Nitrogen stabilizer composition and related method
Urease inhibitor compositions with antioxidants and chaotropic agents address the rapid decomposition of nitrogen fertilizers by enhancing stability and efficiency, ensuring effective nutrient uptake and reduced environmental impact.
Patent Information
- Application Number
- JP2025574357
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-06-22
- Filing Date
- 2024-06-18
- Publication Date
- 2026-07-13
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Abstract
Description
[Technical Field]
[0001] The subject matter of this disclosure concerns compositions containing antioxidants and, optionally, chaotropic agents. The use of these compositions in agriculture to increase nutrient uptake and inhibit urease enzyme activity will be further described. [Background technology]
[0002] Nitrogen is an essential plant nutrient considered important for healthy and robust foliage. Urea is a major nitrogen fertilizer due to its high nitrogen content. In the presence of soil moisture, natural or synthetic urea is converted to ammonium ions, which are then absorbed by plants. Ammonium can be further converted to nitrates through the nitrification process by bacteria in the soil. Nitrates are also absorbed by plants. However, the efficiency of urea utilization by plants is low. Urea-containing fertilizers are currently used worldwide on a scale of several million tons per year and are the main fertilizers used, but about 30% of the fertilizer applied never reaches the intended target zone (roots).
[0003] In practice, nitrogen fertilizers are often applied only once, at the beginning of the growing season. Typically, nitrogen fertilizers are formulated as dry granules, prilli, or as a fluid consisting of urea alone, or as a fluid mixed with ammonium nitrate, such as UAN (a mixture containing urea, ammonium nitrate, and water). Urea is also present in animal manure. These forms of urea have a major drawback: they decompose rapidly when applied to soil, producing ammonia gas. This is because the urease enzyme is present in the soil, and this enzyme reacts with urea to produce ammonium bicarbonate and ammonia. This general series of processes is known in the art as volatilization. Volatilization results in reduced efficiency of nitrogen fertilizer use, decreased yields, symptoms of nitrogen deficiency in plants, undesirable odors, and potentially harmful ammonia gas concentrations. In addition, the ammonia produced can also be converted to nitrates by bacteria in the soil, a process called nitrification. Excess nitrates can be converted to nitric oxide or nitrous oxide by certain types of bacteria in the soil, a process called denitrification.
[0004] Urease enzyme inhibitors have been developed that can delay the decomposition of nitrogen fertilizers, thereby reducing losses due to nitrogen decomposition products that would otherwise occur in the absence of these inhibitors. The use of urease enzyme inhibitors in combination with nitrogen fertilizers tends to extend the period during which nitrogen sources remain in the soil and are available for absorption by plants, thus increasing the effectiveness of the fertilizer and positively impacting crop yield and quality. However, issues related to cost, safety, convenience, and stability limit the use of these types of inhibitors. Currently, the Agrotain® product line contains the urease enzyme inhibitor N-(n-butyl)thiophosphate triamide (NBPT), which is often used to improve the availability of nitrogen fertilizers and minimize ammonia volatilization. However, products such as Agrotain® exhibit various drawbacks, including their chemical stability and the potential to interfere with nitrogen uptake and assimilation in target crops (Zanin L, Tomasi N, Zamboni A, Varanini Z and Pinton R (2015) The Urease Inhibitor NBPT Negatively Affects DUR3-mediated Uptake and Assimilation of Urea in Maize Roots. Front. Plant Sci. 6:1007; Zanin L, Venuti S, Tomasi N, Zamboni A, De Brito Francisco RM, Varanini Z and Pinton R (2016) Short-Term Treatment with the Urease Inhibitor N-(n-Butyl)Thiophosphoric Triamide (NBPT) Alters Urea Assimilation and Modulates Transcriptional Profiles of Genes Involved in Primary and Secondary Metabolism in Maize Seedlings. Front. Plant Sci. 7:845).Therefore, it would be highly desirable to find urease inhibitors that are stable and safe for the environment and animals, and that are non-toxic to crops.
[0005] Therefore, despite ongoing research efforts to improve existing products, there remains a significant need in the art to develop superior methods for urease inhibition and compositions containing urease inhibitors that offer excellent stability while enabling efficient control of enzyme-induced urea degradation. [Overview of the project]
[0006] This disclosure relates to the development of urease inhibitor compositions containing an antioxidant alone or in combination with chaotropic agents. Such urease inhibitor compositions disclosed herein may be useful in improving the effectiveness of nitrogen fertilizers, particularly solid urea-containing fertilizers.
