiamide and / or alkyl thiophosphorictriamide, methods for combining such compositions with agricultural fertilizer compositions, agricultural fertilizer compositions comprising dicyandiamide and / or alkyl thiophosphorictriamide, and uses of such compositions. Background Art

[0003] In the agrochemical industry, farmers use different fertilizers to supply macronutrients to plants by applying to the soil or to the leaves of plants. Nitrogen, phosphorus, potassium, calcium, magnesium and sulfur are macronutrients that farmers must manually provide to plants and soil. In many crops, the amount of nitrogen provided is crucial to the overall quality and growth of the crops. Nitrogen is typically provided in a nitrogenous form, i.e., a nitrogenous precursor, a fertilizer compound, such as urea, ammonium nitrate or ammonium phosphate fertilizer compounds. However, due to the high water solubility of these salts, the nitrogen value provided may be lost due to runoff and leaching of the nitrogen fertilizer compound. Once applied, the nitrogen fertilizer compound is typically degraded into nitrogen species, such as NH4, for example by microorganisms present in the soil. + 、NO2 - 、NO3 - and ammonia, which may be even more susceptible to loss through evaporation, runoff, and leaching than the fertilizer compounds themselves. If the degradation of fertilizer compounds occurs at a faster rate than the plants can utilize the nitrogen-containing degradation products, the nitrogen value in the degradation products is at increased risk of loss.

[0004] Nitrification inhibitors and / or urease inhibitors have potential use in delaying the degradation of fertilizer compounds and thereby reducing the loss of nitrogen-containing degradation products that would otherwise occur in the absence of the inhibitors. The use of nitrification inhibitors and / or urease inhibitors in conjunction with nitrogen fertilizer compounds tends to increase the amount of time the nitrogen source remains in the soil and is available for uptake by plants, which tends to increase the effectiveness of the fertilizer and have a positive impact on crop yield and quality.

[0005] End-use aqueous fertilizer solutions are typically prepared by diluting a commercially available concentrated fertilizer composition with water on site. Commonly used concentrated fertilizer compositions include concentrated ammonium nitrate compositions, such as, for example, UAN 18, UAN 28, UAN 30 and UAN 32.

[0006] Dicyandiamide is potentially useful as a nitrification inhibitor in such end-use aqueous fertilizer compositions, but dicyandiamide has a very low solubility in water (about 41 grams per liter ("g / l")) and is therefore difficult to incorporate into the end-use aqueous fertilizer compositions, particularly under field conditions. Summary of the invention

[0007] Urease inhibitors can be used with fertilizers (i.e., combined with fertilizers containing urea, such as urea and urea ammonium nitrate (UAN)) to slow down the conversion of ammonium to ammonia and thus slow down the loss of ammonia to evaporation, thus making ammonium available to plants in the soil for a longer period of time. In many crops, the amount of nitrogen provided is crucial for the overall quality and growth of the crops. Nitrogen is supplied in the form of either urea or ammonium phosphate. However, due to the high water solubility of these salts, a large amount of nitrogen applied is lost due to runoff and leaching. In ammonium-based products, if nitrogen is not lost due to leaching or runoff, it is converted into ammonia by an enzyme called urease. Although ammonia can bind to soil particles, the conversion that occurs near the soil surface does not allow binding, and therefore, ammonia is lost to the atmosphere. Urease inhibitors are used to protect farmers' investment in fertilizers by preventing urease from decomposing urea, and soil microorganisms are responsible for converting urea into ammonia available in the soil. This increases the amount of time that the nitrogen is retained in the soil and is available for plant absorption.

[0008] Similarly, nitrification inhibitors can be used with fertilizers (i.e., in combination with urea-containing fertilizers, such as urea and urea ammonium nitrate (UAN)) to slow the conversion of ammonium to nitrate and the subsequent loss of nitrate to leaching, thus making ammonium available to plants for a longer period of time in the soil. Ammonium is one of the main forms of nitrogen that can be used by plants. Increasing the amount of time that nitrogen is available to plants increases the effectiveness of the fertilizer, which has a positive impact on crop yield and quality.

[0009] In one embodiment, the fertilizer is a conventional water-soluble inorganic fertilizer providing nutrients, such as a phosphorus-based, nitrogen-based, potassium-based or sulfur-based fertilizer. Examples of such fertilizers include: for nitrogen as a nutrient: nitrates and or ammonium salts, such as ammonium nitrate, including in combination with urea, for example as an Uram-type material, calcium ammonium nitrate, ammonium nitrate sulfate, ammonium phosphates, particularly monoammonium phosphate, diammonium hydrogen phosphate and ammonium polyphosphate, ammonium sulfate and the less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride. It should be understood that the fertilizer composition may contain one or a combination of the fertilizers described herein.

[0010] However, typical urease inhibitors, alkylthiophosphoric triamides, and, more particularly, NBPT (N-n-butylthiophosphoric triamide), face drawbacks in their applications because NBPT is extremely difficult to handle. NBPT is a viscous, waxy, heat and water-sensitive material that cannot be used in its solid form because its use at low concentrations makes it difficult to distribute evenly on urea pellets (i.e., large granules) and in the soil. In order to distribute NBPT evenly on urea, the NBPT should be dispersed in a carrier before spraying the NBPT on the urea. Therefore, the use of a solvent system containing NBPT is desirable because, in its liquid form, the solvent system is able to distribute the NBPT into granular urea (such as urea pellets) and into liquid fertilizers containing urea. By introducing NBPT into a liquid fertilizer containing urea (e.g., urea-ammonium nitrate solution or UAN) in a solvent system, the NBPT can be better dispersed in the liquid fertilizer.

[0011] Dicyandiamide is useful as a nitrification inhibitor in aqueous agricultural applications, such as end-use fertilizer compositions, but suffers from similar drawbacks as urease inhibitors. Nitrification inhibitors, such as dicyandiamide, generally have very low solubility in water (about 41 grams per liter ("g / l")) and are therefore difficult to incorporate into the end-use aqueous fertilizer composition, especially under field conditions. As nitrification inhibitors, such as dicyandiamide, have generally low solubility, their use in low concentrations in water makes it difficult to distribute evenly on pellets (i.e., large particles) containing urea and in the soil. In order to evenly distribute dicyandiamide on pellets or particles containing urea, the dicyandiamide should be dispersed in a solvent carrier before spraying the dicyandiamide onto the urea. Therefore, the use of a solvent system containing dicyandiamide (also referred to herein as "DCD") is desirable because, in its liquid form, the solvent system is capable of distributing the dicyandiamide onto urea granules or pellets, urea ammonium nitrate granules or pellets, or other urea-containing granules or pellets, and into liquid fertilizers containing urea or urea ammonium nitrate. By introducing the dicyandiamide into a liquid fertilizer containing urea (e.g., urea-ammonium nitrate solution or UAN) in a solvent system, the dicyandiamide is better dispersed in the liquid fertilizer.

[0012] In one embodiment, the concentrated fertilizer composition includes a concentrated ammonium nitrate composition, such as, for example, UAN 18, UAN 28, UAN 30, and UAN 32.

