Agricultural compositions and methods of making and using the same

Abstract

The present disclosure relates to an agricultural composition comprising paraformaldehyde, a nitrification inhibitor, urea, an ammonia source or a combination thereof and one or more reaction products prepared from paraformaldehyde, a nitrification inhibitor, urea, an ammonia source and an optional solvent, wherein the one or more reaction products are present in an amount of at least 20% by weight of the total weight of the agricultural composition. A fertilizer composition comprising the agricultural composition and a nitrogen source is also disclosed. A method for preparing the agricultural composition is also disclosed.

Description

[0001] Related patent applications

[0002] This patent application claims priority to U.S. Provisional Application No. 63 / 251,697, filed on October 4, 2021, the entirety of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to an agricultural composition comprising a relatively high concentration of one or more reaction products, also referred to as adducts or active ingredients, prepared from paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent. For example, the agricultural composition contains at least 20% by weight of the reaction products based on the gross weight of the agricultural composition. The present disclosure also includes a fertilizer composition comprising the agricultural composition and a nitrogen source. The composition of the present disclosure has a variety of benefits, including improved efficiency and processability and low water content. A method for preparing an agricultural composition and a fertilizer composition according to the present disclosure is also disclosed.

[0004] Fertilizers can include urea, ammonia, ammonium nitrate, or mixtures thereof from any source to provide a nitrogen source, which is an important nutrient for plant growth. If urea is used as a nitrogen source in fertilizers, urease (an enzyme produced by a variety of fungi and bacteria found in the soil) can hydrolyze the urea into ammonia. Ammonia can be rapidly ionized in the soil to form ammonium. Ammonium (such as in ammonium nitrate) can be oxidized to nitrate (NO) by a series of bacterial oxidation reactions. 3 - ), which is often referred to as "nitrification". However, nitrification of ammonium can occur so rapidly that a large percentage of the nitrogen in the fertilizer may be lost before it can be used by plants.

[0005] Nitrogen in the form of ammonia can also be lost from soils by volatilization to the atmosphere. Nitrates can also be lost through infiltration of rainwater into the subsoil and / or through denitrification, the conversion of nitrates by bacteria into elemental nitrogen.

[0006] Nitrogen losses can be reduced by using urease inhibitors and / or nitrification inhibitors. Urease inhibitors are compounds that can inhibit the catalytic activity of urease in soil to urea. Nitrification inhibitors are compounds that can inhibit bacteria in soil from oxidizing ammonium to nitrates. Nitrification inhibitors themselves can penetrate the soil, away from plants, thereby reducing the nitrification inhibition near plants in need. Nitrification inhibitors can work by temporarily binding to the active site (or near the active site) of ammonia monooxygenase in the bacterium Nitrosomonas europaea. When this binding is temporary, these nitrification inhibitors are considered to be reversible inhibitors and may not cause the death of bacteria. In some embodiments of the present disclosure, nitrification inhibitors are reversible inhibitors. These inhibitors slow down nitrification, but do not completely stop nitrification, thereby making the availability of nitrogen similar to the need for nitrogen in growing plants.

[0007] Compositions containing urease inhibitors and / or nitrification inhibitors can be used to extend the useful life of nitrogen in the soil. Such compositions can be added to a nitrogen source before application to the soil, or can be applied directly to the soil to which a nitrogen source has been applied. Urease inhibitors and / or nitrification inhibitors can also be used in agricultural compositions in the form of adducts. Adducts are described, for example, in U.S. Patents 9,440,890, 10,239,799, 10,125,056, 9,725,372, 10,421,693, and 10,479,737. is a commercial nitrogen stabilizer composition containing Pronitridine (CAS RN 1373256-33-7) as its active ingredient. Pronitridine is identified as the reaction product of urea with ammonium hydroxide, N-cyanoguanidine and formaldehyde. Contains 14% of the active ingredient Pronitridine and 86% of other ingredients. It has a relatively low active ingredient content and is therefore designed for use with gaseous and liquid nitrogen fertilizers. The required application rates are too high for it to be used as an additive to solid fertilizers such as urea or ammonium nitrate.

[0008] The ease of use and efficacy of the agricultural composition containing the adduct depends on a variety of properties, such as concentration, viscosity and water content. For example, concentrated agricultural compositions can have certain advantages in, for example, transportation, storage and use on an industrial scale. In addition, it may be desirable to use agricultural compositions to coat solid nitrogen sources, such as urea, to obtain uniformly coated urea products having crushing strength, fluidity and non-caking properties identical or similar to uncoated solid fertilizers. In addition, it is desirable that such treatments of solid nitrogen sources will not be "sticky", so that both newly treated materials and treated materials stored in both open and closed environments maintain the flow of solid particles. This also reduces the possibility of accumulation on fertilizer application equipment.

[0009] Therefore, there is a need for improved agricultural compositions comprising nitrification inhibiting adducts that provide an extended nitrification inhibition period, and methods of making and using the same. There is also a need for high concentration agricultural compositions that may also have low water content and low viscosity. Such improved agricultural compositions allow for coated urea fertilizers to have beneficial properties, such as good crush strength, flowability, and non-caking.

[0010] The present disclosure relates to agricultural compositions comprising one or more reaction products prepared from paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and optionally a solvent, wherein the one or more reaction products are present in an amount of at least 20 weight percent of the total weight of the agricultural composition.

[0011] The agricultural compositions of the present disclosure may also include paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, an optional solvent, or a combination thereof in their unreacted form, which is not part of the reaction product. In certain embodiments, the unreacted nitrification inhibitor is present in at least 7% by weight of the agricultural composition, such as in an amount ranging from about 7% by weight to about 15% by weight. In at least one embodiment, the unreacted nitrification inhibitor is present in an amount ranging from about 10% by weight to about 15% by weight.

[0012] In at least one embodiment, the nitrification inhibitor is dicyandiamide.

[0013] In some embodiments, one or more of the reaction products is a compound of Formula (I).

[0014]

[0015] In formula (I), X is O or R 1 , R 2 , R 3 and R 4 Each independently is:

[0016]

[0017] wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula:

[0018]

[0019] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0020] In formula (I), if X is O, then R 1 , R 2 , R 3 or R 4 One or more of

[0021] In some embodiments, one or more of the reaction products is a compound of formula (A), a compound of formula (B), or a compound of formula (C).

[0022]

[0023] In formula (A), formula (B) and formula (C), each R is independently hydrogen, a substituted or unsubstituted alkyl group or Y, wherein Y is represented by the following formula:

[0024]

[0025] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0026] In some embodiments, the agricultural composition further comprises water, and the water content ranges from 10% to 30% by weight of the total agricultural composition.

[0027] In some embodiments, the viscosity of the agricultural composition is less than 150 cps, such as less than 100 cps.

[0028] In some embodiments, the agricultural composition further comprises a dye.

[0029] The present disclosure also includes fertilizer compositions comprising a nitrogen source and an agricultural composition as disclosed herein.

[0030] Also provided are methods of making agricultural and fertilizer compositions. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A portion of an LC-MS chromatogram is depicted.

[0032] Figure 2 is a table of exemplary compositions.

[0033] Figure 3 is a table of exemplary compositions.

[0034] Figure 4 is a table of exemplary reaction compositions.

[0035] Figure 5 is a table of exemplary reaction compositions.

[0036] Figure 6 is a table of exemplary reaction compositions.

[0037] Figure 7 is a table of exemplary reaction conditions.

[0038] Figure 8 is a table of exemplary reaction conditions.

[0039] Fig. 9 is a table of exemplary reaction conditions.

[0040] Fig.10 Stability information for exemplary compositions is provided. DETAILED DESCRIPTION

[0041] Agricultural composition :

[0042] The present disclosure relates to agricultural compositions comprising one or more reaction products prepared from paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent, wherein the one or more reaction products are present in an amount of at least 20% by weight of the total weight of the agricultural composition. In some embodiments, the one or more reaction products are present in an amount of at least 27.5% by weight of the total weight of the agricultural composition. In some embodiments, the one or more reaction products are present in an amount of at least 30% by weight of the total weight of the agricultural composition.

[0043] The agricultural composition of the present disclosure may also include paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, an optional solvent, or a combination thereof in their unreacted form, which are not part of the reaction product. As used herein, "paraformaldehyde" refers to a polyol of the formula HO(CH 2 O) n H compounds, wherein n is greater than 3. The paraformaldehyde may be polydisperse and may include compounds of the formula HO(CH 2 O) n In some embodiments, the paraformaldehyde has an average n greater than 5. In some embodiments, the paraformaldehyde has an average n greater than 8. In some embodiments, the paraformaldehyde has an average n in the range of 8 to 100. In some embodiments, the paraformaldehyde is a solid. It has been surprisingly discovered that the use of paraformaldehyde to prepare the reaction products disclosed herein can provide agricultural compositions with improved properties, such as relatively high concentrations of one or more soluble reaction products.

[0044] As used herein, "nitrification inhibitor" refers to a compound that can inhibit bacteria in the soil from oxidizing ammonium to nitrate. Nitrification inhibitors include, but are not limited to: 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, dicyandiamide, 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6-trichloromethyl-5-triazine, polyether ionophores, 4-amino-1,2,4-triazole, 3 -mercapto-1,2,4-triazole, potassium azide, carbon disulfide, sodium trithiocarbonate, ammonium dithiocarbamate, methylcarbamic acid, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, ammonium thiosulfate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamide, 1,2,4-triazole, 3-methylpyrazole, their derivatives and any combination thereof. In at least one embodiment, the nitration inhibitor is dicyandiamide (DCD).

[0045] Urea can be used in a variety of forms. For example, urea can be a solid in the form of granules, flakes, particles, etc., and / or a solution, such as an aqueous solution. At least a portion of the urea can be in the form of animal waste. Any of these urea sources can be used alone or in any combination.

