WO2025236083A1

WO2025236083A1 - Fertilizer composition and related method

Info

Publication number: WO2025236083A1
Application number: PCT/CA2025/050686
Authority: WO
Inventors: David Fielding
Original assignee: 102177079 Saskatchewan Ltd
Current assignee: 102177079 Saskatchewan Ltd
Priority date: 2024-05-15
Filing date: 2025-05-12
Publication date: 2025-11-20
Anticipated expiration: 2026-11-15

Abstract

A fertilizer composition comprising urea triazone, and method for manufacturing same. The method involves adding methanol to a solution that includes a urea-formaldehyde concentrate, heating the solution to an initial temperature range of about 50°C to about 60°C, adding urea to the solution, adding ammonia to the solution, controlling the rise in temperature to a polymerization temperature range of about 90°C to about 100°C to initiate a polymerization reaction, adding potassium hydroxide to change the pH of the solution from about pH 7.5 to about pH 11 over a defined period of time to produce the urea triazone, and cooling the solution down to below 40°C to terminate the polymerization reaction.

Description

FERTILIZER COMPOSITION AND RELATED METHOD

TECHNICAL FIELD

[0001] The present application relates to a fertilizer composition that contains slow -release nitrogen (SRN) and can slowly release nitrogen over time.

BACKGROUND

[0002] Fertilizers can enhance the fertility of the soil and can replace chemical elements taken from the soil by previous crops. Soil fertility is the quality of a soil that enables it to provide compounds in adequate amounts and proper balance to promote growth of plants. Where fertility of the soil is insufficient, natural or manufactured materials may be added to supply the needed plant nutrients. Fertilizers common to crop production may contain nitrogen in one or more of the following forms: nitrate, ammonia, ammonium, or urea.

SUMMARY

[0003] This Summary is provided to introduce a selection of concepts in simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key aspects or essential aspects of the claimed subject matter.

[0004] All features of exemplary embodiments which are described in this disclosure and are not mutually exclusive can be combined with one another. Elements of one embodiment can be utilized in the other embodiments without further mention. Other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with any accompanying Figures.

[0005] As described herein, an aspect of the present disclosure relates to slow-release nitrogen (SRN) and related methods.

[0006] According to a first broad aspect of the present invention, a method for producing urea triazone is provided which may comprise adding methanol to a solution that includes a urea-formaldehyde concentrate; heating the solution to an initial temperature range of about 50°C to about 60°C after the addition of the methanol and the urea-formaldehyde concentrate; adding urea to the solution; adding ammonia to the solution; controlling the rise in temperature from the previous step to a polymerization reaction temperature range of about 90°C to about 100°C to initiate a polymerization reaction; adding potassium hydroxide to change the pH of the solution from about pH 7.5 to about pH 11 over a defined period of time to produce the urea triazone; and cooling the solution down to below 40°C to terminate the polymerization reaction.

[0007] In various embodiments, the defined period of time may be from about 10 minutes to about 180 minutes.

[0008] In various embodiments, the defined period of time may be from about 15 minutes to about 120 minutes.

[0009] In various embodiments, the defined period of time may be from about 20 minutes to about 100 minutes.

[0010] In various embodiments, the defined period of time may be from about 25 minutes to about 80 minutes.

[0011] In various embodiments, the defined period of time may be from about 25 minutes to about 60 minutes.

[0012] In various embodiments, the defined period of time may be about 30 minutes.

[0013] In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 25 psi to about 55 psi.

[0014] In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 40 psi.

[0015] In various embodiments, the polymerization reaction temperature range can be from about 90°C to about 100°C.

[0016] In various embodiments, temperature in the container can be about 95 °C.

[0017] In various embodiments, adding the potassium hydroxide comprises adding sequentially a plurality of potassium hydroxide portions to the solution over the defined period of time.

[0018] In various embodiments where the plurality of potassium hydroxide portions are added to the solution over the defined period of time, the plurality of potassium hydroxide portions is from about 3 portions to about 30 portions or more of potassium hydroxide portions over the defined period of time.

[0019] In various embodiments, the ammonia may include anhydrous ammonia.

[0020] In various embodiments, the urea-formaldehyde concentrate includes urea formaldehyde 85% concentration (“UF85”). [0021] According to a second broad aspect of the present invention there is provided a fertilizer which may comprise, with respect to the weight of the fertilizer composition, from about 10 weight percent (wt. %) to about 80 wt. % of urea triazone, from about 0.1 wt. % to about 10 wt. % of hexamethyl tetramine (HMTA), from about 0. 1 wt. % to about 10 wt. % of dimethylol urea (DMU), from about 0. 1 wt. % to about 10 wt. % of methylenediurea (MDU), and from about 0. 1 wt. % to about 10 wt. % of dimethylene triurea (DMTU).

[0022] According to a third broad aspect of the present invention there is provided a fertilizer composition which may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), and dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone, the HMTA, the DMU, the MDU and the DMTU is about 1 to about 0.001-1 to about 0.001-1 to about 0.001-lto about 0.001-1.

[0023] In various embodiments, the urea triazone, the HMTA, the DMU, the MDU, and/or the DMTU are produced based on a method disclosed herein.