[0013] Therefore, it is desirable to obtain a solvent system containing alkylthiophosphoric triamides, and in particular (N-n-butylthiophosphoric triamide), which has good toxicological and / or ecological characteristics and desirable characteristics in terms of low volatility, biodegradability or readily biodegradable (i.e. readily biodegradable), low toxicity or low hazard level. It is desirable to obtain a solvent system containing dicyandiamide, which has good toxicological and / or ecological characteristics and desirable characteristics in terms of low volatility, biodegradability or readily biodegradable (i.e. readily biodegradable), low toxicity or low hazard level. It is also desirable to obtain a solvent system containing a combination of dicyandiamide and alkylthiophosphoric triamides, in particular (N-n-butylthiophosphoric triamide), which has good toxicological and / or ecological characteristics and desirable characteristics in terms of low volatility, biodegradability or readily biodegradable (i.e. readily biodegradable), low toxicity or low hazard level.

[0014] The invention described herein, as will become apparent from the following detailed description and examples, comprises, in one aspect, a liquid composition for use in agricultural applications, the liquid composition comprising: at least one of a nitrification inhibitor or a urease inhibitor (and, in some embodiments, both a nitrification inhibitor and a urease inhibitor); and at least one organophosphate compound having formula (VIII) (or, hereinafter, synonymously referred to as an "organophosphate solvent"):

[0015] Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. Optionally, the liquid composition may further comprise at least one co-solvent selected from polar aprotic solvents, amine solvents, heterocyclic alcohol solvents and mixtures thereof. The liquid composition may further comprise one or more stabilizers.

[0016] In another aspect, described herein are methods of making solid or concentrated liquid fertilizer compositions, the methods comprising: treating (including, contacting or spraying) one or more nitrogen fertilizer compounds with a liquid inhibitor composition. The liquid inhibitor composition comprises at least one of a nitrification inhibitor or a urease inhibitor (or in some embodiments, a combination of at least one nitrification inhibitor and at least one urease inhibitor) uniformly dissolved or dispersed in a solvent, the solvent comprising at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above. In one embodiment, the liquid inhibitor composition further comprises at least one co-solvent selected from polar aprotic solvents, amine solvents, heterocyclic alcohol solvents and mixtures thereof.

[0017] The term treatment, in one embodiment, includes spraying the liquid inhibitor composition with one or more nitrogen fertilizer compounds. The term treatment, in one embodiment, includes but is not limited to contacting the inhibitor composition with one or more nitrogen fertilizer compounds. In one embodiment, the nitrification inhibitor is dicyandiamide. In another embodiment, the urease inhibitor is an alkylthiophosphoric triamide.

[0018] In yet another aspect, described herein are concentrated liquid fertilizer compositions comprising, based on the weight of the composition, (a) up to about 99 wt % of one or more nitrogen fertilizer compounds, (b) at least one of dicyandiamide or alkylthiophosphoric triamide (or a combination of both), (c) a solvent comprising at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above.

[0019] In another aspect, described herein are concentrated liquid fertilizer compositions comprising, based on the weight of the composition, (a) up to about 99 wt% of one or more nitrogen fertilizer compounds, (b) at least one of dicyandiamide or alkylthiophosphoric triamide (or, in some embodiments, both), (c) a solvent comprising at least one organic phosphate solvent according to formula (VIII), (d) optionally, at least one co-solvent selected from polar aprotic solvents, amine solvents, heterocyclic alcohol solvents, and mixtures thereof, and (e) optionally water. The concentrated liquid fertilizer composition may further comprise one or more stabilizers.

[0020] In yet another aspect, described herein are solid or substantially solid fertilizer compositions comprising: (a) solid particles of one or more nitrogen-containing fertilizer compounds, and (b) an inhibitor composition comprising at least one of dicyandiamide or an alkylthiophosphoric triamide supported on at least a portion of the solid particles.

[0021] In another aspect, described herein are methods of making liquid or aqueous fertilizer compositions comprising contacting one or more nitrogen fertilizer compounds with a liquid inhibitor composition comprising at least one of a nitrification inhibitor or a urease inhibitor uniformly dissolved or dispersed in a solvent comprising at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above.

[0022] Optionally, the solvent may further comprise a co-solvent selected from polar aprotic solvents, amine solvents, heterocyclic alcohol solvents and mixtures thereof.

[0023] In another aspect, the organic solvent is an organophosphate compound having formula (VIII)

[0024] wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In another embodiment, R1, R2 and R3 are each independently selected from H, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In one embodiment, R1, R2 and R3 are each independently selected from H, C1-C4 alkyl, C4-C8 alkyl, C1-C 12 alkenyl, C1-C4 alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H.

[0025] In yet another embodiment, R1, R2 and R3 are each independently selected from C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 In one embodiment, R1, R2 and R3 are each independently selected from C1-C 12 Alkyl, more typically, C2-C8 alkyl.

[0026] In another aspect, described herein is a method for fertilizing a target plant, the method comprising applying an end-use aqueous fertilizer composition comprising: (a) one or more nitrogen fertilizer compounds, (b) at least one of dicyandiamide or an alkylthiophosphoric triamide, (c) an organic solvent having formula (VIII), wherein R1, R2 and R3 are as described above, and (d) optionally a co-solvent selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dimethyl succinate, dimethyl ethylsuccinate, dimethyl glutarate, dimethyl methylglutarate, and dimethyl adipic acid, diethylenetriamine, or monoethanolamine, methyl-5-(dimethylamino)-2-methyl-oxopentanoate, dimethylaminoethanol, triethanolamine, a heterocyclic alcohol according to structure (IIIb): or mixtures thereof, and optionally (d) water, applied to the target plants or to the environment of the target plants. It should be understood that the term heterocyclic alcohol includes dioxolane compounds. In some embodiments, the end-use fertilizer composition may also include at least one stabilizer. In one embodiment, the stabilizer is monoethanolamine.

[0027] In one embodiment, the alkylthiophosphoric triamide is N-n-butylthiophosphoric triamide. In another embodiment, the liquid composition further comprises a cosolvent selected from the group consisting of: (a) at least one dioxolane compound having formula (III):

[0028] wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; b) at least one dibasic ester; c) at least one compound having formula (IIa): R3OOC-A-CONR4R5 (IIa),

[0029] Where R3 contains C1-C 36 wherein R4 and R5 independently comprise C1-C 36 alkyl, wherein R4 and R5 can optionally form a ring together; and wherein A is a linear or branched divalent C2-C6 alkyl; d) at least one alkyl dimethyl amide; e) at least one alkyl lactate; f) ethyl levulinate; g) at least one alkoxy alcohol, ether alcohol, amine alcohol, amino alcohol or alcohol; h) at least one glycerol or glycerol derivative; i) at least one alkyl carbonate; j) dimethyl sulfoxide; and k) any combination thereof. In one embodiment, the co-solvent is dimethyl sulfoxide.

[0030] In another aspect, the present invention is directed to a nitration inhibitor composition comprising dicyandiamide dissolved in a liquid medium comprising an organic solvent selected from the group consisting of polar aprotic solvents, dibasic esters, amines, amine alcohols, heterocyclic alcohols, and mixtures thereof.

[0031] In yet another aspect, the present invention is directed to a method of making a solid or concentrated liquid fertilizer composition comprising treating (e.g., contacting, spraying, brushing, etc.) one or more nitrogen-containing fertilizer compounds with a nitrification inhibitor composition comprising dicyandiamide dissolved in a liquid medium comprising an organic solvent selected from the group consisting of polar aprotic solvents, amine solvents, heterocyclic alcohol solvents, and mixtures thereof.