[0046] As used herein, the term "ammonia source" refers to ammonia and ammonium compounds that release ammonia when reacting with paraformaldehyde and a nitrification inhibitor. Ammonia sources include, for example, ammonium salts such as ammonium nitrate, ammonia water or ammonium hydroxide, anhydrous ammonia or a combination thereof. Suitable ammonia solutions may have, for example, an ammonia concentration of about 28% by weight, about 30% by weight, about 32% by weight or about 35% by weight. Other suitable ammonia sources include, for example, primary amines or substituted primary amines, such as methylamine, monomethanolamine, aminopropanol or any combination thereof. Difunctional amines such as ethylenediamine or any combination of organic amines may be used, provided that one primary amine group may be used to form a triazone ring. Another source of ammonia may be in the form of animal waste, such as urine and / or feces. Any of these ammonia sources may be used alone or in any combination. Ammonia sources may be used in any form, such as liquid, solid and / or gas.

[0047] The reaction product of the present disclosure may include discrete compounds, polydisperse compounds and / or combinations thereof. For example, the reaction product may include polydisperse oligomers and polymers. The reaction product may have a weight average molecular weight (or molar mass) of about 100Da or more. The molar mass of the reaction product may be about 100Da to about 10,000Da, about 100Da to about 5,000Da, about 100Da to about 1,000Da, or about 100Da to about 500Da. In some embodiments, the molar mass of the reaction product is in the following one or more ranges: 100Da to 200Da; 200Da to 300Da; 300Da to 400Da; 500Da to 1,000Da, 1,000Da to 2,000Da; and 2,000Da and more.

[0048] The reaction products of the present disclosure can be analyzed by standard techniques, such as high performance liquid chromatography (HPLC), liquid chromatography mass spectrometry (LCMS), size exclusion chromatography (SEC), and nuclear magnetic resonance (NMR) spectroscopy.

[0049] In some embodiments, the reaction product has an oligomeric and / or polymeric backbone comprising nitrogen-carbon-nitrogen repeating units. In some embodiments, the oligomeric and / or polymeric backbone is one or more of linear, branched, cyclic, or a combination thereof. In some embodiments, the reaction product having an oligomeric and / or polymeric backbone has one or more side groups selected from:

[0050]

[0051] In some embodiments, one or more reaction products are one or more compounds of Formula (I).

[0052]

[0053] In formula (I), X is O or R 1 , R 2 , R 3 and R 4 Each independently is:

[0054]

[0055] wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula:

[0056]

[0057] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0058] In formula (I), if X is O, then R 1 , R 2 , R 3 or R 4 One or more of

[0059] In some embodiments, one or more of the reaction products is a compound of formula (A), a compound of formula (B), or a compound of formula (C).

[0060]

[0061] In formula (A), formula (B) and formula (C), each R is independently hydrogen, a substituted or unsubstituted alkyl group or Y, wherein Y is represented by the following formula:

[0062]

[0063] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0064] In some embodiments, the agricultural composition also includes water, and the water content is within the range of 10% to 30% by weight of the total agricultural composition. The water content of the agricultural composition of the present disclosure can be reduced by distillation while maintaining the good stability of the resulting composition. In at least one embodiment, distillation can be used to remove at least 3% by weight of water, at least 4% by weight of water, at least 5% by weight of water, at least 6% by weight of water from the agricultural composition. In other embodiments, distillation can be used to remove at least 10% by weight of water. In at least one embodiment, after distillation, the resulting agricultural composition maintains the same stability characteristics as it had before removing the water.

[0065] The viscosity of the agricultural composition disclosed herein can vary. In some embodiments, the viscosity is less than 150cps at 25°C. In some embodiments, the viscosity of the agricultural composition is less than 100cps at 25°C. In some embodiments, the viscosity of the agricultural composition is less than 90cps at 25°C. In some embodiments, the viscosity of the agricultural composition is less than 80cps at 25°C. In some embodiments, the viscosity of the agricultural composition is less than 70cps at 25°C. In some embodiments, the viscosity of the agricultural composition is in the range of 10cps to 150cps at 25°C. In some embodiments, the viscosity of the agricultural composition is in the range of 25cps to 150cps at 25°C. In some embodiments, the viscosity of the agricultural composition is in the range of 50cps to 150cps at 25°C. In some embodiments, the viscosity of the agricultural composition is in the range of 50cps to 100cps at 25°C. In some embodiments, additional water can be removed. In such embodiments, the viscosity is in the range of 150cps to 8000cps at 25°C, such as in the range of 15cps to 1500cps at 25°C. In some embodiments, the viscosity is in the range of 150cps to 1000cps at 25°C. In some embodiments, the viscosity is in the range of 150cps to 500cps at 25°C. In some embodiments, the viscosity is in the range of 150cps to 400cps at 25°C. In some embodiments, the viscosity is in the range of 150cps to 300cps at 25°C. In some embodiments, the viscosity is in the range of 150cps to 250cps at 25°C.

[0066] In some embodiments, the agricultural composition has a pH in the range of 7 to 14, such as in the range of 8 to 10 or 8 to 11.

[0067] In some embodiments, the agricultural composition further comprises a dye. Exemplary dyes include FD&C Blue No. 1, FD&C Red No. 33, FD&C Blue No. 1, FD&C Green No. 3, FD&C Yellow No. 5, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 6, and ULTRA green dye.

[0068] The agricultural composition of the present disclosure may include a total amount of paraformaldehyde, nitrification inhibitor, urea, ammonia source, and one or more reaction products thereof in the range of 30 wt % to 95 wt % based on the total weight of the agricultural composition. In some embodiments, the agricultural composition includes a total amount of paraformaldehyde, nitrification inhibitor, urea, ammonia source, and one or more reaction products thereof in the range of 65 wt % to 85 wt % based on the total weight of the agricultural composition.

[0069] The agricultural composition of the present disclosure may also include one or more solvents. Suitable solvents include, but are not limited to, water, alcohol, alcohol derivatives, glycols, glycol derivatives, primary amines and simple amines, aromatic hydrocarbons, polar aprotic organic solvents, polar protic solvents and ammonia. In some embodiments, alcohol may be methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, benzyl alcohol or a combination thereof. In some embodiments, alcohol derivatives may be isopropylidene glycerol. Other examples of glycols include, but are not limited to, polyethylene glycol (PEG), diethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,7-heptanediol, 1,9-nonanediol, 1,8-octanediol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 2,4-pentanediol, 2,5-hexanediol, 4,5-octanediol and 3,4-hexanediol or a combination thereof. Other examples of diol derivatives include, but are not limited to, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol monostearate, ethylene glycol distearate, ethylene glycol amidostearate, propylene glycol monostearate, propylene glycol dicaprylate, propylene glycol dicaprate diacetate diol, dilaurate diol, dipalmitate diol, diformate diol, dibutyrate diol, dibenzoate diol, dipalmitate diol, dipropionate diol, monoacetate diol, monopalmitate diol, monoformate diol, and diethylene glycol monostearate. Examples of diol derivatives also include, but are not limited to, C 3 -C 12 Triol and / or C 3 -C 12 Triol derivatives, including C 3 -C 6In some embodiments, the agricultural composition comprises triols, glyceryl monostearate, glyceryl distearate, glyceryl monooleate, glyceryl monolaurate, glyceryl dilaurate, glyceryl dipalmitate, glyceryl monopalmitate, glyceryl triacetate, glyceryl tribenzoate, glyceryl tributyrate, glyceryl trimyristate, glyceryl trioleate, glyceryl trilaurate, glyceryl tripalmitate and glyceryl tristearate. In at least one embodiment, alcohol is propylene glycol. In some embodiments, solvent comprises water so that agricultural composition is an aqueous solution. In some embodiments, aprotic organic solvent is selected from N-methyl pyrrolidone (NMP), can be proton or aprotic glycol ether, DMSO, dibasic ester, lactone, lactam and their combination. In some embodiments, the glycol ether can be diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monopentyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monoisobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetra ... In some embodiments, the agricultural composition comprises a non-protonic organic solvent. In some embodiments, the agricultural composition does not contain a polar non-protonic solvent, such as DMSO. In at least one embodiment, the solvent is mixed in the reaction product with paraformaldehyde, nitrification inhibitor, urea and ammonia source. In such embodiments, the agricultural composition can also contain the same or different solvents of unreacted form.

[0070] The agricultural compositions of the present disclosure may include additives suitable for use in agricultural settings, including, for example, pesticides, herbicides, and fungicides.

[0071] In some embodiments, the agricultural composition is a composition made by any of the methods for making an agricultural composition disclosed herein.

[0072] Method for preparing agricultural composition :

[0073] The present disclosure also provides methods of preparing the agricultural compositions according to the present disclosure.

[0074] The agricultural composition according to the present disclosure can be prepared by reacting paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent to obtain one or more reaction products, wherein the resulting agricultural composition contains at least 20% by weight of the one or more reaction products based on the total weight of the agricultural composition. Specifically, the agricultural composition of the present disclosure may contain 20% by weight of a reaction product of paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent, based on the total weight of the agricultural composition. Alternatively, the agricultural composition may contain at least 20% by weight of a combination of multiple reaction products prepared from paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent, such as two or more.

[0075] In some embodiments, the method of preparing an agricultural composition comprises reacting paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent to obtain one or more reaction products. In at least one embodiment, the agricultural composition comprises a total amount of paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and one or more reaction products in the range of 30 wt % to 95 wt % based on the total weight of the agricultural composition. In some embodiments, the method of preparing an agricultural composition comprises reacting paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and an optional solvent to obtain one or more reaction products, wherein the agricultural composition comprises a total amount of paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and one or more reaction products in the range of 65 wt % to 85 wt % based on the total weight of the agricultural composition.

[0076] In some embodiments, one or more reactions of paraformaldehyde, nitrification inhibitor, urea, ammonia source, and optional solvent to obtain one or more reaction products are conducted at a pH greater than 7, such as at a pH in the range of 7 to 10.