[0007] Thus, a first aspect of the present disclosure relates to compositions comprising antioxidants and chaotropic agents. In some embodiments, the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, dozin, guanidinium chloride, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, guanidinium thiocyanate, and combinations thereof.
[0008] Another aspect of the present disclosure relates to an agricultural product comprising granules or prill containing urea and a urease inhibitor component, wherein the urease inhibitor component is an antioxidant or a urease inhibitor composition disclosed herein, the antioxidant being selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the urease inhibitor component is pre-injected into the granules or prill.
[0009] Another aspect of the present disclosure relates to a method for producing urea-containing granules or prills coated with a composition or formulation disclosed herein, the method comprising obtaining urea-containing granules or urea-containing prills and spraying the disclosed composition or formulation onto the surface of the urea-containing granules or urea-containing prills.
[0010] Another method for producing granules or prills containing urea and the compositions disclosed herein comprises obtaining a urea molten product, contacting the urea molten product with the composition described in any one of claims 1 to 16 to obtain a mixture, and cooling the mixture to obtain granules or prills. [Brief explanation of the drawing]
[0011] [Figure 1A] This graph, created in Excel, shows a scatter plot of NH3 generation comparing process 3 with processes 1 and 2. [Figure 1B] This graph, created in Excel, shows a scatter plot of NH3 generation comparing process 4 with processes 1 and 2. [Figure 1C] This graph, created in Excel, shows a scatter plot of NH3 generation comparing process 5 with processes 1 and 2. [Figure 1D] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 6 with Process 1 and Process 2. [Figure 2A] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 3 and Process 2 after subtracting the generation in Process 1. [Figure 2B] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 4 and Process 2 after subtracting the generation in Process 1. [Figure 2C] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 5 and Process 2 after subtracting the generation in Process 1. [Figure 2D] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 6 and Process 2 after subtracting the generation in Process 1. [Figure 3A] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 10 with Process 7 and Process 9. [Figure 3B] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 11 with Process 7 and Process 9. [Figure 3C] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 12 with Process 7 and Process 9. [Figure 3D] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 13 with Process 7 and Process 9. [Figure 3E] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 143 with Process 7 and Process 9. [Figure 4A] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 9 and Process 10 after subtracting the generation in Process 7. [Figure 4B] This is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 9 and Process 11 after subtracting the generation in Process 7. [Figure 4C]It is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 9 and Process 12 after subtracting the generation in Process 7. [Figure 4D] It is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 9 and Process 13 after subtracting the generation in Process 7. [Figure 4E] It is a graph showing a scatter plot of NH3 generation created in Excel, comparing Process 9 and Process 14 after subtracting the generation in Process 7.
Best Mode for Carrying Out the Invention
[0012] The subject matter of the present disclosure will be described more fully hereinafter. However, many modifications and other embodiments of the subject matter of the present disclosure described herein will come to mind to those skilled in the art having the benefit of the teachings presented in the foregoing description. Therefore, it is to be understood that the subject matter of the present disclosure is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. In other words, the subject matter described herein is intended to cover all alternative forms, modifications, and equivalents. If one or more of the incorporated documents, patents, and the like differ from or conflict with the present application (including, but not limited to, defined terms, use of terms, or described techniques), the present application prevails. 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 disclosure pertains. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.
[0013] As already mentioned, urea (especially solid urea) is the most widely used nitrogen fertilizer worldwide. Urea granules are typically produced through a granulation or prillimentation process. Since most urea is applied to the soil early in the growing season, losses are likely to occur both above and below ground. Above-ground losses mainly refer to the release of ammonia after urea is hydrolyzed by urease enzymes in the soil. Below-ground losses mainly refer to the seepage of nitrates through groundwater systems after ammonium undergoes further nitrification by soil microorganisms.
[0014] In current agricultural practices, urease inhibitors and nitrification inhibitors are used as surface coating options for urea granule products to control the hydrolysis and nitrification processes of urea. These are applied at the agricultural retailer's location when the urea granules are ready to be applied to the field.
[0015] The only commercially available product in the United States is called SuperU, manufactured by Koch, in which urea granules are pre-injected with a urease inhibitor (NBPT) through a urea remelting and injection process (US2015 / 0101379). Since most urease inhibitor products are liquid products applied as a surface coating to urea granules, pre-injected urea provides growers with the option of pre-treated urea. This is a great idea that brings convenience and cost savings to growers. However, NBPT is expensive to manufacture and is prone to decomposition during storage or heating, especially in humid environments.