[0032] In another aspect, the present invention is directed to a concentrated liquid fertilizer composition comprising, by weight of the composition: (a) up to about 99 wt % of one or more nitrogen fertilizer compounds, (b) dicyandiamide or alkylthiophosphoric triamides (or both); (c) at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above; (d) optionally, at least one co-solvent selected from polar aprotic solvents, amine solvents, heterocyclic alcohol solvents or mixtures thereof, and (d) optionally, water.

[0033] In another aspect, the present invention is directed to a concentrated solid fertilizer composition comprising: (a) solid particles of one or more nitrogen fertilizer compounds, and (b) dicyandiamide or alkylthiophosphoric triamide supported on at least a portion of the solid particles.

[0034] In yet another aspect, the present invention is directed to a method of making an aqueous end-use fertilizer composition comprising contacting one or more nitrogen fertilizer compounds with a urease inhibitor composition comprising an alkylthiophosphoric triamide dissolved in a liquid medium comprising an organic solvent selected from a polar aprotic solvent, an amine solvent, a heterocyclic alcohol solvent, or a mixture thereof.

[0035] In another aspect, the present invention is directed to a method for fertilizing a target plant, the method comprising applying an aqueous end-use fertilizer composition comprising: (a) one or more nitrogen fertilizer compounds; (b) dicyandiamide, alkylthiophosphoric triamides or mixtures thereof; (c) at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above, (d) optionally, at least one organic solvent selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dimethyl succinate, dimethyl ethylsuccinate, dimethyl glutarate, dimethyl methylglutarate, and dimethyl adipic acid, diethylenetriamine, or monoethanolamine, methyl-5-(dimethylamino)-2-methyl-oxopentanoate, dimethylaminoethanol, triethanolamine, a heterocyclic alcohol according to structure (IIIb): or mixtures thereof; and (e) optionally, water, Apply to these target plants or apply to the environment of these target plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 is a graph illustrating the residual pressure as a function of temperature for both the comparative sample labeled "Unstable" (without the organophosphate compound) and Formulation 1 labeled "Stable" (with the organophosphate compound). DETAILED DESCRIPTION

[0037] As used herein, the term "alkyl" refers to a saturated straight chain, branched or cyclic hydrocarbon group, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl and cyclohexyl.

[0038] As used herein, the term "aryl" refers to a monovalent unsaturated hydrocarbon radical comprising one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, one or more of the carbons of which may be substituted with hydroxy, alkyl, alkenyl, halogen, haloalkyl or amino, including but not limited to phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl and tristyrylphenyl.

[0039] As used herein, the term "alkylene" refers to a divalent saturated straight or branched hydrocarbon group, such as, for example, methylene, dimethylene, trimethylene.

[0040] As used herein, the term "alkoxy" means an oxy group substituted by an alkyl group, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, or butoxy, which alkyl group may be optionally further substituted on one or more carbon atoms of the group.

[0041] As used herein, the term "alkoxyalkyl" refers to an alkyl group substituted with one or more alkoxy substituents, more typically (C1-C 22)alkoxy-(C1-C6)alkyl, such as methoxymethyl and ethoxybutyl.

[0042] As used herein, the term "alkenyl" means an unsaturated straight or branched chain hydrocarbon group containing one or more carbon-carbon double bonds, more typically an unsaturated straight or branched chain (in a specific embodiment, C1-C 75 ) hydrocarbon groups, such as vinyl, n-propenyl, isopropenyl.

[0043] As used herein, the term "aralkyl" refers to an alkyl group substituted with one or more aryl groups, more typically with one or more (C6-C 14 ) substituted with aryl substituents (C1-C 18 ) alkyl, such as, for example, phenylmethyl, phenylethyl, and triphenylmethyl.

[0044] As used herein, the term "aryloxy" means an oxy group substituted with an aryl group, such as, for example, phenoxy, methylphenoxy, isopropylmethylphenoxy.

[0045] As used herein, the term “ r -C s )" refers to an organic group, wherein r and s are each an integer, indicating that the group may contain from r carbon atoms to s carbon atoms per group.

[0046] In one embodiment, non-limiting examples of nitrification inhibitors include any one or more of N-2,5-dichlorophenylsuccinamic acid, dicyandiamide (DCD), zinc ethylene-bis-dithiocarbamate, 2,4,6-trichloroaniline (triehloroaniline), pentachlorophenol, thiourea, ammonium thiosulfate (ATS), or 3,4-dimethylpyrazole phosphate (DMPP).

[0047] In one embodiment, non-limiting examples of urease inhibitors include any one or more of N-butylthiophosphoryl triamide (NBPT), N-(w-butyl)phosphoryl triamide, miophosphoryl triamide, cyclohexylphosphoryl triamide, cyclohexylthiophosphoryl triamide, phosphoryl triamide, hydroquinone, p-benzoquinone, hexamidocyclotriphosphazene, thiopyridine, thiopyrimidine, thiopyridine-N-oxide, N,A'-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, ammonium thiosulfate (ATS), N-cyclohexylphosphoryl triamide (CHPT), phenylphosphoryl diamide (PPT) and 2-nitrophenylphosphoryl triamide (2-NPT).

[0048] Dicyandiamide is a known compound according to formula (I):

[0049] Dicyandiamide, also known as "2-cyanoguanidine," is typically prepared by treating cyanamide with a base and is commercially available.

[0050] In one embodiment, the composition according to the present invention comprises a urease inhibitor such as an alkylthiophosphoric triamide or ammonium thiosulfate, a nitrification inhibitor, or a combination of both a urease inhibitor and a nitrification inhibitor.

[0051] In one embodiment, the alkylthiophosphoric triamide is N-(n-butyl)thiophosphoric triamide ("NBPT"). At least one of the alkylthiophosphoric triamide or dicyandiamide (or a combination thereof) may be present in the liquid agricultural composition in a range of a lower limit of 2% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition in a range of a lower limit of 3% by weight of the composition. At least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition in a range of a lower limit of 5% by weight of the composition.

[0052] In another embodiment, at least one of alkylthiophosphoric triamide or dicyandiamide (or a combination of both) may be present in the liquid agricultural composition at a lower range of 0.5%, or 1%, or 2%, or 3%, or 4%, or 5%, 6%, or 8%, or 10%, or 12%, or 14% by weight of the composition. At least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 75%, or 65%, or 60% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 60% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 55% by weight of the composition. In another embodiment, at least one of alkylthiophosphoric triamides and / or dicyandiamide may be present in the liquid agricultural composition at an upper range of 59%, or 57%, or 55%, or 53%, or 50%, by weight of the composition. In another embodiment, at least one of alkylthiophosphoric triamides and / or dicyandiamide may be present in the liquid agricultural composition at an upper range of 48%, or 46%, or 45%, or 42%, or 40%, by weight of the composition.

[0053] In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 70% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 65% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 60% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 55% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 40% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition at an upper range of 35% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition in an upper range of 30% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide or a combination thereof may be present in the liquid agricultural composition in an upper range of 25% by weight of the composition.