[0077] In at least one embodiment, a method of preparing an agricultural composition according to the present disclosure includes forming a first mixture comprising paraformaldehyde, an optional solvent, a first amount of an ammonia source, a nitrification inhibitor, and a first amount of urea; heating the first mixture to a first temperature in the range of 65°C to 85°C for a first reaction time; adding an optional second amount of an ammonia source and a second amount of urea to the first mixture to form a second mixture; and heating the second mixture to a second temperature in the range of 65°C to 85°C for a second reaction time.

[0078] The method for preparing the agricultural composition according to the present invention may further comprise a cooling step. Other agents such as solvents, dyes or other additives may also be added before or after cooling.

[0079] The first reaction time may, for example, be in the range of 10 minutes to 3 hours. The second reaction time may, for example, be in the range of 10 minutes to 5 hours.

[0080] In some embodiments, the first amount of ammonia source is less than the second amount of ammonia source. In some embodiments, the first amount of ammonia source is 10% to 50% of the second amount of ammonia source. In other embodiments, ammonia is added only once.

[0081] In some embodiments, the first amount of urea is less than the second amount of urea. In some embodiments, the first amount of urea is 10% to 50% of the second amount of urea.

[0082] The method for preparing the agricultural composition disclosed herein may include adding a solvent. In some embodiments, the solvent is water, alcohol, primary amine or simple amine, aromatic hydrocarbon, ammonia or a combination thereof. In some embodiments, the alcohol is methanol, ethanol, isopropanol, ethylene glycol, propylene glycol or a combination thereof. In at least one embodiment, the alcohol is propylene glycol. In some embodiments, the solvent includes water so that the agricultural composition is an aqueous solution. In some embodiments, the aprotic organic solvent is selected from N-methylpyrrolidone (NMP), glycol ethers that can be proton or aproton, DMSO, dibasic esters and combinations thereof. In some embodiments, the method for preparing the agricultural composition does not include aprotic organic solvents. In some embodiments, the method for preparing the agricultural composition does not contain polar aprotic solvents, such as DMSO. In at least one embodiment, the solvent is incorporated into the reaction product together with paraformaldehyde, nitrification inhibitor, urea and ammonia source. In such embodiments, the agricultural composition may also contain the same or different solvents in unreacted form. Solvents may be added at any time point, including before, during or after the first and / or second reaction time.

[0083] In some embodiments, the nitrification inhibitor is dicyandiamide.

[0084] In some embodiments, the weight ratio of paraformaldehyde to urea is in the range of 1:5 to 5:1. In at least one embodiment, the weight ratio of paraformaldehyde to urea is in the range of 1:1 to 2:1, such as 1:1.2 to 2:1. In at least one embodiment, the weight ratio of paraformaldehyde to urea is about 1.4. In another embodiment, the weight ratio of paraformaldehyde to urea is about 2. In another embodiment, the weight ratio of paraformaldehyde to urea is about 3.

[0085] In some embodiments, the weight ratio of paraformaldehyde to ammonia source is in the range of 1:1 to 20:1. In at least one embodiment, the weight ratio of paraformaldehyde to ammonia is in the range of 1:1 to 5:1, such as 1:1.2 to 4:1. In at least one embodiment, the weight ratio of paraformaldehyde to ammonia is about 4:1.

[0086] In some embodiments, the weight ratio of paraformaldehyde to nitrification inhibitor is in the range of 1:5 to 5:1. In at least one embodiment, the weight ratio of paraformaldehyde to nitrification inhibitor is in the range of 1:1 to 2.5:1, such as 1:1.2 to 2:1. In at least one embodiment, the weight ratio of paraformaldehyde to nitrification inhibitor is about 1.6. In another embodiment, the weight ratio of paraformaldehyde to nitrification inhibitor is about 2.

[0087] In some embodiments, one or more reaction products prepared according to the methods disclosed herein are compounds of Formula (I).

[0088]

[0089] In formula (I), X is O or R 1 , R 2 , R 3 and R 4 Each independently is:

[0090]

[0091] wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula:

[0092]

[0093] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0094] In formula (I), if X is O, then R 1 , R 2 , R 3 or R 4 One or more of

[0095] In some embodiments, one or more of the reaction products is a compound of formula (A), a compound of formula (B), or a compound of formula (C).

[0096]

[0097] In formula (A), formula (B) and formula (C), each R is independently hydrogen, a substituted or unsubstituted alkyl group or Y, wherein Y is represented by the following formula:

[0098]

[0099] wherein X and R are as defined above, and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0100] Fertilizer composition :

[0101] The present disclosure also includes fertilizer compositions, which include nitrogen sources and agricultural compositions as disclosed herein. Suitable nitrogen sources include, but are not limited to, urea, ammonium nitrate, anhydrous ammonia, ammoniacal liquor, urea-formaldehyde polymers, or any combination thereof. The nitrogen source may be solid, liquid, gas, or any combination thereof. In at least one embodiment, the nitrogen source may be molten urea. Another suitable nitrogen source may be or may include waste from one or more animals, such as urine and / or feces, such as cattle, sheep, chickens, buffaloes, turkeys, goats, pigs, horses, etc. In some embodiments, the fertilizer composition includes agricultural compositions, urea, and ammonium nitrate.

[0102] In some embodiments, the fertilizer composition is formed by blending an agricultural composition with a composition comprising urea. In some embodiments, the composition comprising urea is urea ammonium nitrate (UAN), urea-formaldehyde polymer (UFP) or a combination thereof. In some embodiments, the fertilizer composition is formed by blending an agricultural composition with a composition comprising urea at a ratio of 1 to 8 quarts of agricultural composition per ton of the composition comprising urea. In some embodiments, the fertilizer composition is formed by blending an agricultural composition with a composition comprising urea at a ratio of 2 to 4 quarts of agricultural composition per ton of the composition comprising urea. In some embodiments, the fertilizer composition is formed by blending an agricultural composition with a composition comprising urea at a ratio of 2 quarts, 3 quarts or 4 quarts of agricultural composition per ton of the composition comprising urea.

[0103] In some embodiments, the fertilizer composition is a liquid. In some embodiments, the viscosity of the fertilizer composition is less than 150cps. In some embodiments, the viscosity of the fertilizer composition is less than 100cps. In some embodiments, the viscosity of the fertilizer composition is less than 90cps. In some embodiments, the viscosity of the fertilizer composition is less than 80cps. In some embodiments, the viscosity of the fertilizer composition is less than 70cps. In some embodiments, the viscosity of the fertilizer composition is in the range of 10cps to 150cps. In some embodiments, the viscosity of the fertilizer composition is in the range of 25cps to 150cps. In some embodiments, the viscosity of the fertilizer composition is in the range of 50cps to 150cps. In some embodiments, the viscosity of the fertilizer composition is in the range of 50cps to 100cps.

[0104] In some embodiments, the fertilizer composition is a solid, such as, for example, coated urea. In some embodiments, the fertilizer composition is a solid, and the crush strength of the solid is equal to or better than uncoated urea. In some embodiments, the fertilizer composition is a solid, and the crush strength of the solid is equal to the crush strength of uncoated urea ± 50%. In some embodiments, the fertilizer composition is a solid, and the crush strength of the solid is equal to the crush strength of uncoated urea ± 25%. In some embodiments, the fertilizer composition is a solid, and the solid does not clump.

[0105] In some embodiments, the fertilizer composition further comprises a urease inhibitor. As used herein, the term "urease inhibitor" refers to an enzyme that reduces, inhibits, or otherwise slows the conversion of urea to ammonium (NH 4 + ). The urease inhibitor may include, for example, N-n-butylthiophosphoric triamide, N-n-butylphosphoric triamide, thiophosphoric triamide, phenylphosphoric diamide, cyclohexylphosphoric triamide, cyclohexylthiophosphoric triamide, phosphoric triamide, hydroquinone, p-benzoquinone, hexaamidocyclotriphosphazene, thiopyridine, thiopyrimidine, thiopyridine-N-oxide, N,N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, 2-nitrophenylphosphoric triamide, derivatives thereof, or any combination thereof. In some embodiments, the urease inhibitor includes N-(n-butyl)thiophosphoric triamide (NBPT). In some embodiments, the urease inhibitor includes one or more reaction products of formaldehyde, urea, and N-(n-butyl)thiophosphoric triamide (NBPT).

[0106] In some embodiments, the nitrogen source can be mixed with the agricultural composition in the soil, on the soil surface or near the soil surface or their combination. For example, the nitrogen source comprises animal waste, such as urine and / or feces deposited on the soil and / or in the soil. In another example, the nitrogen source comprises a fertilizer product previously applied to the soil. Therefore, the agricultural composition can be applied to the soil and mixed with animal waste and / or previously applied fertilizer on the soil surface and / or in the soil. The agricultural composition can be applied to the soil before, during and / or after animal waste and / or fertilizer are deposited on the soil / in the soil. In some embodiments, the nitrogen source comprises animal waste, such as urine and / or feces, which can be collected and placed in a holding tank, a pond, etc., and the agricultural composition can be added to the animal waste to provide a fertilizer composition.

[0107] If the nitrogen source comprises animal waste, such as urine and / or feces, then based on the total amount of nitrogen in one or more nitrogen sources, the amount of the agricultural composition combined with the nitrogen source comprising animal waste is in the range of about 0.1 wt % to about 25 wt %. In some embodiments, based on the total amount of nitrogen in one or more nitrogen sources in fertilizer, the amount of the agricultural composition combined with the nitrogen source comprising animal waste is in the range of about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt % or about 5 wt % to about 10 wt %, about 12 wt %, about 15 wt %, about 18 wt %, about 20 wt % or about 25 wt %. In some embodiments, based on the total amount of nitrogen in one or more nitrogen sources in fertilizer, the amount of the agricultural composition combined with the nitrogen source comprising animal waste can be in the range of about 0.5 wt % to about 3 wt %, about 5 wt % to about 15 wt %, about 8 wt % to about 12 wt % or about 10 wt % to about 20 wt %. In some embodiments, the nitrogen source comprising animal waste further comprises one or more additional nitrogen sources selected from urea, ammonia, ammonium nitrate, and any combination thereof. For example, the agricultural composition can be applied to soil containing fertilizer containing urea, ammonia, ammonium nitrate, animal waste, or any combination thereof.

