Increased longevity of the nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors designed for urea and manure based fertilizers

Abstract

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 urease inhibitors that are co-dissolved or blended solutions of each These novel formulations are designed to apply to fertilizers, especially urea and manure based fertilizers These 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, maintain 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 liquid fertilizer additive formulation comprising a) one or more nitrification inhibitors, b) one or more urease inhibitors, completely dissolved in c) an organo-liquid delivery system comprising i) dimethyl sulfoxide and ii) a solvating agent, wherein the solvating agent is a compound of Formula I:
B—X—Y is Formula I wherein: B is —H, CH.sub.3—O—, or HO—, X is —CH.sub.2—, ##STR00031## or —CH.sub.2—CH.sub.2— wherein W is —H, —CH.sub.2—CH.sub.3, or —CH.sub.3 Y is —CH.sub.2—A , ##STR00032## U, —N(CH.sub.3).sub.2, or ##STR00033## wherein A is —OK, ##STR00034## wherein K is —H, —CH.sub.3, or ##STR00035## wherein R.sup.5 is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein L is —H, —CH.sub.3, or ##STR00036## wherein “AC” is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein a is 1-10 wherein M is —H, —CH.sub.3, ##STR00037## wherein R.sup.6 is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein b is 1-10 wherein Q is H, -—CH.sub.3, ##STR00038## wherein R.sup.7 is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein c is 1-10 wherein d is 1-10 wherein D is —O—“AB”, (OCH.sub.2CH.sub.2).sub.cO, “AD”, ##STR00039## wherein “AB” is —H, —CH.sub.3, ##STR00040## wherein “AG” is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein “AD” is —H, —CH.sub.3, ##STR00041## wherein “AH” is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein e is 1-10 wherein “AE” is —H, —CH.sub.3, ##STR00042## wherein “AI” is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein f is 1-10 wherein “AF” is —H, —CH.sub.3, ##STR00043## wherein “AJ” is —H, —CH.sub.3, —CH(OH)—CH.sub.3 wherein g is 1-10 wherein h is 1-10 wherein J is —CH.sub.3 or —CH.sub.2—CH.sub.3 wherein G is —CH.sub.3, ##STR00044## wherein T is —N(CH.sub.3).sub.2 wherein R.sup.1 is —H, —OH, —CH.sub.2OH wherein R.sup.2 is —CH.sub.3, ##STR00045## wherein R.sup.3 is —H, —OH, —CH.sub.2OH wherein R.sup.4 is —H, —OH, —CH.sub.2OH wherein U is —H, —CH.sub.2—CH.sub.3, —CH.sub.3, —CH.sub.2—OH; wherein the dimethyl sulfoxide and the solvating agent meet 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 with a Chill Point <40° F; and wherein the one or more nitrification inhibitors are one or more members 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, thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine; in the liquid fertilizer additive formulation wherein the one or more nitrification inhibitors are present in an amount that is between about 10-45% of a total formulation amount and the liquid fertilizer additive formulation also contains a mixture of the dimethyl sulfoxide and the solvating agent that are present in ratios that are between about 20/80 to 80/20, and wherein the one or more urease inhibitors is selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphofic triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

2. The liquid fertilizer additive formulation of claim 1, further comprising a nitrification inhibitor that is dicyandiamide.

3. The liquid fertilizer additive formulation of claim 1, further comprising a nitrification inhibitor that is dicyandiamide.

4. The liquid fertilizer additive formulation of claim 3, further comprising one or more members selected from the group consisting of surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, and flow modifiers.

5. The liquid fertilizer additive formulation of claim 1, wherein the nitrification inhibitor (s) is(are) present in an amount that is between about 25-45% of a total formulation amount and the formulation also comprises N-(n-butyl) thiophosphoric triamide.

6. The liquid fertilizer additive formulation of claim 5, wherein the composition is substantially free of water.

7. The liquid fertilizer additive formulation of claim 1, wherein the one or more nitrification inhibitors is not dicyandiamide.