[0054] In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the liquid agricultural composition in an amount between about 7% by weight of the composition and about 55% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the composition in an amount between about 8% by weight of the composition and about 50% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the liquid agricultural composition in an amount between about 7% by weight of the composition and about 45% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the liquid agricultural composition in an amount between about 7% by weight of the composition and about 40% by weight of the composition. In another embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the liquid agricultural composition in an amount between about 7% by weight of the composition and about 35% by weight of the composition.

[0055] At least one of the alkylthiophosphoric triamide or dicyandiamide may be present in the composition in an amount between about 0.5% by weight of the composition and about 60% by weight of the composition, or in another embodiment, they may be present in the composition in an amount between about 1% by weight of the composition and about 40% by weight of the composition, and in another embodiment, they may be present in the composition in an amount between about 0.5% by weight of the composition and about 20% by weight of the composition. In a specific embodiment, at least one of the alkylthiophosphoric triamide or dicyandiamide is present in the composition in an amount between about 1% by weight of the composition and about 30% by weight of the composition. At least one of the alkylthiophosphoric triamide or dicyandiamide means that the alkylthiophosphoric triamide may be present alone, dicyandiamide may be present alone, or a combination of the alkylthiophosphoric triamide and dicyandiamide may be present.

[0056] Compounds suitable as the organic solvent component of the compositions and methods of the present invention are organophosphate solvents according to formula (VIII) (wherein R1, R2 and R3 are as described above), polar aprotic solvents, amine solvents, heterocyclic alcohol solvents or mixtures thereof, which form liquid or otherwise stable compositions with the nitration and / or urease inhibitor at temperatures from -16°C to 54°C, in other embodiments -10°C to 40°C, in other embodiments -5°C to 40°C, in other embodiments -2°C to 40°C, or in other embodiments 0°C to 40°C.

[0057] In another embodiment, compounds suitable as the organic solvent component of the compositions and methods of the present invention are organophosphate solvents according to formula (VIII) (wherein R1, R2 and R3 are as described above), polar aprotic solvents, amine solvents, heterocyclic alcohol solvents or mixtures thereof, at a temperature of -16°C or greater, in alternative embodiments greater than -14°C, in other embodiments greater than -12°C, in other embodiments greater than -10°C, in other embodiments greater than -8°C, in other embodiments greater than -5°C, in other embodiments greater than -3°C, in other embodiments greater than -2°C, in other embodiments greater than 0°C, in other embodiments greater than 2°C, in other embodiments greater than 4°C, in other embodiments greater than 5°C. These solvents form liquid or otherwise stable compositions together with the nitration and / or urease inhibitor.

[0058] In some embodiments, at a specified temperature range or at a temperature greater than a specified temperature (as described herein), the liquid agricultural composition or liquid fertilizer composition is stable, meaning that the one or more ureases and / or nitrification inhibitors do not react with the solvent or solvent component under the expected conditions of manufacture, storage, and use. In one embodiment, at a specified temperature range or at a temperature greater than a specified temperature (as described herein), the liquid agricultural composition or liquid fertilizer composition is stable, meaning that the liquid agricultural composition or liquid fertilizer composition is or is substantially in one phase, i.e., there are no visible crystals, no visible precipitation, and / or no visible multiple liquid phases. In one embodiment, at a specified temperature range or at a temperature greater than a specified temperature (as described herein), the described liquid fertilizer composition is stable, meaning that the degradation of the inhibitor component (which in one embodiment is NBPT) is slow or delayed compared to a fertilizer composition without a stabilizer or stabilizing component as described herein. In one embodiment, the stabilizer or stabilizing component is an organophosphate solvent having formula (VIII):

[0059] Wherein R1, R2 and R3 are each independently selected from H, C1-C16 alkyl, C1-C16 alkenyl, C1-C16 alkoxyalkyl, C7-C30 alkylaralkyl, C7-C30aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In one embodiment, R1, R2 and R3 are each independently C1-C16 alkyl. In one embodiment, R1, R2 and R3 are each independently C1-C8 alkyl. In one embodiment, R1, R2 and R3 are each independently C1-C4 alkyl. In one embodiment, R1, R2 and R3 are each independently C1-C2 alkyl.

[0060] In some embodiments, the liquid agricultural composition or liquid fertilizer composition is stable at a high temperature range or at a temperature greater than a specified temperature (as described herein), meaning that the one or more ureases and / or nitrification inhibitors do not react with the solvent or solvent component under the expected conditions of manufacture, storage and use. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 25°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 27°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 29°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 30°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 32°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 34°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 35°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 37°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 40°C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 42° C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 44° C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 45° C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 47° C. In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable at a temperature greater than 50° C.

[0061] In one embodiment, the liquid agricultural composition or liquid fertilizer composition is stable, meaning that the liquid agricultural composition or liquid fertilizer composition is or is substantially in one phase, i.e., no visible crystals, no visible precipitation, and / or no visible multiple liquid phases, within a specified temperature range or at greater than a specified temperature (as described herein). In another embodiment, the liquid agricultural composition or liquid fertilizer composition is stable, meaning that the liquid agricultural composition or liquid fertilizer composition is or is substantially in one phase and exhibits little or slight discoloration.

[0062] In one embodiment, the solvent comprises at least one of an organophosphate solvent according to formula (VIII) (wherein R1, R2 and R3 are as described above), a polar aprotic solvent, an amine solvent, a heterocyclic alcohol solvent, or a mixture thereof, wherein dicyandiamide has a solubility of greater than or equal to 50 grams per liter (g / l), more typically greater than or equal to 200 g / l at 25°C. In one embodiment, the solvent comprises at least one of an organophosphate solvent according to formula (VIII) (wherein R1, R2 and R3 are as described above), optionally with one or more co-solvents, wherein the inhibitor component has a solubility of greater than or equal to 240 grams per liter (g / l), or greater than or equal to 220 g / l in other embodiments, or greater than or equal to 280 g / l in other embodiments, or greater than or equal to 300 g / l in other embodiments, or greater than or equal to 340 g / l in other embodiments, or greater than or equal to 360 g / l in other embodiments, or greater than or equal to 380 g / l in other embodiments at 25°C. Reference to an "inhibitor component" includes at least one nitrification inhibitor, or in some embodiments, at least one urease inhibitor, or in alternative embodiments, a combination of at least one urease inhibitor and at least one nitrification inhibitor. In a specific embodiment, the inhibitor component includes a combination of NBPT and DCD.

[0063] Suitable polar aprotic organic solvents include, for example, dichloromethane, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, ethyl acetate, hexamethylphosphoramide, dimethyl sulfone, sulfolane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, methyl acetate, ethyl lactate, methylpyrrolidone, tetrahydrofuran, propylene carbonate, and dibasic ester solvents.

[0064] In one embodiment, the formulation as described herein further comprises one or more stabilizers. In one embodiment, the organophosphate compound of formula (VIII) is a stabilizer. In one embodiment, the organophosphate compound of formula (VIII), when added to a formulation / composition as described herein, provides stability to the formulation over a period of at least 24 hours. In one embodiment, the organophosphate compound of formula (VIII), when added to a formulation / composition as described herein, provides stability to the formulation over a period of at least 48 hours. In another embodiment, the organophosphate compound of formula (VIII), when added to a formulation / composition as described herein, provides stability to the formulation over a period of at least 72 hours. In another embodiment, the organophosphate compound of formula (VIII), when added to a formulation / composition as described herein, provides stability to the formulation over a period of at least 4 days, or at least 5 days, or at least 6 days, or at least 7 days, or at least 8 days, or at least 9 days, or at least 10 days, or at least 11 days, or at least 12 days. In another embodiment, the organophosphate compound of formula (VIII), when added to a formulation / composition as described herein, provides stability to the formulation for a period of at least 14 days.