[0108] In some embodiments, agricultural composition is combined with one or more quick-release nitrogen sources and / or one or more controlled-release nitrogen sources to provide fertilizer. As used herein, the term "quick-release nitrogen" refers to free urea, ammonium nitrate, anhydrous ammonia, ammoniacal liquor or any combination thereof. As used herein, the term "controlled-release nitrogen" refers to substituted urea, urea of ​​reaction, such as urea-formaldehyde polymer, or a combination thereof. For example, the fertilizer composition comprises an agricultural composition, urea-formaldehyde polymer (UFP) and a urea (U) aqueous solution, an ammonium nitrate (AN) aqueous solution, a urea-ammonium nitrate (UAN) aqueous solution or any combination thereof. For example, based on the total weight of nitrogen in a controlled-release nitrogen source and a quick-release nitrogen source, a fertilizer composition containing a quick-release nitrogen source and a controlled-release nitrogen source can include a controlled-release nitrogen source of an amount ranging from as low as about 10 wt %, about 20 wt %, about 30 wt % or about 40 wt % to as high as about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt % or about 95 wt %. Based on the total nitrogen in the fast-release nitrogen source, a fertilizer composition containing both a fast-release nitrogen source and a controlled-release nitrogen source may have a reaction product concentration in the range of about 0.5 wt % to about 25 wt %, about 1 wt % to about 15 wt %, about 5 wt % to about 20 wt %, or about 1 wt % to about 20 wt %. In some embodiments, the fertilizer composition comprises an aqueous urea-formaldehyde solution (UF) mixed with a fast-release nitrogen source in a weight ratio of about 90:10 to about 10:90, about 80:20 to about 20:80, about 75:25 to about 25:75, or about 30:70 to about 70:30, and the reaction product may be present in an amount in the range of about 1 wt % to about 20 wt %, based on the total amount of nitrogen in the fast-release nitrogen source.

[0109] In some embodiments, the fertilizer composition further comprises one or more fertilizer nutrient additives. Exemplary fertilizer nutrient additives may include, for example, nutrients based on phosphorus and / or potassium. Commercially available fertilizer nutrients may include, for example, K-Fol 0-40-53, which is a solution containing 40% by weight phosphate and 53% by weight potassium, manufactured and distributed by GBS Biosciences, LLC.

[0110] In some embodiments, the fertilizer composition further comprises one or more pesticides, herbicides, fungicides, or any combination thereof.

[0111] Depending on the specific composition of the fertilizer composition comprising the agricultural composition and one or more nitrogen sources, the application rate to the soil can vary widely. For example, a fertilizer composition having a concentration of one or more reaction products in the range of about 0.5% to about 25% by weight, based on the total amount of nitrogen in the one or more nitrogen sources, can be applied to the soil in an amount ranging from about 5 kg / hectare (kg / ha), about 10 kg / ha, about 20 kg / ha, about 30 kg / ha, about 40 kg / ha, or about 50 kg / ha to about 100 kg / ha, about 150 kg / ha, about 200 kg / ha, about 250 kg / ha, about 300 kg / ha, about 350 kg / ha, or about 400 kg / ha. In some embodiments, the agricultural composition can be applied to the soil in an amount ranging from about 1 kg / ha, about 3 kg / ha, about 5 kg / ha, about 7 kg / ha, or about 10 kg / ha up to about 30 kg / ha, about 35 kg / ha, about 40 kg / ha, about 45 kg / ha, about 50 kg / ha, about 60 kg / ha, about 70 kg / ha, or about 80 kg / ha. When applied alone to the soil, the specific amount of the reaction product can be based at least in part on the amount of nitrogen in and / or on the soil and / or the amount of nitrogen expected to be deposited on and / or in the soil.

[0112] Additional non-limiting exemplary embodiments include:

[0113] 1. An agricultural composition comprising: paraformaldehyde, a nitrification inhibitor, urea, an ammonia source or a combination thereof and one or more reaction products prepared from the paraformaldehyde, the nitrification inhibitor, urea and the ammonia source, wherein the one or more reaction products are present in an amount of at least 20% by weight of the total weight of the agricultural composition.

[0114] 2. The agricultural composition according to embodiment 1, wherein the nitrification inhibitor is dicyandiamide.

[0115] 3. The agricultural composition according to embodiment 1, wherein the one or more reaction products are compounds of formula (I):

[0116]

[0117] Where X is O or R 1 , R 2 , R 3 and R 4 Each independently is:

[0118]

[0119] wherein each R is independently hydrogen, substituted or unsubstituted alkyl or Y, and wherein Y is represented by the formula:

[0120]

[0121] Where X is O or And wherein n is an integer from 0 to 100.

[0122] 4. The agricultural composition of embodiment 1, wherein the one or more reaction products are a compound of formula (A), a compound of formula (B), or a compound of formula (C):

[0123]

[0124] wherein each R is independently hydrogen, substituted or unsubstituted alkyl or Y, and wherein Y is represented by the formula:

[0125]

[0126] Where X is O or And wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0127] 5. The agricultural composition according to embodiment 1, further comprising water, wherein the water content is in the range of 10% to 30% by weight of the total agricultural composition.

[0128] 6. The agricultural composition according to embodiment 1, wherein the viscosity is in the range of 15 cps to 1500 cps.

[0129] 7. The agricultural composition according to embodiment 1, further comprising a dye.

[0130] 8. The agricultural composition according to embodiment 1, further comprising an organic solvent.

[0131] 9. The agricultural composition of embodiment 8, wherein the organic solvent comprises an alcohol.

[0132] 10. The agricultural composition of embodiment 9, wherein the alcohol is a diol.

[0133] 11. The agricultural composition of embodiment 10, wherein the glycol is propylene glycol.

[0134] 12. A fertilizer composition comprising a nitrogen source and the agricultural composition according to embodiment 1.

[0135] 13. A method for preparing an agricultural composition, comprising:

[0136] Paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and optionally a solvent are reacted to obtain one or more reaction products, wherein the resulting agricultural composition comprises at least 20 wt % of the one or more reaction products based on the total weight of the agricultural composition.

[0137] 14. A method for preparing an agricultural composition, comprising: forming a first mixture comprising paraformaldehyde, a first amount of an ammonia source, a nitrification inhibitor, and a first amount of urea; heating the first mixture to a first temperature in the range of 65°C to 85°C for a first reaction time; adding a second amount of urea and optionally a second amount of an ammonia source to the first mixture to form a second mixture; and heating the second mixture to a second temperature in the range of 65°C to 85°C for a second reaction time.

[0138] 15. The method according to embodiment 14, wherein the first reaction time is in the range of 10 minutes to 3 hours.

[0139] 16. The method according to embodiment 14, wherein the second reaction time is in the range of 10 minutes to 10 hours.

[0140] 17. A method according to embodiment 14, wherein the second amount of ammonia source is added and the first amount of ammonia source is less than the second amount of ammonia source.

[0141] 18. The method of embodiment 14, wherein the second amount of ammonia source is added and the first amount of ammonia source is 10% to 50% of the second amount of ammonia source.

[0142] 19. The method of embodiment 14, wherein the second amount of ammonia source is added and the first amount of urea is less than the second amount of urea.

[0143] 20. The method of embodiment 14, wherein the second amount of ammonia source is added and the first amount of the urea is 10% to 50% of the second amount of the urea.

[0144] 21. The method according to embodiment 14, wherein the paraformaldehyde is dissolved in a solvent.

[0145] 22. The method of embodiment 21, wherein the solvent is water, alcohol, ammonia, an aprotic organic solvent, or a combination thereof.

[0146] 23. The method of embodiment 22, wherein the solvent is propylene glycol.

[0147] 24. The method of any one of embodiments 13 to 23, wherein the nitrification inhibitor is dicyandiamide.

[0148] 25. The method of embodiment 14, wherein the weight ratio of the paraformaldehyde to the urea is in the range of 1:5 to 5:1.

[0149] 26. The method of embodiment 14, wherein the weight ratio of the paraformaldehyde to the ammonia source is in the range of 1:1 to 20:1.

[0150] 27. The method of embodiment 14, wherein the weight ratio of the paraformaldehyde to the nitrification inhibitor is in the range of 1:5 to 5:1.

[0151] 28. The method according to embodiment 14, wherein the one or more reaction products are compounds of formula (I):

[0152]

[0153] Where X is O or

[0154] R 1 , R 2 , R 3 and R 4 Each independently is:

[0155]

[0156] wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula:

[0157]

[0158] Where X is O or and wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3;

[0159] And if X is O, then R 1 , R 2 , R 3 and R 4 One or more of

[0160] 29. The method of embodiment 14, wherein the one or more reaction products are a compound of formula (A), a compound of formula (B), or a compound of formula (C):

[0161]

[0162] wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula:

[0163]

[0164] Where X is O or And wherein n is an integer from 0 to 100, preferably 0, 1, 2 or 3.

[0165] 30. The method of embodiment 14, wherein the weight ratio of the nitrification inhibitor to total urea is in the range of 30:1 to 50:1.

[0166] 31. The method of embodiment 14, wherein the second amount of ammonia source is added.

[0167] 32. The method of embodiment 14, further comprising adding a third amount of urea.

[0168] 33. The agricultural composition of embodiment 1, wherein the viscosity is less than 100 cps.