[0024] In various embodiments, the urea triazone, the HMTA, the DMU, the MDU, and/or the DMTU can be products of reactions based on the urea formaldehyde concentrate and the ammonia.

[0025] In various embodiments, the fertilizer composition can include a compound to release a chlorine ion.

[0026] In various embodiments, the fertilizer composition can include a compound to release sulfur in sulfate form, sulfite form, sulfide form, or thiosulfate form.

[0027] In various embodiments, the fertilizer composition can include a compound to release phosphorus in orthophosphate form or polyphosphate form.

[0028] In various embodiments, the fertilizer composition can include a compound to release a potassium ion.

[0029] In various embodiments, the fertilizer composition can include a compound to release a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a cobalt ion, a molybdenum ion, a silica ion, or a boron ion.

[0030] In various embodiments, the fertilizer composition can include a compound to release an organic complex of a chlorine ion, a sulfur ion, a phosphorus ion, a potassium ion, a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a cobalt ion, a molybdenum ion, a silica ion, or a boron ion. [0031] In various embodiments, the organic complexing functionality is acetate, citrate, oxalate, edetate, phenolate, or carboxylate.

[0032] These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures; the invention not being limited to any particular embodiment disclosed.

BRIEF DESCRIPTION OF THE FIGURES

[0033] FIG. 1 illustrates polymerization steps with a plurality of shots of potassium hydroxide according to an embodiment.

DETAILED DESCRIPTION

[0034] A detailed description of one or more embodiments of the present invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of non-limiting embodiments and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured.

[0035] Overview of Disclosure

[0036] The present disclosure is related to slow-release nitrogen (SRN), such as a specific set of polymer-based foliar technologies.

[0037] Definitions and Interpretation

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention pertains. As used herein, and unless stated otherwise or required otherwise by context, each of the following terms shall have the definition set forth below.

[0039] Other embodiments of implementations will become apparent to the person skilled in the art in view of the teachings of the present description and as such, will not be further described here. [0040] Note that titles or subtitles may be used throughout the present disclosure for the convenience of the reader, but in no way should these limit the scope of the invention. Moreover, certain theories may be proposed and disclosed herein; however, in no way should they, whether they are right or wrong, limit the scope of the invention so long as the invention is practiced according to the present disclosure without regard for any particular theory or scheme of action.

[0041] Any and all references cited throughout the specification are hereby incorporated by reference in their entirety for all purposes.

[0042] It will be understood by those of skill in the art that throughout the present specification, the term "a" used before a term encompasses embodiments containing one or more of what the term refers to. It will also be understood by those of skill in the art that throughout the present specification, the term "comprising", which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions, will control.

[0044] As used in the present disclosure, the terms "around", "about" or "approximately" shall generally mean within the error margin generally accepted in the art. Hence, numerical quantities given herein generally include such error margin such that the terms "around", "about" or "approximately" can be inferred if not expressly stated.

[0045] As used in the present disclosure, the term "slow-release nitrogen" or "SRN" refers to that portion or a measurable quantity of nitrogen in a fertilizer that slowly releases to the soil or through the leaf surface. Such slow-release fertilizers are of a molecular weight and complexity high enough to require input energy beyond conventional solution ionization to break the molecular bonds into smaller, more plant usable forms. The energy to break the bonds can be supplied by soil microbes, in an example where solid or liquid polymer SRN is soil applied, or can be supplied by ultraviolet radiation, in an example where liquid polymer SRN is applied directly to the leaf surface. The molecular weight of such fertilizers can routinely be, but not exclusively, measured in the 190 g/mol - 350 g/mol range. Various examples of SRN compounds may include sulfur coated urea and polymer coated urea to slowly release the nitrogen from urea to the soil. Hence, the term slow-release fertilizer (SRN) has been introduced in the field of art. There has been no standard method yet to determine the SRN in solid slow-release fertilizers. This is partially because SRN can be dependent on the soil pH, the soil moisture, and the soil temperature. The slow-release committee of the American Association of Plant Food Control Officials (AAPFCO) has been working on a method that could be used universally for this purpose.

[0046] Detailed Description of Aspects and Embodiments of the Disclosure

[0047] Nitrogen is an essential nutrient for supporting the growth and development of plants, including grasses. Some plants grown to produce food, either for human or animal consumption, are usually given some form of nitrogen fertilizer.

[0048] Urea is one of the most widely used sources of nitrogen fertilizer. While some of the urea is used in a granular form, liquid fertilizers using urea in some form is another example. Some common urea- based liquid fertilizers are aqueous urea solutions and an aqueous solution of urea and ammonium nitrate. Urea contains about 46% by weight of available nitrogen and is used as a plant nutrient. Urea is relatively soluble in water and can provide the plants with its available nitrogen in different forms, such as liquid or solid. Some formulated urea-based plant nutrients have been used to provide nitrogen to the soil slowly and to avoid phytotoxicity and burning of the plants in the case where too much plant nutrient is used.

[0049] Once applied to the soil, urea in such fertilizers can be converted to ammonia by urease, an enzyme produced by endogenous microorganisms in the soil. The ammonia then is hydrolyzed rapidly to ammonium ions. In the soil, some of the ammonium ions, whether from the hydrolyzed ammonia or from ammonium nitrate, are assimilated directly by plants, but most are converted to nitrate by the process of nitrification. Once in the nitrate form, the nitrogen is more readily assimilated directly by plants.