[0065] Suitable dibasic ester solvents include, for example, dialkyl esters of dicarboxylic acids, more typically di(C1-C8) esters of saturated linear or branched (C2-C8) aliphatic carboxylic acids. 12 ) alkyl esters or mixtures thereof. In one embodiment, the dibasic ester composition comprises one or more compounds according to structure (II): R 1 OOC-A-CONR 2 R 3 (II) in: A is a divalent linear or branched (C2-C8) aliphatic hydrocarbon group, and R 1 , R 2 and R 3 Each independently is (C1-C 12 )alkyl, (C1-C 12 ) aryl, (C1-C 12 ) alkylaryl or (C1-C 12 )aralkyl, and R 2 and R 3 Each may be optionally substituted with one or more hydroxy groups.

[0066] In one embodiment, the dibasic ester solvent component of the composition and method of the present invention comprises one or more saturated straight-chain or branched (C4-C6) dimethyl esters of aliphatic carboxylic acids, such as dimethyl succinate, dimethyl ethylsuccinate, dimethyl glutarate, dimethyl methylglutarate, and dimethyl adipic acid, and mixtures thereof. In one embodiment, the dibasic ester component comprises dimethyl succinate, dimethyl glutarate, and optionally dimethyl adipic acid. In another embodiment, the dibasic ester component comprises dimethyl ethylsuccinate, dimethyl methylglutarate, and optionally dimethyl adipic acid.

[0067] In one embodiment, the dibasic ester solvent component in the composition and method of the present invention comprises one or more saturated straight-chain or branched (C4-C6) dialkyl esters of aliphatic carboxylic acids, such as dialkyl esters of succinic acid, dialkyl esters of ethylsuccinic acid, dialkyl esters of glutaric acid, dialkyl esters of methylglutaric acid and dialkyl esters of adipic acid, and mixtures thereof. In one embodiment, the dibasic ester component comprises dialkyl esters of succinic acid, dialkyl esters of glutaric acid and optionally dimethyl esters of adipic acid. In another embodiment, the dibasic ester component comprises dialkyl dimethyl esters of ethylsuccinic acid, dialkyl esters of methylglutaric acid and optionally dialkyl esters of adipic acid. In one embodiment, each alkyl group in the dialkyl group each comprises a C1-C8 alkyl group. In another embodiment, each alkyl group in the dialkyl group, in one embodiment, each comprises a C1-C4 alkyl group. In another embodiment, each alkyl group in the dialkyl group, in one embodiment, each comprises a C1-C6 alkyl group.

[0068] Suitable amine solvents include primary amines, including monoalkylamines such as propylamine; secondary amines, including dialkylamines and diarylamines such as dimethylamine and diphenylamine; and tertiary amines, such as diethylenetriamine and methyl-5-(dimethylamino)-2-methyl-oxopentanoate.

[0069] In one embodiment, the amine solvent component of the compositions and methods of the present invention is selected from aliphatic or aromatic primary, secondary or tertiary amines that do not contain any functional groups other than one or more amino groups.

[0070] In one embodiment, the amine solvent component of the composition and method of the present invention is selected from aliphatic or aromatic primary, secondary or tertiary amines, and in addition to one or more amino groups, may optionally contain one or more additional functional groups, such as hydroxyalkyl, hydroxyl, carbonyl or alkyl ester groups.

[0071] In one embodiment, the organic solvent component of the compositions and methods of the present invention comprises an amino alcohol. Compounds suitable as the amino alcohol solvent component of the compositions and methods of the present invention are those containing at least one primary, secondary, or tertiary amine moiety per molecule and at least one hydroxyalkyl moiety per molecule. More typically, in one embodiment, the amino alcohol is a linear, branched, or cyclic saturated or unsaturated hydrocarbon substituted with an amino group on at least one carbon atom and substituted with a hydroxyalkyl or hydroxyl group on at least one other carbon atom, such as monoethanolamine, ethylaminoethanol, dimethylaminoethanol, isopropylaminoethanol, diethanolamine, triethanolamine, methylethanolamine, aminopropanol, methylaminopropanol, dimethylaminopropanol, aminobutanol, dimethylaminobutanol, aminobutanediol, trihydroxymethylaminoethane, diethylaminopropanediol, 1-amino-cyclopentanemethanol, and aminobenzyl alcohol, or a heterocycle containing at least one nitrogen atom as a ring member and / or substituted with an amino group on at least one carbon atom and substituted with a hydroxyalkyl or hydroxyl group on at least one other carbon atom, such as methylaminomethyl-1,3-dioxolane.

[0072] Suitable heterocyclic alcohol solvents include, for example, 5- or 6-membered heterocycles comprising 1 or 2 oxygen atoms as ring members, the heterocycle being substituted by (C1-C6) hydroxyalkyl on at least one carbon atom of the ring, and the heterocycle being optionally substituted by one or more (C1-C4) alkyl on one or more carbon atoms of the ring. It should be understood that the term heterocyclic alcohol includes dioxolane compounds. In one embodiment, the heterocyclic alcohol component of the present invention comprises one or more compounds selected from heterocyclic alcohols according to structures (IV), (IVa), (V), (VI), and (VII): Where n = 1 or 2,

[0073] In one embodiment, the organic solvent component of the compositions and methods of the present invention comprises one or more organophosphate solvents as described herein, polar aprotic solvents, one or more dibasic ester compounds according to structure (II), one or more amino alcohols, one or more tertiary amines, one or more heterocyclic alcohols according to structure (III), or mixtures thereof.

[0074] In one embodiment, the organic solvent component of the compositions and methods of the present invention comprises dimethyl sulfoxide, dimethylformamide, dimethyl succinate, dimethyl ethylsuccinate, dimethyl glutarate, dimethyl methylglutarate, and dimethyl adipic acid, diethylenetriamine, or monoethanolamine, methyl-5-(dimethylamino)-2-methyl-oxopentanoate, dimethylaminoethanol, triethanolamine, a heterocyclic alcohol according to structure (III), or a mixture thereof.

[0075] In one embodiment, the organic solvent component of the liquid agricultural composition comprises at least one organophosphate compound having formula (VIII):

[0076] wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In another embodiment, R1, R2 and R3 are each independently selected from H, C1-C 12 Alkyl, C1-C 12 Alkenyl, C1-C 12 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In one embodiment, R1, R2 and R3 are each independently selected from H, C1-C4 alkyl, C4-C8 alkyl, C1-C 12 alkenyl, C1-C4 alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H. In one embodiment, the organic phosphate compound having formula (VIII) is the stabilizer.

[0077] In yet another embodiment, R1, R2 and R3 are each independently selected from a linear or branched C1-C 12 Alkyl, linear or branched C1-C 12 Alkenyl, straight or branched C1-C 12 Alkoxyalkyl, linear or branched C7-C 30 Alkyl aralkyl, linear or branched C7-C 30 In one embodiment, R1, R2 and R3 are each independently selected from C1-C 12Alkyl, more typically, C2-C8 alkyl.