[0016] This disclosure describes novel, chemically stable, and environmentally friendly compositions and methods for the application of pre-injected (or pre-treated) urea. Generally, the compositions comprise an antioxidant urease inhibitor and, optionally, one or more chaotropic agents. These compositions can be formulated to be incorporated into a urea production process to produce urea granules pre-injected with the urease inhibitor.
[0017] Furthermore, the compositions disclosed herein can also be formulated as liquids used to surface-coat solid urea when applying urea to farmland.
[0018] Advantageously, the compositions and methods described herein have been shown to provide desirable properties for the use of such urease inhibitors in agriculture, particularly when formulated with urea-containing fertilizers. Specifically, when antioxidants such as tert-butylhydroquinone (tBHQ) were combined with chaotropic agents, beneficial properties were observed, such as, but are not limited to, improved thermal / chemical stability, extended shelf life, ease of handling, sustained / extended urease inhibitory effect, and an environmentally and toxicologically acceptable profile. In addition, combining these disclosed compositions with urea-containing fertilizers yielded agricultural products with improved nitrogen utilization efficiency compared to commercially available products. Such observations were surprising and unexpected based on the current general knowledge in the art.
[0019] Therefore, the compositions disclosed herein not only contribute to increasing the availability of plant nutrients by inhibiting urease enzyme activity, but also extend the duration of their performance as efficient urease inhibitors thanks to the aforementioned beneficial properties.
[0020] definition As used herein, the term “urease inhibitor” refers to the property of a compound to inhibit the activity of the urease enzyme. Inhibition can be quantified as described elsewhere herein.
[0021] As used herein, the term “thermal stability” refers to the stability of a substance when exposed to a thermal stimulus over a given period of time. Examples of thermal stimuli include, but are not limited to, heat generated from an electrical source and / or heat generated from the sun.
[0022] As used herein, the term “chemical stability” refers to the resistance of a substance to structural changes when exposed to external factors such as air (which can cause oxidation), light (e.g., sunlight), moisture / humidity (by water), heat (by the sun), and / or chemicals. Illustrative chemicals include, but are not limited to, any organic or inorganic substances that can degrade the structural integrity of the compound of interest (e.g., tBHQ).
[0023] As used herein, the term “antioxidant” refers to a compound that inhibits oxidation, a chemical reaction that can generate free radicals.
[0024] As used herein, the term “chaotropic agent” refers to a molecule in an aqueous solution that can disrupt the hydrogen bond network between water molecules (i.e., exhibit chaotropic activity). This affects the stability of the intrinsic state of other molecules in the solution, primarily macromolecules (proteins, nucleic acids), by weakening the hydrophobic effect. For example, chaotropic agents can reduce the degree of order in protein structures formed by water molecules, both in bulk water and around hydrophobic amino acids, thereby causing denaturation.
[0025] Thus, chaotropic agents are substances that disrupt the structure of macromolecules such as proteins and nucleic acids (e.g., DNA and RNA), causing them to denature. Chaotropic solutes increase the entropy of a system by disrupting intermolecular interactions mediated by non-covalent forces such as hydrogen bonds, van der Waals forces, and hydrophobic effects. The structure and function of macromolecules depend on the net effect of these forces (see protein folding). Therefore, an increase in chaotropic solutes in a biological system leads to macromolecule denaturation, decreased enzyme activity, and stress on cells (i.e., cells are forced to synthesize stress-protective substances). Third-order folding of proteins depends on hydrophobic forces derived from amino acids throughout the protein sequence. Chaotropic solutes reduce the net hydrophobic effect of hydrophobic regions by disordering water molecules adjacent to the protein. This solubilizes the hydrophobic regions in solution, thereby denaturing the protein. This also applies directly to the hydrophobic regions of the lipid bilayer, where, when chaotropic solutes reach critical concentrations (in the hydrophobic regions of the bilayer), membrane integrity is compromised and cells lyse. [2]
[0026] As used herein, the term “effective amount” means the amount of the urease inhibitor composition and / or the amount of each component in the urease inhibitor composition (i.e., tBHQ and optionally additional components) that is sufficient to achieve urease inhibition, as described below. More illustrative information regarding the amount used, the method of application, and appropriate ratios is given below. Those skilled in the art will be well aware that such amounts can vary over a wide range and depend on various factors, such as weather, target species, locus, application method, soil type, cultivated plants or materials being treated, and climatic conditions.