[0169] 34. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has one or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt% to 60 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt% to 20 wt%, the amount of dicyandiamide is in the range of 5 wt% to 20 wt%, the amount of water is in the range of 5 wt% to 40 wt%, the amount of propylene glycol is in the range of 0 wt% to 30 wt%, the amount of dye is in the range of 0 wt% to 6 wt%, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0170] 35. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has two or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0171] 36. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has three or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0172] 37. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has four or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0173] 38. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has five or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0174] 39. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has six or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0175] 40. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has seven or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0176] 41. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has eight or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 20 wt % to 60 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt % to 20 wt %, the amount of dicyandiamide is in the range of 5 wt % to 20 wt %, the amount of water is in the range of 5 wt % to 40 wt %, the amount of propylene glycol is in the range of 0 wt % to 30 wt %, the amount of dye is in the range of 0 wt % to 6 wt %, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0177] 42. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has the following characteristics: the amount of the one or more reaction products is in the range of 20 wt% to 60 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 4 wt% to 20 wt%, the amount of dicyandiamide is in the range of 5 wt% to 20 wt%, the amount of water is in the range of 5 wt% to 40 wt%, the amount of propylene glycol is in the range of 0 wt% to 30 wt%, the amount of dye is in the range of 0 wt% to 6 wt%, the viscosity is in the range of 15 cps to 1500 cps, the pH is in the range of 8 to 11, and the density is in the range of 9.5 lb / gal to 11.5 lb / gal.

[0178] 43. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has one or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt% to 48 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt% to 16 wt%, the amount of dicyandiamide is in the range of 6 wt% to 16 wt%, the amount of water is in the range of 18 wt% to 26 wt%, the amount of propylene glycol is in the range of 13 wt% to 16 wt%, the amount of dye is in the range of 0 wt% to 5 wt%, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0179] 44. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has two or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt% to 48 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt% to 16 wt%, the amount of dicyandiamide is in the range of 6 wt% to 16 wt%, the amount of water is in the range of 18 wt% to 26 wt%, the amount of propylene glycol is in the range of 13 wt% to 16 wt%, the amount of dye is in the range of 0 wt% to 5 wt%, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0180] 45. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has three or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt % to 48 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt % to 16 wt %, the amount of dicyandiamide is in the range of 6 wt % to 16 wt %, the amount of water is in the range of 18 wt % to 26 wt %, the amount of propylene glycol is in the range of 13 wt % to 16 wt %, the amount of dye is in the range of 0 wt % to 5 wt %, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0181] 46. ​​The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has four or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt % to 48 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt % to 16 wt %, the amount of dicyandiamide is in the range of 6 wt % to 16 wt %, the amount of water is in the range of 18 wt % to 26 wt %, the amount of propylene glycol is in the range of 13 wt % to 16 wt %, the amount of dye is in the range of 0 wt % to 5 wt %, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0182] 47. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has five or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt % to 48 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt % to 16 wt %, the amount of dicyandiamide is in the range of 6 wt % to 16 wt %, the amount of water is in the range of 18 wt % to 26 wt %, the amount of propylene glycol is in the range of 13 wt % to 16 wt %, the amount of dye is in the range of 0 wt % to 5 wt %, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0183] 48. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has six or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt% to 48 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt% to 16 wt%, the amount of dicyandiamide is in the range of 6 wt% to 16 wt%, the amount of water is in the range of 18 wt% to 26 wt%, the amount of propylene glycol is in the range of 13 wt% to 16 wt%, the amount of dye is in the range of 0 wt% to 5 wt%, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0184] 49. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has seven or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt % to 48 wt % of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt % to 16 wt %, the amount of dicyandiamide is in the range of 6 wt % to 16 wt %, the amount of water is in the range of 18 wt % to 26 wt %, the amount of propylene glycol is in the range of 13 wt % to 16 wt %, the amount of dye is in the range of 0 wt % to 5 wt %, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0185] 50. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has the following characteristics: the amount of the one or more reaction products is in the range of 36 wt% to 48 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt% to 16 wt%, the amount of dicyandiamide is in the range of 6 wt% to 16 wt%, the amount of water is in the range of 18 wt% to 26 wt%, the amount of propylene glycol is in the range of 13 wt% to 16 wt%, the amount of dye is in the range of 0 wt% to 5 wt%, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0186] 43. The agricultural composition of embodiment 1 or the method of embodiment 14, wherein the agricultural composition has one or more properties selected from the group consisting of: the amount of the one or more reaction products is in the range of 36 wt% to 48 wt% of the total weight of the agricultural composition, the amount of the reaction products of urea, ammonia and formaldehyde is in the range of 6 wt% to 16 wt%, the amount of dicyandiamide is in the range of 6 wt% to 16 wt%, the amount of water is in the range of 18 wt% to 26 wt%, the amount of propylene glycol is in the range of 13 wt% to 16 wt%, the amount of dye is in the range of 0 wt% to 5 wt%, the viscosity is in the range of 100 cps to 200 cps, the pH is in the range of 8.5 to 9.5, and the density is in the range of 10.1 lb / gal to 10.7 lb / gal.

[0187] Example 1

[0188] 345.0966g propylene glycol, 526.2906g paraformaldehyde (95% purity, 16.649mol formaldehyde equivalent) and 50.6782g 28 wt% ammonia solution (0.833mol) were added to the reaction vessel. The reaction vessel was heated to 75°C. Then, 641.24g dicyandiamide (7.627mol) and 77.965g urea (1.298mol) were added to the reaction vessel. The reaction vessel was kept at 75°C for 1 hour. Next, 446.9406g urea (7.440mol) and 206.0386g 28 wt% ammonia solution (3.388mol) were added to the reaction vessel. Dye (5.75g) was added, and the reaction vessel was kept at 75°C for 1 hour, at which time a 1 liter aliquot was taken to obtain Sample 1A. The reaction vessel was maintained at 75°C for an additional hour, at which time the reaction vessel was cooled to 25°C to obtain Sample 1B. Sample 1A had a pH of 9.55, a viscosity of 118 cps, and a true density of 10.376 lbs / gallon solution. The sample was further distilled to remove about 6% of the water while maintaining good solubility.

[0189] The viscosities of various dilutions of Sample 1A and Sample 1B after dilution with water are shown in Table 1.

[0190] Table 1

[0191] sample Water added (wt%) Viscosity(cps) 4A 3 75 3A 2 86 2A 1 96 1 0 116 6B 5 60 5B 4 67 4B 3 82 3B 2 93 2B 1 106 1B 0 129

[0192] Example 2

[0193] 225.063 g of deionized water, 343.233 g of paraformaldehyde (95% purity, 10.858 mol formaldehyde equivalent) and 33.051 g of 28 wt% aqueous ammonia solution (0.543 mol) were added to the reaction vessel. The reaction vessel was heated to 75° C. Then, 418.200 g of dicyandiamide (4.974 mol) and 50.847 g of urea (0.846 mol) were added to the reaction vessel. The reaction vessel was kept at 75° C. for 1 hour. Next, 291.483 g of urea (4.852 mol) and 134.373 g of 28 wt% aqueous ammonia solution (2.209 mol) were added to the reaction vessel. The reaction vessel was kept at 75° C. for 2 hours, at which time the reaction vessel was cooled to 25° C. to obtain Sample 2. Sample 2 had a pH of 8.90, a viscosity of 18 cps, and a solid weight of 10.3 units per gallon. When kept at -15°C overnight, sample 2 formed crystals. Sample 2 can be further distilled to remove about 6% of the water while maintaining good solubility. Sample 2 can be used to treat urea ammonium nitrate solutions.

[0194] Example 3

[0195] 305.084g DMSO, 457.684g paraformaldehyde (95% purity, 14.5mol formaldehyde equivalent) and 44.068g 28 wt% ammonia solution (0.73mol) were added to the reaction vessel. The reaction vessel was heated to 70°C. Then, 557.6g dicyandiamide (6.64mol) and 67.796g urea (1.13mol) were added to the reaction vessel. The reaction temperature was maintained at 70°C for 1 hour. Next, 179.164g urea (2.99mol) and 388.644g 28 wt% ammonia solution (6.40mol) were added to the reaction vessel. The reaction vessel was maintained at 70°C for 1 hour, at which time the mixture was distilled to remove about 176g of distillate. The remaining mixture was cooled to 25°C to obtain Sample 3. Sample 3 had a reaction product of about 44% and a viscosity of about 4492cPs as determined by NMR. Sample 3 was applied to urea at a rate of 4 quarts / ton, resulting in an undesirable sticky mass.

[0196] Example 4

[0197] 305.084 g propylene glycol (15.25 wt%), 457.644 g paraformaldehyde (95% purity, 22.88 wt%, 14.49 mol formaldehyde equivalent) and 44.068 g 28 wt% aqueous ammonia solution (0.73 mol; 2.2 wt%) were added to the reaction vessel. The reaction vessel was heated to 70°C. Then, 557.6 g dicyandiamide (6.63 mol; 27.88 wt%) and 67.796 g urea (1.13 mol; 3.39 wt%) were added to the reaction vessel. The reaction temperature was maintained at 70°C for 1 hour. Next, 388.644 g urea (6.47 mol; 8.96 wt%) and 179.164 g 28 wt% aqueous ammonia solution (2.95 mol; 19.43 wt%) were added to the reaction vessel. The reaction vessel was held at 70°C for 1 hour, at which time the reaction vessel was cooled to 25°C to obtain Sample 4A, and 0.25 wt% dye was added. About 5.6 wt% of the water was removed by distillation to obtain Sample 4B with a viscosity of about 508 cPs. The sample had a pH of 9.52, a true density of 10.5 lbs / gallon, a refractive index of 1.5166, and a reaction product content of 29.7 wt%. Sample 4 was applied to urea at a rate of 4 quarts / ton to obtain a dry and uniformly coated material.