8. A liquid fertilizer additive formulation, which comprises a) one or more nitrification inhibitors b) one or more urease inhibitors, completely dissolved in c) an organo-liquid delivery system comprising i) dimethyl sulfoxide and ii) a solvating agent, wherein the liquid fertilizer additive formulation is made by heating a mixture comprising the one or more nitrification inhibitors and the one or more urease inhibitors in dimethyl sulfoxide to effectuate mixing of the mixture to attain a completely dissolved mixture wherein the dimethyl sulfoxide and the solvating agent meet 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 with a Chill Point <40° F.; and wherein the one or more nitrification irthibitor(s) is(are) present in an amount that is between about 25-45% of a total formulation amount, wherein the 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, thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine, and wherein the one or more urease inhibitors are 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.

9. The liquid fertilizer additive formulation of claim 8, further comprising a nitrification inhibitor that is dicyandiamide.

10. The liquid fertilizer additive formulation of claim 8, wherein the fertilizer additive further comprises a nitrification inhibitor that is dicyandiamide.

11. The liquid fertilizer additive formulation of claim 8, wherein the one or more urease inhibitors comprises N-(n-butyl) thiophosphoric triamide.

12. The liquid fertilizer additive formulation of claim 8, wherein the one or more nitrification inhibitors is not dicyandiarnide.

Description

EXAMPLE 1

(1) 65 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and 10 grams of tripropylene glycol methyl ether was added. The mixture was cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 2

(2) 69 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 15 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 40° C. and then 10 grams of 2-chloro-6-(trichloromethyl)pyridine was as added and mixed until dissolved. 6 grams of tripropylene glycol methyl ether was added and the mixture was cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 3

(3) 65 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 10 grams of dicyandiamide and 10 grams of thiourea were then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 5 grams of n-butyl thiophosphoric triamide was charged to the vessel and mixed until completely dissolved. 15 grams of propylene glycol was charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 4

(4) 57.1 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 40° C. 20 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, 22.9 grams of dipropylene glycol was charged the mixture was cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 5

(5) 58.3 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 3,4-dimethylpyrazole phosphate was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 4.3 grams of tripropylene glycol methyl ether and 12.5 grams of propylene carbonate were charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 6

(6) 54.4 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 10 grams of 2-chloro-6-(trichloromethyl)pyridine and 15 grams of thiourea were then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 10.6 grams of dipropylene glycol and 10 grams of propylene glycol were charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 7

(7) 45 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 1H-1,2,4-triazole thiol was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 30 grams of N,N-dimethyl 9-decenamide was added to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 8

(8) 50 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 15 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 5 grams of n-butylthiophosphoric triamide was and the resulting product was mixed until dissolved. 30 grams of dipropylene glycol was charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

EXAMPLE 9

(9) 80 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 10

(10) 80 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphoric triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 11

(11) 80 grams of propylene carbonate was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphoric triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 12

(12) 80 grams of tripropylene glycol methyl ether was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 13

(13) 75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 4-amino-4H-1,2,4-triazole was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 14

(14) 50 grams of Example 9 and 50 grams of Example 10 were mixed together for 30 minutes and then packaged off in an appropriate container.

EXAMPLE 15

(15) 58.3 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 4-amino-4H-1,2,4-triazole was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C., 16.7 grams of propylene glycol was added, the formulation was mixed for 30 minutes and then packaged off in an appropriate container.

EXAMPLE 16

(16) 80 grams of dipropylene glycol was charged to a vessel and then placed under strong agitation and heated to 38° C. 20 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. The mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 17

(17) 50 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and 16 grams of propylene carbonate, and 14 grams of propylene glycol were charged to the vessel and then mixed for 15 minutes and packaged off in an appropriate container.

EXAMPLE 18

(18) 80 grams of propylene glycol was charged to a vessel and then placed under strong agitation and then heated to 60° C. 20 grams of thiourea was then charged to the vessel and mixed until completely dissolved. The mixture was cooled to 30° C. and packaged off in an appropriate container.

EXAMPLE 19

(19) 50 grams of dimethyl acetamide was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphate triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and 20 grams of propylene carbonate and 10 grams of propylene glycol were charged to the vessel and mixed for 15 minutes and then packaged off in an appropriate container.

EXAMPLE 20

(20) 75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 3,4-dimethylpyrazole phosphate was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled <30° C. and then packaged off in an appropriate container.

EXAMPLE 21

(21) 75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled <30° C. and then packaged off in an appropriate container.

(22) The below table 1 summarizes the compositions that occur in each of the examples. The presence of an “X” in table 1 means that the particular example composition contains that particular component.