[0078] In one embodiment, R1, R2 and R3 are each independently a C1-C3 alkyl group, typically an ethyl group. In another embodiment, R1, R2 and R3 are each independently a branched C1-C3 alkyl group. 12 Alkyl, typically, 2-ethylhexyl. In one embodiment, R1, R2 and R3 are each independently C1-C 12 Alkoxyalkyl, typically, butoxyethyl.

[0079] In one embodiment, the organic solvent component of the compositions and methods of the present invention comprises dimethyl sulfoxide, dimethylformamide, diethylenetriamine, monoethanolamine, or mixtures thereof.

[0080] In one embodiment, the organic solvent component of the compositions and methods of the present invention comprises a mixture of at least one organophosphate solvent according to formula (VIII) (wherein R1, R2 and R3 are as described above) and dimethyl sulfoxide.

[0081] In one embodiment, the compound used as a solvent or as a component in a solvent blend is a compound having the general formula (II): R3OOC-A-CONR4R5 (ii)

[0082] According to one embodiment, the expression "compound" refers to any compound corresponding to the general formula (II). In other embodiments, the term "compound" also refers to a mixture of several molecules corresponding to the general formula (II). Thus, it can be a molecule of formula (II) or a mixture of several molecules of formula (II), wherein when referring to formula (II), both belong to the definition of the term "compound".

[0083] In certain embodiments, the R3, R4 and R5 groups may be the same, or in other embodiments, they are different. In one embodiment, they may be selected from C1-C 20 In another embodiment, they can be selected from C1-C 12 Alkyl, aryl, alkaryl or aralkyl or phenyl radicals. Particular mention is made of PolarClean (manufactured by Rhodia Inc. of Cranbury, NJ). The R4 and R5 groups may be optionally substituted. In a specific embodiment, the groups are substituted with hydroxyl.

[0084] In one embodiment, R3 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, isoamyl, n-hexyl, cyclohexyl, 2-ethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, tridecyl.

[0085] R4 and R5 groups are identical or different, and in one embodiment, can be especially selected from methyl, ethyl, propyl (n-propyl), isopropyl, n-butyl, isobutyl, n-pentyl, amyl, isopentyl, hexyl, cyclohexyl or hydroxyethyl. R4 and R5 groups can also be such that they form morpholine, piperazine or piperidine groups together with nitrogen-atoms. According to certain embodiments, R4 and R5 are each methyl, or R4 and R5 are each ethyl, or R4 and R5 are each hydroxyethyl.

[0086] According to one embodiment, if A comprises a linear group of formula --CH2--CH2-- and / or of formula --CH2--CH2--CH2--CH2-- and / or of formula --(CH2)8--, then it is a mixture of A groups. According to a specific embodiment, if A is linear, then it is a mixture of A groups, for example a mixture of two or three --CH2--CH2--(ethylene), --CH2--CH2--CH2--(n-propylene), and --CH2--CH2--CH2--CH2--(n-butylene) groups (or their isomers).

[0087] According to a first specific embodiment of the present invention, the A group is a divalent straight-chain alkyl group selected from a group having the following formula: --CH2--CH2--(ethylene), --CH2--CH2--CH2--(n-propylene), --CH2--CH2--CH2--CH2--(n-butylene), and mixtures thereof.

[0088] In one embodiment, based on 100 parts by weight ("pbw") of the inhibitor composition of the present invention, the composition comprises:

[0089] from about 4 pbw to about 60 pbw, more typically from about 10 pbw to about 55 pbw, and even more typically from about 20 pbw to about 40 pbw of dicyandiamide, and

[0090] From about 55 pbw to about 96 pbw, more typically from about 58 pbw to about 90 pbw, and even more typically from about 60 pbw to about 80 pbw of organic solvent.

[0091] In one embodiment, the inhibitor compositions of the present invention comprise one or more urease inhibitors, such as, for example, NBPT or ammonium thiosulfate.

[0092] The nitrogen fertilizer compound is treated with the inhibitor composition by contacting the nitrogen fertilizer compound with an inhibitor composition described herein (eg, a nitrification inhibitor or a urease inhibitor or a combination of both).The nitrogen fertilizer composition can be in solid or liquid form.

[0093] Suitable nitrogen fertilizers are those containing nitrogenous compounds such as urea, nitrates, ammonium salts or mixtures thereof, such as ammonium nitrate, ammonium sulfate, ammonium thiosulfate, ammonium polysulfide, ammonium phosphate, ammonium chloride, ammonium bicarbonate, anhydrous ammonia, calcium nitrate, sodium nitrate, calcium cyanamide. In one embodiment, the nitrogen fertilizer comprises ammonium nitrate. Suitable fertilizers containing ammonium nitrate include, for example, UAN 18, UAN 28 and UAN 30.

[0094] In one embodiment, the nitrogen fertilizer composition is in the form of solid particles, and contacting the nitrogen fertilizer composition with the inhibitor composition is performed by, for example, spraying the composition of the present invention onto the particles of the solid fertilizer composition.

[0095] In one embodiment, the concentrated fertilizer composition of the present invention is a solid fertilizer composition for inhibiting nitrification, comprising, based on 100 pbw of the composition: from about 60 pbw to about 99.999 pbw, more typically from about 70 pbw to about 99.999 pbw, and even more typically from about 80 pbw to about 99.999 pbw of solid particles of one or more nitrogen fertilizer compounds, and From about 0.001 pbw to about 40 pbw, more typically from about 0.001 pbw to about 30 pbw, and even more typically from about 0.001 pbw to about 20 pbw of dicyandiamide.

[0096] In one embodiment, the nitrification inhibiting solid fertilizer composition of the present invention further comprises one or more urease inhibitors, more typically NBPT.

[0097] In one embodiment, the end-use fertilizer composition of the present invention is made by combining the inhibitor composition of the present invention with a solid nitrogen fertilizer to form a nitrification inhibiting solid fertilizer composition, and then dissolving the nitrification inhibiting solid fertilizer composition in an aqueous medium (typically water) at a ratio of up to about 500 pbw, more typically from 100 pbw to 500 pbw, and even more typically from about 100 pbw to about 300 pbw of aqueous medium per 1 pbw of the nitrification inhibiting solid fertilizer composition.

[0098] In one embodiment, the fertilizer compound is in liquid form, and contacting the fertilizer composition with the inhibitor composition is performed by mixing the inhibitor composition with the liquid fertilizer composition.

[0099] In one embodiment, the concentrated fertilizer composition of the present invention is a concentrated liquid fertilizer composition for inhibiting nitrification, comprising, based on 100 pbw of the composition: from about 20 pbw to about 99.989 pbw, more typically from about 30 pbw to about 99.985 pbw, and even more typically from about 40 pbw to about 99.98 pbw of one or more nitrogen fertilizer compounds, From about 0.001 pbw to 40 pbw, more typically from about 0.005 pbw to 30 pbw, and even more typically from about 0.01 pbw to 20 pbw of dicyandiamide, and From about 0.01 pbw to 60 pbw, more typically from about 0.01 pbw to about 40 pbw, and even more typically from about 0.01 pbw to about 30 pbw of an organic solvent or solvent mixture as described herein.