[0198] Example 5

[0199] 305.084 g of butyl carbitol (15.25 wt%), 457.644 g of paraformaldehyde (95% purity, 22.88 wt%, 14.49 mol formaldehyde equivalent) and 44.068 g of 28 wt% aqueous ammonia solution (0.73 mol; 2.2 wt%) were added to the reaction vessel. The reaction vessel was heated to 70°C. Then, 557.6 g of dicyandiamide (6.63 mol; 27.88 wt%) and 67.796 g of urea (1.13 mol; 3.39 wt%) were added to the reaction vessel. The reaction temperature was maintained at 70°C for 1 hour. Next, 388.644 g of urea (6.47 mol; 8.96 wt%) and 179.164 g of 28 wt% aqueous ammonia solution (2.95 mol; 19.43 wt%) were added to the reaction vessel. The reaction vessel was held at 70°C for 1 hour, at which time the reaction vessel was cooled to 25°C to obtain Sample 5, and 0.25 wt% dye was added. About 5.2 wt% of the water was removed by distillation to obtain a viscosity of about 540 cPs. The pH of the sample was 9.15, the true density was 10.34 lbs / gallon, the refractive index was 1.514, and the reaction product content was 29.4 wt%. Sample 5 was applied to urea at a rate of 4 quarts / ton to obtain a dry and uniformly coated material.

[0200] Example 6

[0201] 305.084 g of butyl cellosolve (15.25 wt%), 457.644 g of paraformaldehyde (95% purity, 22.88 wt%, 14.49 mol formaldehyde equivalent) and 44.068 g of 28 wt% aqueous ammonia solution (0.73 mol; 2.2 wt%) were added to the reaction vessel. The reaction vessel was heated to 70° C. Then, 557.6 g of dicyandiamide (6.63 mol; 27.88 wt%) and 67.796 g of urea (1.13 mol; 3.39 wt%) were added to the reaction vessel. The reaction temperature was maintained at 70° C. for 1 hour. Next, 388.644 g of urea (6.47 mol; 8.96 wt%) and 179.164 g of 28 wt% aqueous ammonia solution (2.95 mol; 19.43 wt%) were added to the reaction vessel. The reaction vessel was held at 70°C for 1 hour and 115.2 g of distillate was removed by distillation. The reaction vessel was cooled to 25°C to obtain Sample 6 and 0.25 wt% dye was added. Sample 6 had a viscosity of about 300 cPs, a pH of 9.25, a true density of 10.25 lbs / gallon, a refractive index of 1.5101, and a reaction product content of 29.4 wt%. Sample 6 was applied to urea at a rate of 4 quarts / ton to obtain a dry and uniformly coated material.

[0202] Example 7

[0203] Example 7: 474.5 g (94.9 wt%) Mixed with 25.5 g (5.1 wt%) N-(n-butyl)thiophosphoric triamide (98% purity) to give Sample 7. Sample 7 had a pH of 9.8, a viscosity of 37 cPs, a true density of 10.506 lbs / gallon, and a specific gravity of 1.2628. This sample produced a water clear liquid that did not separate after storage for over 1 year.

[0204] Example 8

[0205] Example 8: 436.5569 g of 50 wt% aqueous formaldehyde solution (7.28 mol; 33.58 wt%) are added to a reaction vessel. The reaction vessel is heated to 60°C and 26 g of 28 wt% aqueous ammonia solution (0.43 mol; 2.00 wt%) are added. The reaction vessel is cooled to 40°C and 234 g of dicyandiamide (2.79 mol; 18.00 wt%) and 56.1041 g of urea (0.94 mol; 4.32 wt%) are added to the reaction vessel. The reaction vessel is heated to 70°C and the pH is adjusted to 9.94 with NaOH. The reaction vessel is kept at 70°C for 30 minutes. Next, 224.4242 g of urea (3.74 mol; 17.26 wt%) and 98.9703 g of 28 wt% aqueous ammonia solution (1.63 mol; 7.61 wt%) are added to the reaction vessel. The reaction vessel was maintained at 70°C for 30 minutes, at which time the mixture was distilled to remove about 611 g of distillate. Next, 223.9445 g of NMP was added and the reaction was cooled to 25°C to yield Sample 8 with a pH of 9.8, a refractive index of 1.5226, and a viscosity of 172 cPs. Karl Fischer titration showed that Sample 9 contained 9.35% water.

[0206] Example 9

[0207] Example 9: 167.424 g of 28 wt % aqueous ammonia solution (2.75 mol; 11.16 wt %) are added to the reaction vessel. 352.504 g of paraformaldehyde (92.5% purity, 23.5 wt %, 10.87 mol formaldehyde equivalent) are slowly added for exothermic control. The reaction vessel is heated to 75°C. Then, 418.2 g of dicyandiamide (4.98 mol; 27.88 wt %) and 50.847 g of urea (0.85 mol; 3.39 wt %) are added to the reaction vessel. The reaction vessel is maintained at 75°C for 1 hour. Next, 291.513 g of urea (4.86 mol; 19.43 wt %) is added to the reaction vessel. The reaction vessel is maintained at 75°C for 2 hours, at which time the reaction vessel is cooled to 50°C and maintained at 50°C for 30 minutes. The reaction vessel was cooled to 25°C, at which time 215.757 g of propylene glycol (14.38 wt%) was added and the reaction was allowed to proceed for 15 minutes. K3-B violet dye was added to obtain sample 9. The pH of sample 9 was 9.0, the viscosity was 130 cps, and the true density was 10.3 lb / gal. The composition of sample 9 was similar to The comparison is shown in Table 2.

[0208] Table 2

[0209]

[0210]

[0211] Additional compositions were prepared similar to the examples provided above. Figure 2 and Figure 3 Included are tables summarizing various aspects of those compositions. "F" indicates that solvent was added before the first reaction time. "B" reflects the addition of solvent after the second reaction time. "Hyde" refers to paraformaldehyde (92.5% or 95%) or formaldehyde (50%). Stable refers to a clear, precipitate-free composition from the time of synthesis to the time of reporting at the following temperatures: -15°C, 0°C, 25°C, 45°C.

[0212] Embodiments 10 to 26 are additional exemplary embodiments. The various features of these embodiments are Figures 4 to 10 in the table.

[0213] Example 10

[0214] Without applying any heat, 223.2320 g of 28% ammonium hydroxide (3.67 mol), 470.012 g of 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6 g of dicyandiamide (6.632 mol) was added over 19 minutes, followed by 67.796 g of urea (1.1288 mol) over 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 388.684 g of urea (6.472 mol) was added to the vessel over 16 minutes and maintained at 72°C for 4 hours, sample 10A was taken at 0.5 hours, sample 10B was taken at 1 hour, sample 10C was taken at 2 hours, sample 10D was taken at 3 hours and sample 10E was taken at 4 hours. 14.4838 wt % of propylene glycol (PG) was added to each sample at 25°C.

[0215] Embodiment 11

[0216] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added within 19 minutes, followed by 67.796g urea (1.1288mol) within 4 minutes. The reaction vessel was heated to 72°C and kept for 2 hours. Next, 388.684g urea (6.472mol) was added to the container within 16 minutes and kept at 72°C for 1 hour. The reaction vessel was cooled to 50°C and 855g sample (sample 11A) was taken out, cooled to 25°C with an ice bath and 13.4838% by weight propylene glycol was added. 20g ammonium hydroxide (0.329mol) was added to the remaining material in the container and kept at 50°C for 30 minutes. The reaction vessel contents were then cooled to 25°C and 13.4838 wt% propylene glycol was added (Sample 11B).

[0217] Example 12

[0218] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added within 19 minutes, followed by 67.796g urea (1.1288mol) within 4 minutes. The reaction vessel was heated to 72°C and kept for 2 hours. Next, 388.684g urea (6.472mol) was added to the container within 16 minutes and kept at 72°C for 2 hours. The reaction vessel was cooled to 50°C and 855g sample (sample 12A) was taken out, cooled to 25°C with an ice bath and 13.4838% by weight propylene glycol was added. 20g ammonium hydroxide (0.329mol) was added to the contents in the container and kept at 50°C for 30 minutes. The reaction vessel contents were then cooled to 25°C and 13.4838 wt % propylene glycol was added (Sample 12B).

[0219] Embodiment 13

[0220] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added within 19 minutes, followed by 67.796g urea (1.1288mol) within 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 388.684g urea (6.472mol) was added to the container within 16 minutes and maintained at 72°C for 3 hours. The reaction vessel was cooled to 50°C, 20g ammonium hydroxide (0.329mol) was added, and maintained at 50°C for 30 minutes. The reaction vessel contents were then cooled to 25°C and 14.4838 wt% propylene glycol was added.

[0221] Embodiment 14

[0222] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added within 19 minutes, followed by 67.796g urea (1.1288mol) within 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 388.684g urea (6.472mol) was added to the container within 16 minutes and maintained at 72°C for 3 hours. The reaction vessel was cooled to 50°C, 20g ammonium hydroxide (0.329mol) was added to the contents in the container, and maintained for 60 minutes. The reaction vessel contents were then cooled to 25°C and 14.4838 wt% propylene glycol was added.

[0223] Embodiment 15

[0224] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added within 19 minutes, followed by 67.796g urea (1.1288mol) within 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 388.684g urea (6.472mol) was added to the container within 16 minutes and maintained at 72°C for 3 hours. The reaction vessel was cooled to 50°C and 570g sample (sample 15A) was taken out, cooled to 25°C with an ice bath and 13.4838% by weight propylene glycol was added. 20g ammonium hydroxide (0.329mol) was added to the contents in the container and maintained for 120 minutes. A 570 g sample (Sample 15B) was removed, cooled to 25°C with an ice bath and 13.4838 wt% propylene glycol was added. The reaction vessel contents were then stirred for an additional 60 minutes, cooled to 25°C and 14.4838 wt% propylene glycol was added.

[0225] Example 16

[0226] Without applying any heat, 279.04g 28% ammonium hydroxide (4.588mol), 587.515g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 697g dicyandiamide (8.291mol) was added within 19 minutes, followed by 84.745g urea (1.4110mol) within 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 485.855g urea (8.0895mol) was added to the container within 16 minutes and maintained at 72°C for 4 hours. The reaction vessel was cooled to 50°C and 427.6g sample (Sample 7A) was taken out, cooled to 25°C with an ice bath and 13.4838 wt% propylene glycol was added. 20 g of ammonium hydroxide (0.329 mol) was added to the contents of the container and maintained at 50° C. for 180 minutes, with a total of 427.6 g of samples taken after 30 minutes (sample 16B), 60 minutes (sample 16C), 120 minutes (sample 16D), and 180 minutes (sample 16E). After each sample was taken, the sample was cooled to 25° C. and 14.4838 wt % propylene glycol was added.