[0027] As used herein, the term “micronutrient” should be understood as a nutrient essential for plant growth and health that is required in very small amounts. An unrestricted list of micronutrients required by plants includes zinc (Zn), iron (Fe), manganese (Mn), copper (Cu), boron (B), molybdenum (Mo), and chlorine (Cl).
[0028] As used herein, the term “Size Guide Number (SGN)” refers to the diameter of fertilizer granules expressed as millimeters × 100, based on the median (or midpoint) within a batch. This means that half of the fertilizer granules are larger than the set SGN and the other half are smaller. This is determined by passing the fertilizer through various sieves and calculating the SGN using the amount held by each sieve. For example, for a fertilizer with an SGN of 250, 50% of its particles would be held on or around a sieve with an opening of 2.5 millimeters.
[0029] As used herein, the term “median” refers to the value, usually recorded in millimeters (mm), at which half of the particles in a population are above this value and half of the particles are below this value. In the case of particle size distribution, the median is the d of the particles. 50 It is called [name].
[0030] As used herein, the term “Uniformity Index (UI)” refers to a variable that represents the relative variability of particle size. A UI value within the range of approximately 40 to 60 indicates uniform particle size. A higher UI value indicates more uniform particle size variation in the product. Values outside this range indicate greater variability in the particle size distribution. For a specific granular composition, UI is calculated by multiplying the ratio of larger granules (d95) to smaller granules (d10) by 100. The formula for calculating UI is D10 ÷ D95 × 100, where D10 is the particle size corresponding to 10% passage (mm) and D95 is the particle size corresponding to 95% passage (mm). For example, a product with a UI of 50 means that the average small particle (0.80 mm) is half the size of the average large particle (1.6 mm). Products with varying particle sizes and densities can result in an inconsistent distribution of the product and lead to inconsistent results.
[0031] As used herein, the term “mesh size” refers to the U.S. mesh size (or U.S. sieve size), defined as the number of openings per square inch of the screen. For example, a 36-mesh screen has 36 openings, while a 150-mesh screen has 150 openings. As the screen size (square inch) remains constant, a higher mesh count results in smaller openings in the screen, allowing smaller particles to pass through. Generally, U.S. mesh sizes are measured using screens up to 325 mesh (325 openings per square inch).
[0032] Product mesh sizes may be indicated by either a minus (-) or plus (+) sign. These signs indicate that all particles are either smaller (-) or larger (+) than that mesh size. For example, a product identified as 100 mesh contains only particles that passed through a 100 mesh screen. A +100 grade product contains particles that did not pass through a 100 mesh screen. If a product grade is preceded by a dash or slash, this indicates that the product contains particles that fall within a range of two mesh sizes. For example, a 30 / 70 grade or 30-70 grade would contain only particles smaller than 30 mesh and larger than 70 mesh.
[0033] As used herein, the term "particle density" means lbs / ft 3 or kg / m 3 This refers to the mass-to-volume ratio of particles and / or granules, as recorded. Unlike bulk density, particle density is a measurement of the particle density itself, and does not include the gaps between individual particles.
[0034] As used herein, the term “soil” should be understood as a natural body composed of living organisms (e.g., microorganisms (bacteria and fungi, etc.), animals, and plants) and non-living matter (e.g., minerals and organic matter (e.g., organic compounds of varying degrees of decomposition), liquids, and gases), existing on the surface of land, and characterized by a soil strata distinguishable from the original material as a result of various physical, chemical, biological, and anthropogenic processes. From an agricultural perspective, soil is primarily considered the fixed base and primary nutrient base (plant habitat) for plants.
[0035] As used herein, the term “fertilizer” should be understood as a chemical compound applied to promote the growth of plants and fruits. Fertilizers are typically applied through the soil (for uptake by plant roots) or by foliar application (for uptake through leaves). The term “fertilizer” can be subdivided into two main categories: a) organic fertilizers (consisting of decaying plant / animal matter) and b) inorganic fertilizers (consisting of chemicals and minerals). Organic fertilizers include manure, slurry, earthworm castings, peat, seaweed, sewage sludge, and guano. Green manure crops are also cultivated regularly to add nutrients (especially nitrogen) to the soil. Produced organic fertilizers include compost, blood meal, bone meal, and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal. Decomposing crop residues from previous years are another source of fertility. In addition, naturally occurring minerals such as mined phosphate rock, potassium sulfate, and limestone are also considered inorganic fertilizers. Inorganic fertilizers are typically produced through chemical processes (such as the Haber-Bosch process) or by chemically transforming naturally occurring minerals (e.g., concentrated superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mined phosphate rock, and limestone.