[0100] In one embodiment, the concentrated liquid fertilizer composition of the present invention that inhibits nitrification further comprises one or more urease inhibitors, more typically NBPT.

[0101] In one embodiment, the end-use fertilizer composition of the present invention is made by combining the inhibitor composition of the present invention with a concentrated nitrogen fertilizer to form a nitrification inhibiting concentrated liquid fertilizer composition, and then diluting the nitrification inhibiting concentrated liquid fertilizer composition with an aqueous medium (typically water) at a ratio of up to about 500 pbw, more typically from about 10 pbw to about 500 pbw, and even more typically from about 100 pbw to about 300 pbw of aqueous medium per 1 pbw of the nitrification inhibiting concentrated liquid nitrogen fertilizer composition.

[0102] In one embodiment, the end-use fertilizer composition of the present invention is made by combining the inventive composition, a solid or concentrated liquid nitrogen fertilizer, and an aqueous medium.

[0103] In one embodiment, the end-use fertilizer composition of the present invention is an aqueous liquid composition comprising water, one or more nitrogen fertilizer compounds and typically from 2×10 -6 pbw to 4 pbw of dicyandiamide.

[0104] In one embodiment, the end-use fertilizer composition of the present invention comprises water and the following based on 100 parts by weight of the composition: from about 0.04 pbw to about 10 pbw, more typically from about 0.06 pbw to about 10 pbw, and even more typically from about 0.08 pbw to about 10 pbw of one or more nitrogen fertilizer compounds, From about 2 × 10 -6 pbw to about 4 pbw, more typically from about 1×10 -5 pbw to about 3 pbw, and even more typically from about 2×10 -4 to about 2 pbw of dicyandiamide, and From about 2 × 10 -4 pbw to about 6 pbw, more typically from about 2×10 -4 pbw to about 4 pbw, and even more typically from about 2×10 -4 to about 3 pbw of organic solvent.

[0105] In one embodiment, the end-use fertilizer composition of the present invention comprises one or more urease inhibitors (more typically NBPT), alone or in combination with a nitrification inhibitor.

[0106] In one embodiment, the end-use fertilizer composition of the present invention comprises from about 0.001 pbw to about 5 pbw, more typically from about 0.01 pbw to about 2 pbw of dicyandiamide per 100 pbw of one or more nitrogen fertilizer compounds.

[0107] In one embodiment, the end-use fertilizer composition is applied to the target plant or to the target plant's environment (i.e., to the land in or on which the target plant is or will be growing) at a rate of from about 0.01 pounds to about 5 pounds of the fertilizer composition, more typically from about 0.05 pounds to about 2 pounds of the fertilizer composition per 100 square feet of soil.

[0108] In one embodiment, the end-use fertilizer composition is applied to the target plant or to the environment of the target plant at a rate effective to provide a dosage of from about 0.01 pounds to about 5 pounds of the fertilizer compound, more typically from about 0.05 pounds to 2 pounds of the nitrogen fertilizer compound of the fertilizer composition per 100 square feet of soil.

[0109] In one embodiment, the end-use fertilizer composition is applied to the target plant or to the environment of the target plant at a rate effective to provide a dosage of dicyandiamide from about 0.01 pounds to 5 pounds of dicyandiamide per 1000 square feet of soil, more typically from about 0.05 pounds to 2 pounds of dicyandiamide.

[0110] The compositions of the present invention provide improved ease of handling of dicyandiamide, improved solubility characteristics, low toxicity of organic solvents, good storage characteristics, and excellent miscibility with aqueous compositions such as aqueous nitrogen fertilizer formulations.

[0111] In one embodiment, the composition comprises at least 50 wt% DCD and / or NBPT, the remainder being a solvent or a mixture of solvents, based on the weight of the composition. By way of example, in one embodiment, the fertilizer composition comprises at least 50 wt% NBPT and less than or equal to 50 wt% DMSO and a solvent blend of at least one organophosphate solvent according to formula (VIII), based on the weight of the composition, wherein R1, R2, and R3 are as described above. By way of another example, in one embodiment, the fertilizer composition comprises at least 50 wt% DCD and 50 wt% DMSO and a solvent blend of at least one organophosphate solvent according to formula (VIII), based on the weight of the composition, wherein R1, R2, and R3 are as described above. By way of another example, in one embodiment, the fertilizer composition comprises at least 50 wt% DCD and less than or equal to 50 wt% of at least one organophosphate solvent according to formula (VIII), based on the weight of the composition, wherein R1, R2, and R3 are as described above. Optionally, other components such as dyes and the like may be added.

[0112] In one embodiment, the composition comprises at least 25 wt% or 30 wt% DCD and / or NBPT, based on the weight of the composition, with the remainder being a solvent or a mixture of solvents. By way of example, in one embodiment, the fertilizer composition comprises at least 25 wt% of a combination of DCD and NBPT and less than or equal to 70 wt% of a solvent blend of the following, based on the weight of the composition: (i) at least one dioxolane compound having formula (III):

[0113] wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; and

[0114] (ii) at least one organic phosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above. Optionally, other components such as dyes etc. may be added.

[0115] By way of example, in another embodiment, the fertilizer composition comprises at least 25 wt%, typically at least 30 wt%, by weight of the composition, of a combination of DCD and NBPT and less than or equal to 70 wt% of a solvent blend of: (i) at least one dioxolane compound having formula (III):

[0116] wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; and

[0117] (ii) at least one organic phosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above. Optionally, other components such as dyes etc. may be added.

[0118] In one embodiment, the composition comprises greater than 40 pbw DCD and / or NBPT, with the remainder being solvent or a mixture of solvents, based on the weight of the composition.

[0119] In one embodiment, the composition comprises greater than 35 pbw DCD and / or NBPT, with the remainder being solvent or a mixture of solvents, based on the weight of the composition.

[0120] In one embodiment, the composition comprises greater than 45 pbw of DCD and / or NBPT, based on the weight of the composition, with the remainder being solvent or a mixture of solvents. By way of example, in one embodiment, the fertilizer composition comprises 45 wt% DCD and 55 wt% of a solvent blend of: (i) at least one dioxolane compound of formula (III), wherein R6 and R7 are as described above; and (ii) at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above.

[0121] In one embodiment, the composition comprises greater than 55 pbw of DCD and / or NBPT, based on the weight of the composition, with the remainder being solvent or a mixture of solvents. By way of example, in one embodiment, the fertilizer composition comprises at least 55 wt% of DCD and / or NBPT and less than or equal to 45 wt% of a solvent blend of: (i) at least one dioxolane compound having formula (III), wherein R6 and R7 are as described above; and (ii) at least one organophosphate solvent according to formula (VIII), wherein R1, R2 and R3 are as described above.

[0122] experiment:

[0123] Preparation 1

[0124] Preparation 2

[0125] A comparative sample was prepared using the same NBPT and solvent source as Formulation 1, except that the comparative sample did not contain TEP as a stabilizer. Both Formulation 1 and the comparative sample were kept at 45°C for 2 weeks. It was observed that both Formulation 1 and the comparative sample showed color evolution, both were initially colorless. After 2 weeks, the comparative sample was observed to turn dark amber. However, Formulation 1 turned a slightly yellow transparent color, which showed a lower NBPT degradation profile compared to the comparative example that did not contain the stabilizer.