[0227] Embodiment 17

[0228] Without applying any heat, 279.04g 28% ammonium hydroxide (4.588mol), 587.515g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 697g dicyandiamide (8.291mol) was added in 19 minutes, followed by 84.745g urea (1.4110mol) in 4 minutes. The reaction vessel was heated to 72°C and kept for 1 hour. Next, 485.855g urea (8.0895mol) was added to the container in 16 minutes and kept for 3 hours at 80°C. Samples (713g) were taken out at 1 hour (sample 17A) and 2 hours (713g, sample 17B). The reaction vessel was cooled to 50°C, 20g ammonium hydroxide (0.1598mol) was added to the contents in the container, and kept for 30 minutes (sample 17C). The reaction vessel contents were then cooled to 25°C and 14.4838 wt% propylene glycol was added.

[0229] Embodiment 18

[0230] Without applying any heat, 279.04g of 28% ammonium hydroxide (4.588mol), 587.515g of 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 697g of dicyandiamide (8.291mol) was added over 19 minutes, followed by 84.745g of urea (1.4110mol) over 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 485.855g of urea (8.0895mol) was added to the container over 16 minutes and maintained at 85°C. Samples (713g) were taken out and cooled to 25°C at 1 hour (sample 18A) and 2 hours (475g, sample 18B), and an appropriate amount of propylene glycol ("PG") (14.4838 wt%) was added. The reaction vessel was cooled to 50°C, 20 g of ammonium hydroxide (0.329 mol) was added to the contents of the vessel and held for 30 minutes. After holding for 30 minutes, a sample (475 g, sample 18C) was taken out, cooled to 25°C and PG was added. The remaining contents of the vessel were held at 50°C for another 30 minutes and cooled to 25°C, where 14.4838 wt% of PG (sample 18D) was added.

[0231] Embodiment 19

[0232] Without applying any heat, 279.04g 28% ammonium hydroxide (4.588mol), 587.515g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 697g dicyandiamide (8.291mol) was added within 19 minutes, followed by 169.49g urea (2.8220mol) within 8 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 401.11g urea (6.678mol) was added to the container within 12 minutes and maintained at 75°C for 3 hours. Samples (712.66 grams each) were taken out at 1 hour (sample 19A) and 2 hours (sample 19B), cooled to 25°C, and 14.4838% by weight of PG was added. At the end of the 3-hour maintenance, the reaction vessel was cooled to 25°C and 14.4838% by weight of PG (sample 19C) was added.

[0233] Embodiment 20

[0234] Without applying any heat, 279.04 g of 28% ammonium hydroxide (4.588 mol), 587.515 g of 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 697 g of dicyandiamide (8.291 mol) was added over 19 minutes, followed by 84.745 g of urea (1.4110 mol) over 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. 1098.87 g of the contents were removed and the following operations were performed:

[0235] First, 161.95 g (2.696 mol) of urea was added to the remaining contents in the container (549.43 g) and kept at 75° C. for 1 hour. The container was cooled to 50° C., 8.3 g of urea (0.1382 mol) was added and kept for 30 minutes, then cooled to 25° C., and then 14.4838 wt% of PG (Sample 20A) was added.

[0236] Second, 549.43 g of the 1098.87 g removed from the container was added to an empty container, heated to 75°C, 161.95 g of urea (2.6965 mol) was added and maintained for 2 hours. The contents were cooled to 50°C, 8.3 g of urea (0.1382 mol) was added and maintained for 30 minutes. After 30 minutes, the contents were cooled to 25°C, and PG (14.4838 wt%) was added (Sample 20B).

[0237] Third, 549.43 g of the 1098.87 g removed from the container was added to an empty container, heated to 75°C, 161.95 g (2.6965 mol) of urea was added and maintained for 3 hours. The contents were cooled to 50°C, 8.3 g (0.1382 mol) of urea was added and maintained for 30 minutes. After 30 minutes, the contents were cooled to 25°C, and PG (14.4838 wt%) was added (Sample 20C).

[0238] Embodiment 21

[0239] Without applying any heat, 334.848g 28% ammonium hydroxide (5.505mol), 705.018g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 836.4g dicyandiamide (9.97mol) was added in 19 minutes, followed by 101.694g urea (1.6932mol) in 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Then, 583.026g urea (9.7084mol) was added to the container in 16 minutes, and maintained at 72°C for 3 hours. The contents were cooled to 25°C, and 14.4838% by weight of PG was added. The product was divided into 6 equal samples.

[0240] Sample 21A: As received, pH 9.

[0241] Sample 21B: As received, with violet dye (0.15 wt%), pH 9.

[0242] Sample 21C: The pH was adjusted to 9.54 with 50% NaOH.

[0243] Sample 21 D: The pH was adjusted to 9.54 with 50% NaOH and violet dye (0.15 wt %) was added.

[0244] Sample 21E: The pH was adjusted to 10.29 with 50% NaOH.

[0245] Sample 21F: The pH was adjusted to 10.29 with 50% NaOH and violet dye (0.15 wt%) was added.

[0246] Embodiment 22

[0247] Without applying any heat, 334.848g 28% ammonium hydroxide (5.505mol), 705.018g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 836.4g dicyandiamide (9.948mol) was added in 19 minutes, followed by 101.694g urea (1.6932mol) in 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Then, 583.026g urea (9.707mol) was added to the container in 16 minutes, and maintained at 72°C for 3 hours. The contents were cooled to 25°C, and 14.4838% by weight of PG was added. The product was divided into 6 samples.

[0248] Sample 22A: As received, pH was 8.98.

[0249] Sample 22B: As received, with violet dye (0.15 wt%), pH 8.98.

[0250] Sample 22C: The pH was adjusted to 9.86 with 50% NaOH.

[0251] Sample 22D: The pH was adjusted to 9.86 with 50% NaOH and violet dye (0.15 wt%) was added.

[0252] Sample 22E: The pH was adjusted to 10.56 with 50% NaOH.

[0253] Sample 22F: The pH was adjusted to 10.56 with 50% NaOH and violet dye (0.15 wt%) was added.

[0254] Embodiment 23

[0255] Without applying any heat, 223.2320g 28% ammonium hydroxide (3.67mol), 470.012g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 557.6g dicyandiamide (6.632mol) was added in 19 minutes, followed by 67.796g urea (1.1288mol) in 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Then, 388.684g urea (6.472mol) was added to the container in 16 minutes and maintained at 72°C. 855g sample (sample 23A) was taken out at 1 hour, cooled and 14.4838% by weight of PG was added. After 4 hours, the contents in the container were cooled to 25°C, and 14.4838% by weight of PG was added to produce sample 23B.

[0256] Embodiment 24

[0257] Without applying any heat, 334.848g 28% ammonium hydroxide (5.505mol), 600g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 836.4g dicyandiamide (9.9477mol) was added in 19 minutes, followed by 101.694g urea (1.6932mol) in 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 583.026g urea (9.7074mol) was added to the container in 16 minutes and maintained at 72°C for 3 hours. The sample was taken out when it was maintained for 2 hours.

[0258] Sample 24A: 613.9 g sample + 108 g PG after cooling to 25°C in an ice bath.

[0259] Sample 24B: 613.9 g sample + 134.9 g PG after cooling to 25°C in an ice bath.

[0260] At the end of the 3 hour hold, the remaining vessel contents were cooled to 25°C.

[0261] Sample 24C: 613.9 g from container + 108 g PG added.

[0262] Sample 24D: 613.9 g + 134.9 g PG added.

[0263] Embodiment 25

[0264] Without applying any heat, 223.232g 28% ammonium hydroxide (3.67mol), 705.018g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 836.4g dicyandiamide (9.9477mol) was added within 19 minutes, followed by 101.694g urea (1.6932mol) within 4 minutes. The reaction vessel was heated to 72°C and maintained for 1 hour. Next, 583.026g urea (9.7074mol) was added to the container within 16 minutes and maintained at 72°C. Sample (855g) (sample 25A) was taken out while maintaining for 2 hours, cooled and 14.4838% by weight of PG was added. The remaining material in the container was stirred for another 1 hour, cooled to 25°C, and 14.4838% by weight of PG (sample 25B) was added.

[0265] Embodiment 26

[0266] Without applying any heat, 334.848g 28% ammonium hydroxide (5.505mol), 600g 92.5% paraformaldehyde were slowly added to the reaction vessel. The reaction vessel was then adjusted to 45°C and 836.4g dicyandiamide (9.9477mol) was added in 19 minutes, followed by 101.694g urea (1.6932mol) in 4 minutes. The reaction vessel was heated to 72°C and kept for 1 hour. Then, 583.026g urea (9.7074mol) was added to the container in 16 minutes and kept for 3 hours at 72°C. The container material was divided into 17 samples for studying the stability at -15°C, 0°C, 25°C and 45°C.

[0267] Sample 26A: 136.8 g from container + 14.4838 wt % solvent (1 / 3 diethylene glycol butyl ether and 2 / 3 propylene glycol).

[0268] Sample 26B: 136.8 g from container + 14.4838 wt % solvent (2 / 3 diethylene glycol butyl ether and 1 / 3 propylene glycol).

[0269] Sample 26C: 136.8 g from container + 14.4838 wt % solvent (butyl diglycol ether).

[0270] Sample 26D: 136.8 g from container + 14.4838 wt % solvent (1 / 3 diethylene glycol methyl ether and 2 / 3 propylene glycol).

[0271] Sample 26E: 136.8 g from container + 14.4838 wt % solvent (2 / 3 diethylene glycol methyl ether and 1 / 3 propylene glycol).

[0272] Sample 26F: 136.8 g from container + 14.4838 wt% solvent (diethylene glycol methyl ether).

[0273] Sample 26G: 136.8 g from container + 14.4838 wt % solvent (1 / 3 ethylene glycol butyl ether and 2 / 3 propylene glycol).