[0036] As used herein, the term "manure" refers to organic matter used as organic fertilizer in agriculture. Based on its structure, manure can be classified into liquid manure, semi-liquid manure, manure or solid manure, and bedding-derived manure. Manure can also be classified by its origin into animal or plant-derived manure. Common forms of animal manure include feces, urine, farm slurry (liquid manure), or farm manure (FYM), although FYM also contains a certain amount of plant material (typically bedding) that may have been used as animal bedding. Animals from which manure can be obtained include horses, cattle, pigs, sheep, chickens, turkeys, and rabbits, as well as guano derived from seabirds and bats. The application rate of animal manure when used as fertilizer depends largely on its origin (type of animal). Plant manure can be derived from any type of plant, but plants may also be cultivated with the explicit purpose of being incorporated into the soil (e.g., legumes), thereby improving soil structure and fertility. Furthermore, plant materials used as manure may include the rumen contents of slaughtered ruminants, used hops (residue after beer brewing), or seaweed.
[0037] As used herein, the term “seed” includes all types of seeds, such as, for example, maize seeds, fruits, tubers, seedlings, and similar forms. The seeds used may be the seeds of the useful plants mentioned above, but may also be the seeds of transgenic plants or plants obtained by conventional breeding methods.
[0038] Throughout this specification and the claims, the words “comprise,” “comprises,” and “comprising” are used in a non-exclusive sense, synonymous with “including,” “containing,” or “characterized by,” unless the context requires otherwise, meaning that it is open-ended and does not exclude additional elements or method steps not enumerated.
[0039] Where used herein, the term “about” means, when referring to a value, to include variations of ±5%, ±2%, ±1%, ±0.5%, and ±0.1% from the specified amount in some embodiments, such variations are appropriate for carrying out the disclosed method or employing the disclosed composition.
[0040] Where a range of values is provided, unless otherwise explicitly indicated in the context, it is understood that it includes each intermediate value between the upper and lower limits of that range, up to one-tenth of the lower limit unit, and any other listed or intermediate values within that range. The upper and lower limits of these smaller ranges, which may independently be contained within smaller ranges, are also included, subject to any specifically excluded limits within the listed range. If the listed range includes one or both of the limits, it also includes any range that excludes one or both of those included limits.
[0041] Additional definitions may be provided below.
[0042] composition The subject of this disclosure relates to urease inhibitor compositions containing antioxidants. As already mentioned above, these urease inhibitor compositions can exhibit desirable properties such as improved chemical / thermal stability, extended shelf life, reduced volatility, reduced application rate, ease of handling, sustained / extended urease inhibitory effect, and superior profiles from environmental and toxicological viewpoints, all of which generally contribute to improved field performance.
[0043] In some embodiments, the urease inhibitor composition is in liquid form. For example, in such embodiments, the urease inhibitor composition may further contain an organic solvent. In such embodiments where an organic solvent is present, the antioxidant cannot be tBHQ. The amount and type of organic solvent will be described in detail below.
[0044] In some embodiments, the urease inhibitor composition is in solid form. For example, in some embodiments, the urease inhibitor composition is in powder form. In such embodiments, the urease inhibitor composition is selected from coarse powder, medium-coarse powder, medium-fine powder, fine powder, and fine powder. In some embodiments, the particle size of the powder composition is about 10 μm to about 1,700 μm, about 10 μm to about 1,200 μm, about 10 μm to about 1,000 μm, about 10 μm to about 710 μm, about 10 μm to about 355 μm, about 10 μm to about 180 μm, about 10 μm to about 150 μm, about 10 μm to about 125 μm, about 10 μm to about 90 μm, about 10 μm to about 75 μm, about 10 μm to about 50 μm, or about 10 μm to about 25 μm. In some embodiments, the urease inhibitor composition is a coarse powder having an average particle size of about 355 μm to about 1,700 μm. In some embodiments, the urease inhibitor composition has an average particle size of about 355 μm to about 710 μm (d 50 It is a medium-coarse powder having ). In some embodiments, the urease inhibitor composition has an average particle size (d) of about 180 μm to about 355 μm. 50It is a medium-fine powder having ). In some embodiments, the urease inhibitor composition is a fine powder having an average particle size of about 125 μm to about 180 μm. In some embodiments, the urease inhibitor composition is a fine powder having an average particle size of less than about 125 μm.
[0045] Average particle size of powder (d 50 ) may vary. In some embodiments, the average particle size is less than about 1,000 μm, less than about 900 μm, less than about 800 μm, less than about 700 μm, less than about 600 μm, less than about 500 μm, less than about 400 μm, less than about 300 μm, less than about 200 μm, less than about 100 μm, or less than about 50 μm.