[0126] refer to Figure 1 Both Formulation 1 and the comparative sample were analyzed in a stainless steel test cell using the standard HWS (Hot Wait Search Mode) method by ARC (Accelerated Rate Calorimetry) up to 100°C. The test was conducted under air atmosphere. An onset of about 76°C was determined for the unstable sample (i.e., the comparative sample), while no onset was determined for the stable sample (i.e., Formulation 1). It is believed that this onset is an exothermic reaction that gives an indication of instability. Again referring to Figure 1 , which illustrates the residual pressure as a function of temperature for both the comparative sample (without the organophosphate compound, ie, unstable) and Formulation 1 (with the organophosphate compound, ie, stable).

[0127] Lower residual pressure is an indication of less volatile components, an indirect measure of degradation. In other words, there are less volatile components measured over the temperature range for the stable formulation (Formulation 1) as compared to the comparative sample. The measurement of less volatile components over the temperature range indicates that less NBPT is degraded in Formulation 1 as compared to the comparative sample (i.e., more NBPT is degraded in the comparative sample). This is supported by the visual observation of both samples after 2 weeks at 45°C, where the comparative sample turned a much darker color, indicating more NBPT degradation compared to Formulation 1.

Claims

1. A liquid agricultural composition comprising - at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof; - An organic phosphate solvent having formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H; and - Optionally, at least one co-solvent selected from: (a) at least one dioxolane compound having the formula (III): (III) wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; b) at least one dibasic ester; c) at least one compound of formula (IIa): R3OOC-A-CONR4R5 (IIa), Where R3 contains C1-C 36 wherein R4 and R5 independently comprise C1-C 36 Alkyl, wherein R4 and R5 may optionally form a ring together; and wherein A is a linear or branched divalent C2-C6 alkyl group; d) at least one alkyl dimethyl amide; e) at least one alkyl lactate; f) ethyl levulinate; g) at least one alkoxy alcohol, ether alcohol, amine alcohol, amino alcohol or alcohol; h) at least one glycerol or a glycerol derivative; i) at least one alkylene carbonate; or j) Dimethyl sulfoxide.

2. The liquid agricultural composition of claim 1, wherein the nitrification inhibitor is dicyandiamide.

3. The liquid agricultural composition of claim 1, wherein the urease inhibitor is N-(n-butyl)-thiophosphoric triamide.

4. The liquid agricultural composition of claim 1, wherein the at least one co-solvent is present and comprises at least one dioxolane compound having formula (III): (III) wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10.

5. The liquid agricultural composition of claim 1, wherein the composition comprises: - at least one nitrification inhibitor; - An organic phosphate solvent having formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H; and - Dimethyl sulfoxide.

6. The liquid agricultural composition of claim 1, wherein the at least one of the nitrification inhibitor, the urease inhibitor, or a mixture thereof is present in an amount up to 65 wt% based on the total weight of the composition.

7. The liquid agricultural composition of claim 1, wherein the at least one of the nitrification inhibitor, the urease inhibitor, or a mixture thereof is present in an amount up to 55 wt% based on the total weight of the composition.

8. The liquid agricultural composition of claim 1, wherein the at least one of the nitrification inhibitor, the urease inhibitor, or a mixture thereof is present in an amount up to 50 wt% based on the total weight of the composition.

9. The liquid agricultural composition of claim 1, wherein the organophosphate solvent has formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl or aryl.

10. A method of making a solid or concentrated liquid fertilizer composition, the method comprising: One or more nitrogen fertilizer compounds are treated with a liquid inhibitor composition comprising at least one of dicyandiamide or an alkylthiophosphoric triamide, the inhibitor composition being dispersed in a liquid medium comprising at least one solvent having formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H.

11. The method of claim 10, wherein the organophosphate solvent has formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl or aryl.

12. The method of claim 10, wherein the liquid medium further comprises dimethyl sulfoxide.

13. The method of claim 10, wherein the liquid inhibitive composition further comprises at least one stabilizer.

14. A concentrated liquid fertilizer composition, based on 100 parts by weight of the composition, comprising: (a) up to about 99 parts by weight of one or more nitrogen fertilizer compounds, (b) at least one of dicyandiamide and alkylthiophosphoric triamide, (c) at least one organophosphate solvent having the formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H, and (d) Optionally, at least one co-solvent.

15. The concentrated liquid fertilizer composition of claim 14, wherein the organophosphate solvent is of formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl or aryl.

16. The concentrated liquid fertilizer composition of claim 14, wherein the at least one co-solvent (d) is present and comprises: (a) at least one dioxolane compound having the formula (III): (III) wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; b) at least one dibasic ester; c) at least one compound of formula (IIa): R3OOC-A-CONR4R5 (IIa), Where R3 contains C1-C 36 wherein R4 and R5 independently comprise C1-C 36 Alkyl, wherein R4 and R5 may optionally form a ring together; and wherein A is a linear or branched divalent C2-C6 alkyl group; d) at least one alkyl dimethyl amide; e) at least one alkyl lactate; f) ethyl levulinate; g) at least one alkoxy alcohol, ether alcohol, amine alcohol, amino alcohol or alcohol; h) at least one glycerol or a glycerol derivative; i) at least one alkylene carbonate; j) dimethyl sulfoxide; or k) any combination thereof.

17. The concentrated liquid fertilizer composition of claim 14, comprising: (a) up to about 99 parts by weight of one or more nitrogen fertilizer compounds, (b) alkylthiophosphoric triamides, (c) at least one organophosphate solvent having the formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H, and (d) Dimethyl sulfoxide.

18. A method of making an aqueous end-use fertilizer composition, the method comprising: One or more nitrogen fertilizer compounds are contacted with an inhibitor composition comprising at least one of dicyandiamide or an alkylthiophosphoric triamide, the inhibitor composition being dispersed in a liquid medium comprising at least one solvent having formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from H, C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl, or aryl; provided that at least one of R1, R2 or R3 is not H.

19. The method of claim 18, wherein the liquid medium further comprises at least one co-solvent selected from: (a) at least one dioxolane compound having the formula (III): (III) wherein R6 and R7 independently comprise hydrogen, alkyl, alkenyl or phenyl, wherein n is an integer from 1 to 10; b) at least one dibasic ester; c) at least one compound of formula (IIa): R3OOC-A-CONR4R5 (IIa), Where R3 contains C1-C 36 wherein R4 and R5 independently comprise C1-C 36 Alkyl, wherein R4 and R5 may optionally form a ring together; and wherein A is a linear or branched divalent C2-C6 alkyl group; d) at least one alkyl dimethyl amide; e) at least one alkyl lactate; f) ethyl levulinate; g) at least one alkoxy alcohol, ether alcohol, amine alcohol, amino alcohol or alcohol; h) at least one glycerol or a glycerol derivative; i) at least one alkylene carbonate; or j) Dimethyl sulfoxide.

20. The method of claim 18, wherein the liquid medium comprises: - at least one solvent having formula (VIII): (VIII) Wherein R1, R2 and R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Alkenyl, C1-C 16 Alkoxyalkyl, C7-C 30 Alkyl aralkyl, C7-C 30 Aralkyl or aryl; and - Dimethyl sulfoxide.

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