[0050] Urea-formaldehyde (UF) condensation products, commonly known as urea forms, have been used as sources of slow- and controlled-release plant food nitrogen. Urea-formaldehyde resin fertilizers have been formulated and used as a way of providing a more controlled (sometimes characterized as an extended) release of the nitrogen values, or as SRN, so that the availability of the nitrogen may be tailored more closely to the time-course nitrogen requirements of the plants. In this way, it is thought that the nitrogen loss commonly associated with the quick release nitrogen fertilizers, such as urea and UAN solutions, can be reduced. A variety of fertilizers have been developed based on the reaction between urea and formaldehyde. When formulated at high solids contents to maximize the total nitrogen value, these liquid fertilizers sometimes can be relatively less stable. Urea-formaldehyde concentrate solutions have been used in the resin and plant nutrient industries.

[0051] Feed material molar ratio, pH, and temperature are controlling parameters in the formation of resins and liquid plant nutrients prepared by the reaction of urea and formaldehyde. A urea molecule behaves like an amino acid amide molecule due to the fact that it reacts in the tautomeric iso -urea form in which the two nitrogen atom groups plainly are differentiated as shown below:

0 - H

[0052] The H2N group in this structure may react as an amine, whereas the :NH group reacts as an imide forming only simple monomethylol derivatives or methylene-bis derivatives.

[0053] Monomethylol urea (MMU), dimethylol urea (DMU), and methylene diurea (MDU) form the reaction of urea and formaldehyde. The liquid-based products typically contain a substantial number of some of these urea-formaldehyde reaction products: MMU, DMU, and MDU have limited solubility in water. Excess amounts of these materials will precipitate upon storage.

[0054] The products derived from the reaction of urea and formaldehyde may contain substantial unreacted urea, depending on how the products are manufactured.

[0055] Some literature discloses formaldehyde reaction products, suitable as plant nutrients. For example, U.S. Patents 2,955,390, 3,119,683, and 3,235,370, disclose example manufacturing of a urea form plant nutrient mixture from urea and UF85 in the presence of KOH, contents of each of which are incorporated by reference herein in their entireties.

[0056] In various embodiments, a nitrogenous compound that contains a high yield of cyclic nitrogenous compound, such as triazone, may be produced.

[0057] The primary reaction products of formaldehyde and urea can be methylolureas. When an excess of formaldehyde is used in strong aqueous solutions (e.g., pH>10), mono, di, tri, and some tetramethylol derivatives can be present. Under acidic conditions, these condensate products can eventually lead to the formation of complex resins, causing cloudiness or thickening of the aqueous solution. Under the base catalyzed reaction at pH 8-10 and a temperature of 70-90 °C, the majority of the urea-formaldehyde condensate product can be dimethylol urea.

[0058] In the presence of ammonia (or ammonium compounds) and an excess of formaldehyde, DMU reacts to form the cyclic triazone compound that contains three nitrogen atoms (one from ammonia and two from DMU). The ammonia nitrogen in the ring can undergo further substitution by formaldehyde, urea or MMU or DMU.

[0059] Various factors such as insufficient reaction time, low reaction temperature, insufficient ammonia, or low pH can cause a high MMU content. High DMU content typically can be caused by low pH, pH above 11 during reaction, or insufficient ammonia. Uow triazone content can be caused by insufficient formalin, low reaction temperature, insufficient reaction time, or very low or excess ammonia. High-unreacted urea can be caused by such factors as low reaction temperature, insufficient reaction time, or very low or excess ammonia.

[0060] Other factors such as insufficient cooling may prolong the production of polymer units inside the solution that may not be wanted. Over-polymerization can result in solutions that are too viscous to pass through farm spraying machines or may require so much additional water to alter the viscosity that the “sprayable” product is no longer economically viable. The rate of polymerization increases two-fold for every ten degrees Celsius increased. Thus, it is desirable to sufficiently cool the final SRN solution to such a degree that the post-production increase in polymerization is at a minimum. This will become apparent to those skilled in the art that such a limitation exists below a temperature of about 35 °C to about 40°C.

[0061] A composition containing SRN may give off a foul smell, may chemically bum leaves on contact, may have a short shelf-life, or may not be able to mix as readily with other liquid solutions other than water as other fertilizer compounds. This may be due to the contents of an unreacted reactant to form a polymer for the slow-release process, in which the unreacted reactant can include ammonia.

[0062] For example, physical properties of liquid products, including how products smell, can be a determinant buying characteristic regarding various consumer types. For example, if two liquid sulfur products are considered side by side, and no other difference can be seen (price, concentration, etc.), if one product smells like rotten eggs and the other does not, a consumer or a buyer such as a farmer may likely choose the product that is less odious. In the case of a composition containing SRN, foul odor of the composition may come from ammonia such as un-reacted ammonia.

[0063] If the ammoniacal fraction is not fully reacted in the polymer mix, free units of ammonia can permeate the system. This free ammonia mixes with atmospheric water vapor when applied to a plant and the resulting ammonium hydroxide solution can chemically bum or brown the leaf surface.