[0046] The powder fluidity of urease inhibitor compositions can vary. The fluidity of the powder is characterized by its Carr index. In some embodiments, the Carr index of the urease inhibitor composition is in the range of about 0% to about 50%, about 0% to about 40%, about 0% to about 37%, about 0% to about 31%, about 0% to about 25%, about 0% to about 20%, about 0% to about 15%, or about 0% to about 10%. In some embodiments, the urease inhibitor composition has a Carr index of about 0% to about 10%, about 11% to about 15%, about 16% to about 20%, or about 21% to about 25%.
[0047] The bulk density of the powdered urease inhibitor composition may vary. In some embodiments, the bulk density of the powder is approximately 0.01 g / mL to approximately 2 g / mL, approximately 0.1 g / mL to approximately 1.5 g / mL, approximately 0.1 g / mL to approximately 1.25 g / mL, approximately 0.1 g / mL to approximately 1.0 g / mL, approximately 0.1 g / mL to approximately 0.7 g / mL, approximately 0.1 g / mL to approximately 0.50 g / mL, or approximately 0.1 g / mL to approximately 0.25 g / mL.
[0048] The water content of the powdered urease inhibitor composition may vary. In some embodiments, the water content of the powder is about 0% to about 40%, about 0% to about 35%, about 0% to about 30%, about 0% to about 25%, about 0% to about 20%, about 0% to about 15%, about 0% to about 10%, about 0% to about 5%, or about 0% to about 2.5%. In some embodiments, the water content of the powder is less than about 40%, less than about 30%, less than about 20%, less than about 15%, less than about 10%, less than about 8%, less than about 5%, less than about 2.5%, less than about 1%, or less than about 0.5%.
[0049] In some embodiments, the urease inhibitor composition includes an antioxidant and a chaotropic agent. The relative amounts of the antioxidant and chaotropic agent present in the urease inhibitor composition may vary. In some embodiments, the amounts of antioxidants and chaotropic agents present in the urease inhibitor composition are in the range of molar ratios of antioxidants to chaotropic agents of approximately 1:1000 to 1000:1, approximately 1:500 to 500:1, approximately 1:250 to 250:1, approximately 1:150 to 150:1, approximately 1:100 to 100:1, approximately 1:75 to 75:1, approximately 1:50 to 50:1, approximately 1:25 to 25:1, approximately 1:15 to 15:1, approximately 1:10 to 10:1, approximately 1:8 to 8:1, approximately 1:5 to 5:1, approximately 1:3 to 3:1, or approximately 1:2 to 2:1. In some embodiments, the antioxidants and chaotropic agents are present in the urease inhibitor composition in a molar ratio of 1:1.
[0050] The antioxidants, chaotropic agents, and / or organic solvents that may be present in the disclosed urease inhibitor composition are described in more detail below.
[0051] Antioxidants The urease inhibitor compositions disclosed herein include antioxidants. Exemplary antioxidants include, but are not limited to, tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the antioxidant is tert-butylhydroquinone (tBHQ). Tert-butylhydroquinone (tBHQ, tert-butylhydroquinone) is a synthetic aromatic organic compound, a derivative of hydroquinone (a type of phenol) substituted with a tert-butyl group, and has the following chemical structure. [ka]
[0052] TBHQ is primarily used in food as a preservative for unsaturated vegetable oils and many edible animal fats, where it acts as an antioxidant. In addition, tBHQ is used in other applications, such as (a) in flavorings (as a fixative to reduce evaporation rates and improve stability), (b) in industry (as a stabilizer to inhibit the self-polymerization of organic peroxides), (c) in fuels (as an antioxidant, for example in biodiesel), and (d) as an additive to varnishes, lacquers, resins, and oilfield additives.
[0053] However, its effect on urease inhibition, particularly in soil, has not been disclosed previously. Therefore, it was unexpected and surprising to find that antioxidants such as tert-butylhydroquinone exhibit strong urease enzyme inhibitory properties when exposed to soil alone, in combination with chaotropic agents, and even in combination with fertilizers, especially urea-containing fertilizers.