(23) TABLE-US-00001 TABLE 1 Example No. DMSO DCD TPGME CTMP thiourea NBPT PG DPG DMPP PC TT DD AT DMA 1 X X X 2 X X X X 3 X X X X X 4 X X X 5 X X X X 6 X X X X X 7 X X X 8 X X X X 9 X X 10 X X 11 X X 12 X X 13 X X 14 X X X X 15 X X X 16 X X 17 X X X X 18 X X 19 X X X X 20 X X 21 X X DMSO—dimethylsulfoxide DCD—dicyandiamide TPGME—tripropylene glycol methyl ether CTMP—2-chloro-6-(trichloromethyl)pyridine NBPT—n-butyl thiophosphoric triamide PG—propylene glycol DPG—dipropylene glycol DMPP—3,4 dimethylpyrazole phosphate PC—propylene carbonate TT—1H-1,2,4,-triazole thiol DD—N,N-dimethyl 9-decenamide AT—4-amino-4H-1,2,4-triazole DMA—dimethyl acetamide

(24) Samples from Examples 1-21 were evaluated for physical properties and the results are shown in the below Table 2:

(25) TABLE-US-00002 TABLE 2 Stability Chill Human Flash Aquatic Sample 24 hrs Point Health Point Toxicity # @ 20° C. ° F. Rating ° F. Rating Ex 1 Stable <−5° 1.0 >145° Low Ex 2 Stable <−5° 1.0 >145° Low Ex 3 Stable <−5° 1.0 >145° Low Ex 4 Stable  23° F. 1.0 >145° Low Ex 5 Stable <−5° 1.0 >145° Low Ex 6 Stable  .sup. 5° 1.0 >145° Low Ex 7 Stable  .sup. 10° 2 >145° Medium Ex 8 Stable  .sup. 5° 1 >145° Low Ex 9 Stable  .sup. 25° 1 >145° Low Ex 10 Stable  .sup. 32° 1 >145° Low Ex 11 cloudy  .sup. 72° 1 >145° Low Ex 12 Not soluble N/A 1 >145° Low Ex 13 Stable 37.4 1 >145° Low Ex 14 Stable <−5° 1 >145° Low Ex 15 Stable <−5 1 >145° Low Ex 16 Not soluble N/A 1 >145° Low Ex 17 Stable <−5° 1 >145° Low Ex 18 Not soluble N/A 1 >145° Low Ex 19 Stable <−5° 3 <145° Medium Ex 20 Stable  .sup. 55° 1 >145° Low Ex 21 Stable  .sup. 55° 1 >145° Low

(26) The Human Health rating is based on the HMIS (Hazardous Materials Information System) rating on Health of any organo solvent component>2%

(27) The Flash Point is based on the flash point of any organo solvent component>5%.

(28) The Aquatic Toxicity Rating is based on any organo solvent component at any level.

(29) It should be apparent from the above table 2 that a combination of factors will produce an organo-liquid delivery system that provides or gives a solution that includes at least one of the following characteristics: a. soluble b. Are environmentally safe; c. Have flashpoints above 145° F.; d. Are inherently rated safe for contact with humans and animals; e. Maintain the nitrification inhibitors at levels of 1-50% in solution to storage temperatures down to at least 10° C. f. Provides improved even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules

(30) In an embodiment, the composition results in a formulation that satisfies more than one of the above functional properties. In a variation, the formulations may have two of the above functional properties, or alternatively, three of the above functional properties, or alternatively, four of the above functional properties, or alternatively five of the above functional properties or alternatively all six of the above functional properties. Each of the functional properties may be desired (or emphasized) relative to the other functional properties based upon the intended use and transport of the compositions of the present invention. For example, one functional property may be emphasized based upon storage conditions of the formulations, or the shipping conditions of the formulations, or how the formulation is used, or based upon some other desired property. For example, if one knows that the formulation is likely to be stored at high temperatures for a long period of time, the functional property that provides the greatest stability of the formulation is likely to be used. Environmental safety may be emphasized if the formulations of the present invention are to be used where any potential run-off of the formulation is to be used near a drinking source.

(31) In one embodiment of the present invention, compositions were made that gave favorable properties for most of the above listed functional properties. That is, the compositions of the present invention attempted to emphasize solubility, environmental safety, a low freeze chill point, a high flash point, even coating of a fertilizer particle and a composition that could be handled safely by both humans and/or animals.