Photosynthesis can take place normally in the non-browned areas, and the burning or browning may result in the photosynthetic potential of the overall plant being lower than it otherwise would be. The polarity of the mixture is such that it can interact on the leaf surface without causing harmful effects to the plant. For example, Salt Index, based on soluble or dissolved salts in a plant nutrient, has long been used to estimate the "bum potential" of soil applied plant nutrient but has not proven useful for estimating bum potential of foliarly applied plant nutrient. Osmolality is a measure of osmotic potential of the total dissolved solids in a solution which, in turn, is related to the osmotic pressure across plant tissue surface which may cause cell dehydration with resulting tissue necrosis. There are strong direct correlations between osmolality values and phytotoxic potential of foliar plant nutrients.

[0064] The primary constituent produced in the process disclosed herein is urea triazone. Due to the symmetrical molecular geometry of the urea triazone molecule it is generally regarded as nonpolar. Nonpolar species of chemicals pass more easily through the leaf surface due to their affinity for sharing electrons equally. This nonpolar quality can also be expressed in the weighted proportional sum of the differential in electronegativity values for each molecular bond within the total unit. This nonpolar quality can also be expressed in the measurable value of dielectric constant wherein the lower the dielectric constant the more nonpolar an entity is. Generally, the higher the concentration of urea triazone created via the example processes disclosed herein, the more nonpolar the total solution is.

[0065] Nonpolar units are not the only complex carbon-containing units that may be created by the example processes disclosed herein. Hexamethyltetramine, for example, is polar unit which would allow for a portion of the SRN solution to mix readily with other polar units. Because of the mix of polar and nonpolar parts created, SRN has the unique ability to mix into both polar and nonpolar solutions, which may be especially useful in mixing with foliar applied fertilizer and agricultural chemicals which routinely exist as both polar and nonpolar species.

[0066] Common constituents of commercially available fungicides consist of an organic complex joined with a halogen from group 17 of the periodic table. Halogens are the mixing product of choice because of their high oxidative potential. In the presence of a high oxidative potential chemical, a fungal cell wall will oxidize away efficiently eliminating it. As such, all fungicides containing halogens are “contact” fungicides as a default because they will oxidize biotic species on the surface of a plant. Many contact fungicides have a specific “mode of action” inside the plant. This mode of action is granted because many fungicides contain a nonpolar hydrocarbon, like naphthalene. This nonpolar hydrocarbon allows the fungicide to pass through the waxy outer layer of the plant effectively pulling the fungicide into the plant itself. After this point the mode of action observed inside the plant is fungicide chemistry specific. Because SRN can readily mix with halogens, and because SRN has nonpolar constituents, mixing SRN with a halogen can be used as a contact fungicide and as a fungicide with an in-plant mode of action. [0067] Common constituents of commercially available insecticides consist of an organic complex joined with a halogen, a sulfur, or both. Through these combinations an insecticide will act as a contact insecticide agent first, then will be pulled into the plant itself with a nonpolar fraction to provide a chemistry specific mode of action. Thus, SRN added to a halogen or a sulfur or both may act as a contact insecticide and as an insecticide with an in-plant mode of action.

[0068] A complaint regarding existing compositions containing SRN may be about stability. For example, compositions containing SRN may not last the full season without falling out or, for example, precipitating solids out of solution. These solids represent product that cannot be used for its intended purpose, such as foliar application, and can cause a problem, such as a mechanical problem when the product is applied in the field by clogging filters or sprayer nozzles. Moreover, preparing compositions containing SRN such as a solution containing SRN may create end products with relatively un-reacted or under-reacted anhydrous ammonia which may be heat sensitive. Anhydrous ammonia will likely vaporize when heated inside a vented storage tank. By losing this unit to the atmosphere, any support function it was being utilized for inside the SRN system may no longer perform as effectively or units may fall out. Also, when preparing a composition containing SRN, the pH range that the resulting polymers exist within may not handle large temperature fluctuations and may get too low to contain all of the units possible in higher pH ranges.

[0069] The present disclosure is related to a composition containing SRN and a compound containing SRN that is relatively more fully reacted with as few free units of salt as possible. For example, the primary causes of un-reacted materials may come from three sources: 1) Raw material selection 2) Reaction conditions 3) Reaction time. Considerations for production may include UF85 over urea and formaldehyde separately. Considerations for production may include anhydrous ammonia over ammonium hydroxide (NH4OH allows for ionic NH3 - and NH4 can act as a carrier for ions to exist). Considerations for production may include pressurized vessel over unpressurized vessel . Considerations for production may include constant reaction temperature over variable temperature control, or relatively fuller time allowed for reaction.

[0070] In various embodiments, the reaction time can be increased to create more polymer units.

[0071] In various embodiments, SRN can mix within formulations that are stable for a longer period of time (years instead of months). SRN can act as a carrier for nutrients and agricultural chemicals into the plant through the leaf surface. In various embodiments, a variety of nutrients in various forms can be used in formulations containing SRN. Such nutrients can be various forms of nitrogen, phosphorus, potassium, sulfur, chlorine, fluorine, iodine, bromine, astatine, tennessine, copper, manganese, zinc, iron, magnesium, calcium, molybdenum, cobalt, or boron. Because the binding of such units with a nonpolar source can traverse the waxy outer layer of the plant surface, the nonpolar SRN fraction effectively acts as an ionophore for the units that pass the plant outer layer with it. Such agricultural chemicals can be various forms of herbicide, insecticide, fungicide, rodenticide, pH stabilizing agent, drift reduction agent, or vaporization reduction agent.