[0054] The amount of antioxidant present in the urease inhibitor composition may vary. For example, in some embodiments, the amount of antioxidant is in the range of about 0.001% to about 99% by weight, about 0.01% to about 90% by weight, about 0.1% to about 85% by weight, about 1% to about 80% by weight, about 10% to about 75% by weight, about 15% to about 70% by weight, about 20% to about 65% by weight, about 25% to about 60% by weight, about 30% to about 55% by weight, about 35% to about 50% by weight, or about 40% to about 45% by weight, based on the total weight of the urease inhibitor composition. In some embodiments, the amount of antioxidant present in the urease inhibitor composition is less than about 90% by weight, about 85% by weight, about 80% by weight, about 75% by weight, about 70% by weight, about 65% by weight, about 50% by weight, about 45% by weight, about 40% by weight, about 35% by weight, about 30% by weight, about 25% by weight, about 20% by weight, about 15% by weight, about 10% by weight, about 5% by weight, or less than about 1% by weight, based on the total weight of the urease inhibitor composition.
[0055] Chaotropic agents The compositions disclosed herein may also contain chaotropic agents. Exemplary chaotropic agents include, but are not limited to, magnesium chloride, guanidinium chloride, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, sodium perchlorate, dozin, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, and combinations thereof. In some embodiments, the chaotropic agent is selected from the group consisting of magnesium chloride, guanidinium thiocyanate, guanidinium chloride, thiourea, monoethanolamine borate, and combinations thereof.
[0056] The amount of chaotropic agent present in the urease inhibitor composition may vary. For example, in some embodiments, the amount of chaotropic agent is in the range of about 0.001% to about 99% by weight, about 0.01% to about 90% by weight, about 0.1% to about 85% by weight, about 1% to about 80% by weight, about 10% to about 75% by weight, about 15% to about 70% by weight, about 20% to about 65% by weight, about 25% to about 60% by weight, about 30% to about 55% by weight, about 35% to about 50% by weight, or about 40% to about 45% by weight, based on the total weight of the urease inhibitor composition. In some embodiments, the amount of chaotropic agent present in the urease inhibitor composition is less than about 90% by weight, about 85% by weight, about 80% by weight, about 75% by weight, about 70% by weight, about 65% by weight, about 50% by weight, about 45% by weight, about 40% by weight, about 35% by weight, about 30% by weight, about 25% by weight, about 20% by weight, about 15% by weight, about 10% by weight, about 5% by weight, or less than about 1% by weight, based on the total weight of the urease inhibitor composition.
[0057] Organic solvents As previously stated, the urease inhibitor compositions disclosed herein may further contain organic solvents. Such liquid urease inhibitor compositions must contain a chaotropic agent when the antioxidant is tBHQ. In some embodiments, the organic solvent is one or more polar organic solvents. In some embodiments, one or more polar organic solvents are EPA approved. EPA approved solvents are found in the Electronic Code of Federal Regulations, for example, Title 40, Chapter I, Subchapter E, Part 180. EPA approved solvents include, but are not limited to, the solvents listed in Table 1. [Table 1-1] [Table 1-2]
[0058] In some embodiments, the organic solvent is selected from sulfones, sulfoxides, aromatic solvents, halogenated solvents, glycol-based solvents, fatty acid-based solvents, acetate-containing solvents, ketone-containing solvents, ether polyol-containing solvents, amide-containing solvents, and combinations thereof. In some embodiments, the organic solvent is environmentally friendly, for example, a green solvent, a safe solvent, or a combination thereof.
[0059] In some embodiments, one or more organic solvents are all relatively water-free. In some embodiments, the organic solvents contain less than about 10% w / w, about 9% w / w, about 8% w / w, about 7% w / w, about 6% w / w, about 5% w / w, about 4% w / w, about 3% w / w, about 2% w / w, about 1% w / w, about 0.9% w / w, about 0.8% w / w, about 0.7% w / w, about 0.6% w / w, about 0.5% w / w, about 0.4% w / w, about 0.3% w / w, or less than about 0.1% w / w of water, based on the total weight of the solvent. In some embodiments, the organic solvents are liquid at 20°C.
[0060] In some embodiments, the organic solvent is a sulfone. A sulfone is a solvent containing a sulfonyl functional group bonded to two carbon atoms and is generally represented by the structure R'-S(=O)2-R'' (both R groups contain carbon atoms). The sulfone solvent may, but is not limited to, sulfolane, methylsulfolane (3-methylsulfolane), dimethylsulfone, or a combination thereof. In some embodiments, the organic solvent is a sulfoxide. A sulfoxide solvent contains a sulfinyl (SO) functional group bonded to two carbon atoms and is generally represented by R'-S(=O)-R'' (both R groups contain carbon atoms). The sulfoxide solvent may, but is not limited to, dimethyl sulfoxide.