[0274] Sample 26H: 136.8 g from container + 14.4838 wt % solvent (2 / 3 ethylene glycol butyl ether and 1 / 3 propylene glycol).

[0275] Sample 261: 136.8 g from container + 14.4838 wt % solvent (ethylene glycol butyl ether).

[0276] Sample 26J: 136.8 g from container + 14.4838 wt % solvent (1 / 3 NMP and 2 / 3 propylene glycol).

[0277] Sample 26K: 136.8 g from container + 14.4838 wt % solvent (2 / 3 NMP and 1 / 3 propylene glycol).

[0278] Sample 26L: 136.8 g from vessel + 14.4838 wt% solvent (NMP).

[0279] Sample 26M: 136.8 g from container + 14.4838 wt % solvent (1 / 3 DMSO and 2 / 3 propylene glycol).

[0280] Sample 26N: 136.8 g from container + 14.4838 wt % solvent (2 / 3 DMSO and 1 / 3 propylene glycol).

[0281] Sample 260: 136.8 g from container + 14.4838 wt% solvent (DMSO).

[0282] Sample 26P: 136.8 g from container without any added solvent.

[0283] Sample 26Q: 205.2 g from container, having 14.4838 wt % propylene glycol.

[0284] Figures 4 to 10 Exemplary reaction compositions, reaction conditions, and stabilities for Examples 10 to 26 are depicted.

[0285] Adhesion test

[0286] Table 3 shows the results of the tack test performed on a Thwing Albert Vantage NX tensile tester. Tack is a measure of the adhesiveness or "stickiness" of a material. For this test, the material itself is tested. The higher the number, the higher the tack, i.e. it is a more tacky product.

[0287] Table 3

[0288]

[0289] Analysis of structural components

[0290] Sample 9 was characterized by liquid chromatography-mass spectrometry (LC-MS). Figure 1 A portion of the LC-MS chromatogram of sample 9 is depicted, and Table 4 describes the retention time, peak area % and possible corresponding structure of sample 9.

[0291] Table 4

[0292]

[0293]

[0294] UAN Processing

[0295] Urea ammonium nitrate solution (UAN-32) was treated with Sample 1A at a rate of 2.5 gallons of Sample 1A per ton of UAN-32. This required adding 2.6 g of Sample 1A to 200 g of UAN. The sample was then clear and remained clear for more than two months.

[0296] Urea ammonium nitrate solution (UAN-32) was treated with Sample 1B at a rate of 2.5 gallons of Sample 1B per ton of UAN-32. This required adding 2.6 g of Sample 1A to 200 g of UAN. The sample was then clear and remained clear for more than two months.

[0297] Urea treatment

[0298] Urea was treated with samples 4A and 4B at a rate of 2 quarts / ton, 3 quarts / ton, and 4 quarts / ton, each mixed for 4 minutes at about 24 rpm using a ribbon blender. The urea blend had good fluidity when it flowed out of the blender, and no blend looked "wet". When the treated urea was wiped with a paper towel, the dye did not transfer to the paper towel. The treated urea was not sticky. The treatment of urea did not change the crushing strength of the urea particles. The treated urea composition maintained good crushing strength, fluidity, and non-caking characteristics when stored under ambient conditions. No caking was observed when the treated urea composition was stored under ambient conditions for three months. Even under warm and humid conditions, the urea composition can be handled well. The dye enables visual observation of the uniformity of the coating. All formulations were uniformly coated with urea after mixing at 24 rpm for 4 minutes in a ribbon blender. When the treated urea composition was contacted with a paper towel, the color did not transfer, thus indicating that the coating quickly penetrated the urea surface and dried. Urea was treated with Sample 7 at the rates shown in Table 5 (quarts of Sample 7 per ton of urea).

[0299] Table 5

[0300]

[0301]

Claims

1. An agricultural composition comprising: paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, or a combination thereof, and one or more reaction products of a reaction between paraformaldehyde, a nitrification inhibitor, urea and an ammonia source, wherein the one or more reaction products are present in an amount of at least 20% by weight of the total weight of the agricultural composition, The nitrification inhibitors include 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, dicyandiamide, 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6-trichloromethyl-5-triazine, polyether ion carrier, 4-amino-1,2,4-triazole , 3-mercapto-1,2,4-triazole, potassium azide, carbon disulfide, sodium trithiocarbonate, ammonium dithiocarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, ammonium thiosulfate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamide, 1,2,4-triazole, 3-methylpyrazole, their derivatives and any combination thereof.

2. The agricultural composition according to claim 1, further comprising an organic solvent.

3. The agricultural composition of claim 2, wherein the organic solvent comprises an alcohol.

4. The agricultural composition of claim 3, wherein the alcohol is a diol.

5. The agricultural composition of claim 4, wherein the glycol is propylene glycol.

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

7. The agricultural composition of claim 1, wherein the one or more reaction products are compounds of formula (I): Formula (I) Where X is O or ; R 1 , R 2 , R 3 and R 4 Each independently is: , , , , , , or wherein each R is independently hydrogen, substituted or unsubstituted alkyl or Y, and wherein Y is represented by the formula: , , or Where X is O or , and wherein n is an integer from 0 to 100.

8. The agricultural composition of claim 1, wherein the one or more reaction products are a compound of formula (A), a compound of formula (B), or a compound of formula (C): Formula (A) Formula (B) Formula (C) wherein each R is independently hydrogen, substituted or unsubstituted alkyl or Y, and wherein Y is represented by the formula: , , or Where X is O or , and wherein n is an integer from 0 to 100.

9. The agricultural composition according to claim 8, wherein n is 0, 1, 2 or 3.

10. The agricultural composition of claim 1, further comprising water, wherein the water content ranges from 10% to 30% by weight of the total agricultural composition.

11. The agricultural composition according to claim 1, wherein the viscosity is in the range of 15 cps to 1500 cps.

12. The agricultural composition of claim 1, further comprising a dye.

13. A fertilizer composition comprising a nitrogen source and the agricultural composition according to claim 1.

14. A method for preparing an agricultural composition, include: reacting paraformaldehyde, a nitrification inhibitor, urea, an ammonia source, and optionally a solvent to obtain one or more reaction products, wherein the resulting agricultural composition comprises at least 20% by weight of the one or more reaction products based on the total weight of the agricultural composition, The nitrification inhibitors include 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, dicyandiamide, 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6-trichloromethyl-5-triazine, polyether ion carrier, 4-amino-1,2,4-triazole , 3-mercapto-1,2,4-triazole, potassium azide, carbon disulfide, sodium trithiocarbonate, ammonium dithiocarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, ammonium thiosulfate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamide, 1,2,4-triazole, 3-methylpyrazole, their derivatives and any combination thereof.

15. A method for preparing an agricultural composition, include: forming a first mixture comprising paraformaldehyde, a first amount of an ammonia source, a nitrification inhibitor, and a first amount of urea; heating the first mixture to a first temperature in the range of 65° C. to 85° C. for a first reaction time; adding a second amount of urea and optionally a second amount of ammonia source to the first mixture to form a second mixture; and heating the second mixture to a second temperature in the range of 65° C. to 85° C. for a second reaction time, wherein the resulting agricultural composition comprises one or more reaction products of a reaction between paraformaldehyde, a nitrification inhibitor, urea and an ammonia source and wherein the one or more reaction products are present in an amount of at least 20 weight percent of the total weight of the agricultural composition, The nitrification inhibitors include 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, dicyandiamide, 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6-trichloromethyl-5-triazine, polyether ion carrier, 4-amino-1,2,4-triazole , 3-mercapto-1,2,4-triazole, potassium azide, carbon disulfide, sodium trithiocarbonate, ammonium dithiocarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, ammonium thiosulfate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamide, 1,2,4-triazole, 3-methylpyrazole, their derivatives and any combination thereof.

16. The method of claim 15, wherein the paraformaldehyde is dissolved in a solvent.

17. The method of claim 16, wherein the solvent is water, alcohol, ammonia, an aprotic organic solvent, or a combination thereof.

18. The method of claim 17, wherein the solvent is propylene glycol.

19. The method of claim 15, wherein the first reaction time is in the range of 10 minutes to 3 hours.

20. The method of claim 15, wherein the second reaction time is in the range of 10 minutes to 10 hours.

21. The method of claim 15, wherein the second amount of ammonia source is added and the first amount of ammonia source is 10% to 50% of the second amount of ammonia source.

22. The method of claim 15, wherein the second amount of ammonia source is added and the first amount of the urea is 10% to 50% of the second amount of the urea.

23. The method of claim 15, wherein the nitrification inhibitor is dicyandiamide.

24. The method of claim 15, wherein the weight ratio of the paraformaldehyde to the urea is in the range of 1:5 to 5:

1.

25. The method of claim 15, wherein the weight ratio of the paraformaldehyde to the ammonia source is in the range of 1:1 to 20:

1.

26. The method of claim 15, wherein the weight ratio of the paraformaldehyde to the nitrification inhibitor is in the range of 1:5 to 5:

1.

27. The method of claim 15, wherein the one or more reaction products are compounds of formula (I): Formula (I) Where X is O or ; R 1 , R 2 , R 3 and R 4 Each independently is: , , , , , , or wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula: , , or ; Where X is O or , and wherein n is an integer from 0 to 100; and in, If X is O, then R 1 , R 2 , R 3 and R 4 One or more of .

28. The method of claim 27, wherein n is 0, 1, 2 or 3.

29. The method of claim 15, wherein the one or more reaction products are a compound of formula (A), a compound of formula (B), or a compound of formula (C): Formula (A) Formula (B) Formula (C); wherein each R is independently hydrogen, substituted or unsubstituted alkyl, or Y, wherein Y is represented by the formula: , , or ; Where X is O or , and wherein n is an integer from 0 to 100.

30. The method of claim 29, wherein n is 0, 1, 2 or 3.

31. The method of claim 15, further comprising adding a third amount of urea.

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