[0072] In various embodiments, the fertilizer can include a compound to release a chlorine ion.

[0073] In various embodiments, the fertilizer can include a compound to release a fluorine ion.

[0074] In various embodiments, the fertilizer can include a compound to release an iodine ion.

[0075] In various embodiments, the fertilizer can include a compound to release a bromine ion.

[0076] In various embodiments, the fertilizer can include a compound to release an astatine ion.

[0077] In various embodiments, the fertilizer can include a compound to release a tennessine ion.

[0078] In various embodiments, the fertilizer can include a compound to release sulfur in sulfate form, sulfite form, sulfide form, or thiosulfate form.

[0079] In various embodiments, the fertilizer can include a compound to release phosphorus in orthophosphate form or polyphosphate form.

[0080] In various embodiments, the fertilizer can include a compound to release a potassium ion.

[0081] In various embodiments, the fertilizer can include a compound to release a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a molybdenum ion, a cobalt ion, a silica ion, or a boron ion.

[0082] In various embodiments, the fertilizer can include a compound to release an organic complex of a chlorine ion, a sulfur ion, a phosphorus ion, a potassium ion, a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a molybdenum ion, a cobalt ion, a silica ion, or a boron ion.

[0083] In various embodiments, the organic complexing functionality is acetate, citrate, oxalate, edetate, phenolate, or carboxylate.

[0084] For example, SRN can act as a carrier for chloride, fluorine, iodine, bromine, astatine, or tennessine for a fungicidal effect. For example, SRN can act as a carrier for sulfur for an effect of insecticide. For example, SRN can act as a surfactant. For example, SRN can act as a carrier for phosphorus or potassium to provide foliar nutrition of plant macro -nutrients. For example, SRN can act as a carrier for copper, manganese, zinc, iron, magnesium, calcium, molybdenum, cobalt, or boron to provide foliar nutrition of plant micro-nutrients.

[0085] The present disclosure is related to SRN more fully reacted into the polymer units created from the reaction. For example, because the reaction time is long enough and the reaction conditions (temperature and pressure) do not allow the ammonia to escape, a composition containing SRN may exhibit relatively reduced foul odor.

[0086] The present disclosure is related to SRN more fully reacted into the polymer units to release SRN in a reaction and a related method of producing SRN more fully reacted into the polymer units. For example, the reaction time can be set to be long enough or the reaction conditions (e.g., temperature, pressure, etc.) can be set or controlled to be contained within a specified range, such that the molecular units contained within the SRN are relatively more thoroughly cross -linked, for example, to a degree that long term molecular stability is maintained and will not break without excess external energy input. An example of such energy input can include an input from ultraviolet radiation, heat, or chemical reaction(s) with organisms within the soil.

[0087] The present disclosure is related to SRN more fully reacted into the polymer units to release SRN in a reaction and a related method of producing SRN more fully reacted into the polymer units. For example, the reaction time can be set to be long enough or the reaction conditions (e.g., temperature, pressure, etc.) can be set or controlled to be contained within a specified range, such that, when the SRN is mixed with aqueous solutions containing ionized metals the ionized metals can interact with the SRN polymer to form organic complexes now integrated into the polymer matrix. Such organic metal complexes can be relatively more plant available than their ionized counterparts. Such organic metal complexes, being integrated into the polymer matrix, may require excess eneigy input to be released just like the SRN and can be thus also relatively slowly released. Such organic metal complexes also can have a lower osmotic potential due to their higher resistance to electron flow as compared to their salt counterparts.

[0088] The present disclosure is directed to relatively more fully reacted polymer units than salt units and a process to create relatively more fully reacted polymer units than salt units. The polymer can be relatively non-polar, compared to salts that are relatively polar.

[0089] The present disclosure is related to increasing or maximizing the concentration of the slow- release molecules, which can increase a longer shelf life for the polymer. [0090] In various embodiments, primary constituents (e.g., as "building blocks") of a compound containing SRN may include Urea Triazone, Hexamethyl Tetramine (HMTA), Dimethylol Urea (DMU), Methylenediurea (MDU), or Dimethylene Triurea (DMTU).

[0091] In various embodiments, Urea Triazone may be produced using a method disclosed herein, for example, when UF85, urea, and anhydrous ammonia are combined and when the pH is alkaline. In various embodiments, HMTA, DMU, MDU, or DMTU may be produced using a corresponding method herein. For example, HMTA, DMU, MDU, or DMTU are created during a polymerization step. In various embodiments, HMTA, DMU, MDU, or DMTU are created during a polymerization step, which takes place under temperature and pressure with a plurality of shots of potassium hydroxide. In various embodiments, adding potassium hydroxide (KOH) (e.g., adding continuously or adding a plurality of KOH portions shots) can be implemented as each individual polymer unit made may be a result of a temperature, pressure, time, or a pH range in order to be created effectively.