(32) The results as shown in the above table 2 demonstrate that the usage of a single organo-liquid solvent may in some instances show a much higher chill point product versus blends of the various solvents. For example, comparing examples 4, 21 and 16 shows that a blend of DMSO with other organo-liquid solvents has a beneficial effect as it relates to the lower chill point and improving solubility. Other trends can be observed by comparing a) examples 9, example 1, example 12 and example 17, b) example 13 to example 15, and c) example 5 and example 20.

(33) In one embodiment of the present invention, it is contemplated and therefore within the scope of the invention that compositions such as examples 2, 3 and 6 that contain more than one nitrification inhibitor will have superior performance in inhibiting the conversion of ammonia to nitrite and/nitrate over compositions containing only one nitrification inhibitor due to the expected differences in mechanisms by which each nitrification inhibitor operates, the variation of enzymatic sites and the fact that this conversion is basically orchestrated by two groups of organisms, ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). The flexibility of the organo-liquid delivery system in solubilizing the various nitrification inhibitors in certain embodiments provides stable, environmentally responsible and safe compositions. Thus, in certain embodiments, these compositions can be added easily and economically to a broad range of manmade and natural fertilizers, thus improving the longevity of these applied fertilizers.

EXAMPLE 22

(34) To better visualize coating and penetration on the urea prills, Example 17 was dyed with powdered ‘Rhodamine 6G’ dye (Sigma-Aldrich). The powdered dye (20 mg) was added to 10 mL of Example 17 and mixed thoroughly. The resulting product was reddish-purple in color. It was then topically applied to granulated urea at an application rate equivalent to 3 qt/ton. The resulting product was thoroughly mixed for three minutes, providing uniform coverage to the prills. The product was then allowed to sit for 3 hours.

(35) Eight spherical prills of relatively uniform size were selected at random from the red-dyed covered urea. The prills were split in half with a razor blade. One half of each prill was glued to a piece of paper with the split face (middle) facing up, and the prills were photographed.

(36) The coverage on the urea prills was equally uniform as was the penetration of the prills. The average prill diameter was 3.2 mm (⅛ inch). Example 17 penetrated the prills approximately one-sixth of the diameter, or to a depth of 0.5 mm ( 1/48 inch). The penetration depth of 0.5 mm is visually demonstrated in FIG. 1. The average diameter of each urea covered prill is shown in FIG. 1 as well as well as the average penetration depth 2.

EXAMPLE 23

(37) An inhibition study was conducted as described below.

(38) Experimental Outline:

(39) A 12 week laboratory experiment was conducted in an incubation chamber set to a constant air temperature of 85° F. The experiment consisted of 4 replicate 1 quart disposal plastic tubs, each filled with 250 grams of wetted soil (a Marvyn loamy sand, which is approximately 80% sand), each of which was submitted to the appropriate treatments. Prior to placing the soil in the jar the sample was sieved through a 2 mm screen and wetted to an uniform water content (˜70% of field capacity). The background soil sample indicated the following parameters: soil pH: 5.6, phosphorus: 15 lb/A, potassium: 32 lb/A, magnesium: 20 lb/A, and calcium: 139 lb/A. No lime or additional fertilizers were added to this soil.

(40) The following 5 treatments were evaluated, and there were four replications of each treatment.

(41) TABLE-US-00003 Sample Treatment 1 4 quarts of Example 17 per ton of urea 2 6 quarts of Example 17 per ton of urea 3 8 quarts of Example 17 per ton of urea 4 Urea only control 5 No fertilizer control

(42) The correct amount of Example 17 to treat one pound of urea was calculated, and that amount was sprayed on to the urea using an air brush sprayer. Example 17 was not diluted, and a uniform coating was achieved. The treated (and untreated) ureas were then mixed at an N ratio of 120 pounds N/acre. The corresponding N ratio was calculated using the area of the plastic tub.

(43) The soil-fertilizer mix was placed into the incubator. Each week thereafter (for 12 weeks) the following occurred: 1) each bin was removed from the incubator, opened and lightly mixed before sampling, 2) a 2 g subsample of soil was removed for soil-water content determination, and, 3) a 2 g subsample of soil was removed for soil nitrate and ammonium concentration (via 2M KCl extraction). The bins were resealed and returned to the incubator until the next sampling date.