[0092] In various embodiments, during a polymerization step, for example, in a solution in a reaction container, potassium hydroxide can be added to the reaction container to change the pH of the solution from about pH 7.5 to about pH 11 over a defined period of time. For example, the potassium hydroxide can be added to the reaction container to change the pH of the solution from about pH 7.6, about pH 7.7, about pH 7.8, about pH 7.9, about pH 8.0, about pH 8.1, about pH 8.2, about pH 8.3, about pH 8.4, about pH 8.5, about pH 8.6, or about pH 8.7. For example, the potassium hydroxide can be added to the reaction container to change the pH of the solution to about pH 8.6, about pH 8.7, about pH 8.8, about pH 8.9, about pH 9.0, about pH 9.1, about pH 9.2, about pH 9.3, about pH 9.4, about pH 9.5, about pH 9.6, about pH 9.7 about pH 9.8, about pH 9.9, about pH 10.0, about pH 10. 1, about pH 10.2, about pH 10.3, about pH 10.4, about pH 10.5, about pH 10.6, about pH 10.7 about pH 10.8, about pH 10.9, about pH 11.0, about pH 11.1, about pH 11.2, about pH 11.3, about pH 11.4, or about pH 11.5.

[0093] For example, during a polymerization step, potassium hydroxide can be added, e.g., continuously or sequentially in a plurality of portions, to change pH of the mixture of a ureaformaldehyde concentrate (e.g., UF85), urea, and ammonia from about pH 8 to about pH 9.

[0094] In various embodiments, a method of producing a compound containing SRN may comprise adding methanol to a solution that includes a urea-formaldehyde concentrate, heating the solution, adding urea to the solution, adding ammonia to the solution, and adding potassium hydroxide, to change the pH of the solution from about pH 7.5 to about pH 11 over a defined period of time to produce urea triazone.

[0095] In various embodiments, the defined period of time can be in various ranges, for example, to control or increase the polymerization of an SRN polymer. [0096] In various embodiments, the defined period of time may be from about 10 minutes to about 180 minutes. In various embodiments, the defined period of time may be from about 15 minutes to about 180 minutes. In various embodiments, the defined period of time may be from about 20 minutes to about 180 minutes. In various embodiments, the defined period of time may be from about 25 minutes to about 180 minutes. In various embodiments, the defined period of time may be from about 30 minutes to about 180 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 170 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 160 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 150 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 140 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 130 minutes. In various embodiments, the defined period of time can be from about 10 minutes to about 120 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 110 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 100 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 90 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 80 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 70 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 60 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 50 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 40 minutes. In various embodiments, the defined period of time may be from about 10 minutes to about 30 minutes.

[0097] For example, in various embodiments, the defined period of time can be about 10 minutes, about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, about 60 minutes, about 65 minutes, about 70 minutes, about 75 minutes, about 80 minutes, about 85 minutes, about 90 minutes, about 95 minutes, about 100 minutes, about 105 minutes, about 110 minutes, about 115 minutes, or about 120 minutes. For example, the defined period of time can be from about 15 minutes to about 100 minutes. For example, the defined period of time can be from about 20 minutes to about 90 minutes. For example, the defined period of time can be from about 25 minutes to about 75 minutes. For example, the defined period of time can be from about 25 minutes to about 60 minutes. For example, the defined period can be about 30 minutes.

[0098] In various embodiments, when adding the potassium hydroxide, the solution can be contained in a container under various pressure levels, for example, to control or increase the polymerization of an SRN polymer. [0099] In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 15 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 20 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 25 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 30 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 35 psi to about 70 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 65 psi. In various embodiments, when adding the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 60 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 55 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 50 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 45 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 40 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 35 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 30 psi.

[0100] For example, in various embodiments, when adding the ammonia and the potassium hydroxide, the solution may be contained in a container under a pressure of from about 10 psi to about 40 psi.

[0101] In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 25 psi to about 55 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 26 psi to about 54 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 27 psi to about 53 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 28 psi to about 52 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 29 psi to about 51 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 30 psi to about 50 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 31 psi to about 49 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 32 psi to about 48 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 33 psi to about 47 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 34 psi to about 46 psi. In various embodiments, when adding the ammonia and the potassium hydroxide, the solution can be contained in a container under a pressure of about 35 psi to about 45 psi. In various embodiments, the solution can be under a pressure of about 36 psi to about 44 psi. In various embodiments, the solution can be under a pressure of about 37 psi to about 43 psi. In various embodiments, the solution can be under a pressure of about 38 psi to about 42 psi. In various embodiments, the solution can be under a pressure of about 39 psi to about 41 psi. For example, the solution can be contained in a container under a pressure of about 40 psi. For example, the pressure can be about 30 psi.

[0102] In various embodiments, the solution can be heated to various temperature levels, for example, to control or increase the polymerization of an SRN polymer.

[0103] In various embodiments, the solution can be heated to a temperature in a polymerization temperature range of about 90°C to about 100°C. In various embodiments, the solution can be heated to a temperature in a polymerization temperature range of about 90°C to about 98°C. In various embodiments, the solution can be heated to a polymerization temperature of about 90°C, about 91 °C, about 92°C, about 93°C, about 94°C, about 95°C, about 96°C, about 97°C, about 98°C, about 99°C, or about 100°C. For example, the polymerization temperature can be about 95°C.

[0104] Weighted average polymerization temperature (WAPT) may be used in some embodiments. WAPT is the weighted average temperature summation from the start of the step of addition of anhydrous ammonia/aqua ammonia through the step of addition of potassium hydroxide/sodium hydroxide. During this time, the temperature is increasing from approximately 40°C up to about 100°C. After urea is added, the temperature is about 40°C and increases to about 100°C. While the temperature does increase during these steps, it is not instantaneous but is instead gradual. According to one exemplary method for calculating WAPT, a timer is started at the addition of potassium hydroxide and temperature is measured every two minutes thereafter. The temperature may be documented in a table similar to the one shown below:

Time Temperature

9:05 84.2

9:07 85.3

9:09 86.9

9: 11 89.9

9: 13 90.1

These times may be expected to align with the addition of each potassium hydroxide shot into the system. At the end of the addition of potassium hydroxide, which may be for one non-limiting example 40-60 minutes, each two-minute interval represents a fractional part of the total time, each fractional part is then multiplied by its corresponding temperature, and the summation of those products is the WAPT of the batch. For example, the WAPT of the above table is 87.28. From this weighted average one may be able to derive a quality control target diagram that illustrates on a per-batch basis how accurate an operator came to making the desired batch. A sample illustration of a batch taiget map is shown below:

Batch Number:

WAPT [0105] In various embodiments, during a polymerization step, a substance, an alkali, or a base within the common chemical category of "lyes" can be added in various ways, for example, to control or increase the polymerization of an SRN polymer.

[0106] In various embodiments, during a polymerization step, sodium hydroxide can be added in various ways, for example, to control or increase the polymerization of an SRN polymer.

[0107] In various embodiments, during a polymerization step, aqueous calcium hydroxide can be added in various ways, for example, to control or increase the polymerization of an SRN polymer.

[0108] In various embodiments, during a polymerization step, potassium hydroxide can be added in various ways, for example, to control or increase the polymerization of an SRN polymer.

[0109] In various embodiments, potassium hydroxide can be added (e.g., can be added in a plurality of portions or can be continuously added) to change the pH.

[0110] In various embodiments, during a polymerization step, potassium hydroxide can be added (e.g., can be added in a plurality of portions or can be continuously added), for example, to control the rate of pH change.

[oni] In various embodiments, during a polymerization step, potassium hydroxide can be added (e.g., can be added in a plurality of portions or can be continuously added), for example, to change pH of the mixture of a urea-formaldehyde concentrate, urea, and ammonia from about pH 7.5 to about pH 11.

[0112] In various embodiments, during a polymerization step, potassium hydroxide can be added (e.g., can be added in a plurality of portions or can be continuously added), to change pH of the mixture of a urea-formaldehyde concentrate, urea, and ammonia from about pH 8 to about pH 9.

[0113] In various embodiments, a plurality of potassium hydroxide portions can be added to the solution over the defined period of time.

[0114] In various embodiments, during a polymerization step, from about 3 portions to about 30 portions or more of potassium hydroxide portions can be added.

[0115] In various embodiments, during a polymerization step, about 23 or more shots of potassium hydroxide can be added.

[0116] In various embodiments, during a polymerization step, about 23 shots of potassium hydroxide can be added. [0117] In the present disclosure, a method based on various embodiments may result in a fertilizer composition with content ranges of various polymers containing SRN. In various embodiments, the fertilize or fertilizer composition may contain content ranges of hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU).

[0118] In various embodiments, a fertilizer may comprise, with respect to the weight of the fertilizer composition, from about 10 weight percent (wt. %) to about 80 wt. % of urea triazone, from about 0.1 wt. % to about 10 wt. % of hexamethyl tetramine (HMTA), from about 0.1 wt. % to about 10 wt. % of dimethylol urea (DMU), from about 0.1 wt. % to about 10 wt. % of methylenediurea (MDU), and from about 0.1 wt. % to about 10 wt. % of dimethylene triurea (DMTU).

[0119] In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the HMTA is about 1 to from about 0.001 to about 1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the HMTA is about 1 to from about 0.001 to about 0.1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the DMU is about 1 to from about 0.001 to about 1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the DMU is about 1 to from about 0.001 to about 0.1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the MDU is about 1 to from about 0.001 to about 1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the MDU is about 1 to from about 0.001 to about 0.1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the DMTU is about to from about 0.001 to about 1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), or dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone to the DMTU is about to from about 0.001 to about 0.1. In various embodiments, a fertilizer composition may comprise urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), and dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone, the HMTA, the DMU, the MDU and the DMTU is about 1 to about 0.001-1 to about 0.001-1 to about 0.001-1 to about 0.001-1.

[0120] Examples

[0121] Example 1 : Polymerization Process

[0122] According to an example, FIG. 1 illustrates a polymerization steps with 23 shots of potassium hydroxide according to an embodiment.

[0123] Referring to FIG. 1, a reason for a plurality of portions (e.g., 23 portions or shots of potassium hydroxide) is because each individual polymer unit made requires a temperature, pressure, time, and pH range in order to be created effectively. For example, a reason for 23 smaller shots is to achieve as many of the polymer units as possible to be made before moving to the next pH range that is acceptable to create a new polymer unit. For example, slowly moving from pH 8 to pH 9 allows for the creation of DMTU, MDU, and DMU instead of just DMU. Having a lower number of shots, such as three shots, would result in creation of more DMU while moving pH, instead of DMTU, MDU, and DMU. Adding a plurality of potassium hydroxide portions or continuously adding potassium hydroxide, resulting in slowly moving through the pH progressions, allows for relatively more amount of polymer units to be created giving the product more functionality than exists in current art. As a result of this process, a resulting compound containing SRN is relatively more shelf stable, for example, for a plurality of years.