(44) Conclusions:

(45) Application of Example 17 at 4 qt/T significantly increased soil ammonium-N at weeks 4, 5 and 6. When Example 17 was applied at 6 qt/T there was more soil ammonium-N (as compared to the urea only treatment) at weeks 3 and 6. The best inhibition of nitrification was observed when the Example 17 was applied at 8 qt/T, as soil ammonium in that treatment was greater than measured in the urea only treatment at weeks 2, 3, 4, 5, 6 and 7. This ratio gives the best inhibition of nitrification.

(46) If nitrification is inhibited, the nitrogen content resulting from ammonium will accumulate, as the ammonium to nitrate conversion is slowed. Since nitrate-N production is slowed, the treatments to which an inhibitor should have reduced nitrate-N. This was observed when the highest rate of Example 17 was applied (8qt/T) and the effect was significant (as compared to the urea only treatments) in weeks 4, 5, 6 and 7. When lower rates of Example 17 were applied, the effect was only significant at weeks 5 and 7.

(47) In this one time 8 week incubation study, when Example 17 was applied to urea at 8 qt/Ton, it exhibited significant nitrification inhibitory properties.

EXAMPLE 24

(48) A degradation study was performed using 2-chloro-6-(trichloromethyl)pyridine/nBPT in DMSO.

(49) A 2-chloro-6-(trichloromethyl)pyridine/NBPT=1/1 (w/w) mixture was dissolved in DMSO. LC (liquid chromatography) was performed to analyze the content decrease versus time. All samples were sealed and protected under N.sub.2. All samples were stored 50° C.

(50) Analysis Condition:

(51) A C18 column was used, and measured at 255 nm. Retention time: 40 min. Temperature: 30° C. 15 μL injection. Peak area percentages were calculated to analyze the concentration and are shown in below Table 3.

(52) TABLE-US-00004 TABLE 3 Solvent DMSO solute 2-chloro-6- n-butylthiophosphoric Week # (trichloromethyl)pyridine triamide 1 100 100 2 99 99.6 3 99.4 98 4 98.3 97.6 6 95.3 96.5 7 93.2 95.3 8 92.3 94.7 9 90.8 93 10 88 92.2 11 86.7 92.1 12 86.4 91.7 13 85 91 14 84.33 90.88 15 83.56 90.01 16 81.45 99.55 17 81 89.06 18 80.09 88.6
Both actives show good stability in DMSO at 50° C. for 18 weeks.

(53) In an embodiment, the present invention relates to a composition comprising one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following:

(54) Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols:
ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether.
wherein the organo-liquid delivery system meets the following criteria: a. soluble b. Are environmentally safe; c. Have flashpoints above 145° F.; d. Are inherently rated safe for contact with humans and animals; e. Maintain the nitrification inhibitors at levels of 1-50% in solution to storage temperatures down to at least 10° C.; f. Provides improved even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules

(55) In an embodiment the composition comprises a nitrification inhibitor that is 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.

(56) In an embodiment, the present invention relates to a composition comprising one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following in Formula I:
B—X—Y is Formula I
wherein:
B is —H, CH.sub.3—O—, or HO—,
X is —CH.sub.2—,

(57) ##STR00016##
or —CH.sub.2—CH.sub.2—

(58) wherein W is —H, —CH.sub.2—CH.sub.3, or —CH.sub.3

(59) Y is —CH.sub.2-A,

(60) ##STR00017##
U, —N(CH).sub.2, or

(61) ##STR00018##

(62) wherein A is —OK,

(63) ##STR00019##

(64) wherein K is —H, —CH.sub.3, or

(65) ##STR00020##

(66) wherein R.sup.5 is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(67) wherein L is —H, —CH.sub.3,

(68) ##STR00021##

(69) wherein “AC” is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(70) wherein a is 1-10

(71) wherein M is —H, —CH.sub.3,

(72) ##STR00022## wherein R.sup.6 is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(73) wherein b is 1-10

(74) wherein Q is H, —CH.sub.3,

(75) ##STR00023## wherein R.sup.7 is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(76) wherein c is 1-10