[0124] When a system is relatively more salt solution with relatively less polymer such as more salt in a solution than polymer, which can be due to improper reaction time or poor reaction quality, more units in SRN are available to react if combination products are sought. More reaction sites mean more unwanted reaction combinations that can fall out of solution and cause aforementioned problems.

[0125] Many existing products also are not in the proper pH range to be stable as a mixed product. For example, even with similar or effectively the same raw material(s), if the mixed products created were less than pH 8 the final formulation would fall out of solution.

[0126] Of note, the exemplary embodiments of the disclosure described herein do not limit the scope of the invention since these embodiments are merely examples of the embodiments of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

CLAIMS:

1. A method for producing urea triazone, the method comprising the steps of: adding methanol to a solution that includes a urea-formaldehyde concentrate; heating the solution to an initial temperature range of about 50°C to about 60°C; adding urea to the solution; adding ammonia to the solution; controlling the rise in temperature from the previous step to a polymerization reaction temperature range of about 90°C to about 100°C to initiate a polymerization reaction; adding potassium hydroxide to change the pH of the solution from about pH 7.5 to about pH 11 over a defined period of time to produce the urea triazone; and cooling the solution down to below 40°C to terminate the polymerization reaction.

2. The method of claim 1, wherein the defined period of time is from about 10 minutes to about 180 minutes.

3. The method of claim 1, wherein the defined period of time is from about 15 minutes to about 120 minutes.

4. The method of claim 1, wherein the defined period of time is from about 20 minutes to about 100 minutes.

5. The method of claim 1, wherein the defined period of time is from about 25 minutes to about 80 minutes.

6. The method of claim 1, wherein the defined period of time is from about 25 minutes to about 60 minutes.

7. The method of claim 1, wherein the defined period of time is about 30 minutes.

8. The method of claim 1, wherein, when adding the ammonia and the potassium hydroxide, the solution is contained in a container under a pressure of from about 25 psi to about 55 psi.

9. The method of claim 1, wherein, when adding the ammonia and the potassium hydroxide, the solution is contained in a container under a pressure of about 40 psi.

10. The method of claim 1, wherein the polymerization reaction temperature range is controlled from about 90°C to about 100°C.

11. The method of claim 9, wherein temperature in the container is controlled to about 95 °C.

12. The method of claim 1, wherein the adding of the potassium hydroxide comprises adding sequentially a plurality of potassium hydroxide portions to the solution over the defined period of time.

13. The method of claim 12, wherein the plurality of potassium hydroxide portions is from about 3 portions to about 30 portions or more of potassium hydroxide portions over the defined period of time.

14. The method of claim 1, wherein the ammonia includes anhydrous ammonia.

15. The method of claim 1, wherein the urea-formaldehyde concentrate includes urea formaldehyde

85% concentration.

16. A fertilizer composition comprising, with respect to the weight of the fertilizer composition, from about 10 wt. % to about 80 wt. % of urea triazone, from about 0. 1 wt. % to about 10 wt. % of hexamethyl tetramine (HMTA), from about 0. 1 wt. % to about 10 wt. % of dimethylol urea (DMU), from about 0. 1 wt. % to about 10 wt. % of methylenediurea (MDU), and from about 0. 1 wt. % to about 10 wt. % of dimethylene triurea (DMTU).

17. A fertilizer composition comprising urea triazone, hexamethyl tetramine (HMTA), dimethylol urea (DMU), methylenediurea (MDU), and dimethylene triurea (DMTU), wherein the weight ratio of the urea triazone, the HMTA, the DMU, the MDU and the DMTU is about 1 to about 0.001-1 to about 0.001- 1 to about 0.001-1 to about 0.001-1.

18. The fertilizer composition of either one of claims 16 and 17, wherein one or more of the urea triazone, the HMTA, the DMU, the MDU and the DMTU are produced using the method of claim 1.

19. The fertilizer composition of either one of claims 16 and 17, wherein one or more of the urea triazone, the HMTA, the DMU, the MDU, the DMTU are products of reactions based on the urea formaldehyde concentrate and ammonia.

20. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release a chlorine ion.

21. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release sulfur in sulfate form, sulfite form, sulfide form, or thiosulfate form.

22. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release phosphorus in orthophosphate form or polyphosphate form.

23. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release a potassium ion.

24. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a cobalt ion, a molybdenum ion, a silica ion, or a boron ion.

25. The fertilizer composition of any one of claims 16-19, further comprising a compound configured to release an organic complex of a chlorine ion, a sulfur ion, a phosphorus ion, a potassium ion, a zinc ion, a manganese ion, an iron ion, a copper ion, a magnesium ion, a calcium ion, a cobalt ion, a molybdenum ion, a silica ion, or a boron ion.

26. The fertilizer composition of claim 25, wherein functionality associated with the organic complex is acetate, citrate, oxalate, edetate, phenolate, or carboxylate.