(77) wherein d is 1-10

(78) wherein D is —O-“AB”, (OCH.sub.2CH.sub.2—).sub.eO“AD”,

(79) ##STR00024##

(80) wherein “AB” is —H, —CH.sub.3,

(81) ##STR00025## wherein “AG” is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(82) wherein “AD” is —H, —CH.sub.3,

(83) ##STR00026## wherein “AH” is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(84) wherein e is 1-10

(85) wherein “AE” is —H, —CH.sub.3,

(86) ##STR00027## wherein “AI” is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(87) wherein f is 1-10

(88) wherein “AF” is —H, —CH.sub.3,

(89) ##STR00028## wherein “AJ” is —H, —CH.sub.3, —CH(OH)—CH.sub.3

(90) wherein g is 1-10

(91) wherein h is 1-10

(92) wherein J is —CH.sub.3 or —CH.sub.2—CH.sub.3

(93) wherein G is —CH.sub.3,

(94) ##STR00029##
wherein T is —N(CH.sub.3).sub.2
wherein R.sup.1 is —H, —OH, —CH.sub.2OH
wherein R.sup.2 is —CH.sub.3,

(95) ##STR00030##
wherein R.sup.3 is —H, —OH, —CH.sub.2OH
wherein R.sup.4 is —H, —OH, —CH.sub.2OH
wherein U is —H, —CH.sub.2—CH.sub.3, —CH.sub.3, —CH.sub.2—OH;
wherein the organo-liquid delivery system meets the following criteria: a. soluble b. Are environmentally safe; c. Have flashpoints above 145° F.; d. Are inherently rated safe for contact with humans and animals; e. Maintain the nitrification inhibitors at levels of 1-50% in solution to storage temperatures down to at least 10° C.; f. Provides improved even application to fertilizer granules of nitrification inhibitors while not causing clumping of the granules.

(96) In one variation, the composition comprises an organo-liquid delivery system in the mixture that is dimethyl sulfoxide. In a variation, dimethyl sulfoxide comprises between about 10 and 90% of the total composition.

(97) In one embodiment, the 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 organo-liquid solvents in ratios that are between about 20/80 to 80/20.

(98) In an embodiment, the composition further comprises: surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed nitrification inhibitors, dispersed urease inhibitor(s), crystallization inhibitors and/or flow modifiers.

(99) In an embodiment, the 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.

(100) In one embodiment, the composition is substantially free of water.

(101) In an embodiment, the present invention relates to a fertilizer granule or liquid additive, which comprises one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following: Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols: ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether.

(102) In an embodiment, the fertilizer granule or liquid additive comprises one or more nitrification inhibitors such as 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.

(103) In a variation, the fertilizer granule or liquid additive may further comprise one or more urease inhibitors such as phosphoric triamides, thiophosphoric triamides or alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

(104) In an embodiment, the fertilizer granule or liquid additive may contain one or more nitrification inhibitors such as 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; wherein the one or more urease inhibitors comprises phosphoramides.

(105) In an embodiment, the present invention relates to making the compositions and fertilizer granules and liquid additives of the present invention. In one variation, the method relates to making a composition to be added to a fertilizer comprising:

(106) heating a mixture comprising one or more nitrification inhibitors in an organo liquid delivery system comprising an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following:

(107) Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols:

(108) ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether and cooling the mixture to a temperature that optionally allows an addition of one or more of:

(109) surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed nitrification inhibitors, dispersed urease inhibitor(s), crystallization inhibitors and/or flow modifiers.

(110) In a variation, the method further comprises adding the composition to a fertilizer granule or liquid as an additive.

(111) In one variation, the method makes a composition 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.

(112) In one variation, the method uses 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.

(113) In one variation, the method uses one or more nitrification inhibitors such as 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.

(114) In one variation of the method, the method employs steps so as to make sure that the composition is substantially free of water.

(115) The following references are incorporated by reference in their entireties. U.S. Pat. No. 4,234,332 to Michaud U.S. Pat. No. 4,294,604 to Evrard U.S. Pat. No. 5,024,689 to Sutton et al. U.S. Pat. No. 5,106,984 to Halpern U.S. Pat. No. 6,488,734 to Barth U.S. Pat. No. 8,562,711 to Sutton, and WO 2008/000196.

(116) 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. It is also contemplated that any feature or member of a group can be omitted from a list of possible features and/or members. 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.