[0061] In some embodiments, the organic solvent is an ether polyol. Ether polyols contain multiple hydroxyl groups. The ether-polyol solvent may be, but is not limited to, polyethylene glycol, polypropylene glycol, polyalkylene glycol, and related compounds. In some embodiments, polyethylene glycol has two terminal alcohols (e.g., polyethylene glycol 3350). Exemplary polyethylene glycols include, but are not limited to, diethylene glycol, triethylene glycol, or combinations thereof. Exemplary polypropylene glycols include, but are not limited to, dipropylene glycol, tripropylene glycol, or combinations thereof. In some embodiments, polypropylene glycol has three terminal alcohols. Exemplary polypropylene glycols having three terminal alcohols, known as propoxylated glycerols, include, but are not limited to, Dow PT250 (a glyceryl ether polymer with a molecular weight of 250 and containing three terminal hydroxyl groups) and Dow PT700 (a glyceryl ether polymer with a molecular weight of 700 and containing three terminal hydroxyl groups). In some embodiments, the ether polyol comprises polyethylene or polypropylene glycol with a molecular weight range of about 200 to about 10,000 Da. In some embodiments, one or more of the hydroxyl groups present in the ether polyol are modified. For example, in some embodiments, one or more of the hydroxyl groups present in the ether polyol are alkylated and / or esterified. Exemplary modified ether polyols include, but are not limited to, triacetin, n-butyl ether of diethylene glycol, ethyl ether of diethylene glycol, methyl ether of diethylene glycol, acetate of ethyl ether of dipropylene glycol, or combinations thereof.
[0062] In some embodiments, the organic solvent is a glycol-based solvent. A glycol is an alcohol containing two hydroxyl (-OH) groups bonded to different carbon atoms (e.g., terminal carbon atoms). Exemplary glycol-based solvents include, but should not be limited to, ethylene glycol and / or propane 1,2,3-triol.
[0063] In some embodiments, the organic solvent is a fatty acid-based solvent. Generally, fatty acids are characterized as compounds having carboyl acid and an aliphatic chain containing multiple carbon atoms, and can be saturated or unsaturated. In some embodiments, fatty acids contain 3 to about 20 carbon atoms. Examples of fatty acid-based solvents include, but are not limited to, dialkylamides of fatty acids (e.g., dimethylamide). Examples of dimethylamides of fatty acids include dimethylamide of caprylic acid, C8-C 10 This includes, but is not limited to, fatty acid dimethylamides (Agnique AMD810), dimethyl lactamides (Agnique AMD3L), or combinations thereof.
[0064] In some embodiments, the organic solvent is a ketone-containing solvent, which can be any solvent containing a carbonyl functional group (C=O). Examples of ketone-containing solvents include, but are not limited to, isophorone, trimethylcyclohexanone, or combinations thereof.
[0065] In some embodiments, the organic solvent is an acetate-containing solvent. Examples of acetate-containing solvents include, but are not limited to, acetate, hexyl acetate, heptyl acetate, or combinations thereof.
[0066] In some embodiments, the organic solvent is an amide-containing solvent, which can be any solvent containing amide functionality (-NR'C(=O)R'', where R is an alkyl group). Examples of amide-containing solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), N,N'-dimethylpropylene urea (DMPU), Rhodiasolv ADMA10 (CAS Registry No. 14433-76-2, N,N-dimethyloctanamide), dimethylolumamide (DMF), Rhodiasolv ADMA810 (CAS Registry No. 1118-92-9 / 14433-76-2, a blend of N,N-dimethyloctanamide and N,N-dimethyldecanamide), Rhodiasolv PolarClean (CAS Registry No. 1174627-68-9, methyl 5(dimethylamino)-2-methyl 5-oxopentanoate), or combinations thereof.
[0067] In some embodiments, the organic solvent is a halogenating solvent, which can be any solvent containing one or more halogens (i.e., chlorine, bromine, iodine, and fluorine). In some embodiments, the halogenating solvent is a halogenated aromatic hydrocarbon. An example of a halogenated aromatic hydrocarbon is chlorobenzene. In some embodiments, the halogenating solvent is a halogenated aliphatic hydrocarbon. An example of a halogenated aliphatic hydrocarbon is 1,1,1-trichloroethane.
[0068] In some embodiments, the organic solvent is an aromatic solvent. In some embodiments, the aromatic solvent is an aromatic hydrocarbon. Exemplary aromatic hydrocarbons include, but are not limited to, benzene, naphthalene, or combinations thereof. In some embodiments, the aromatic hydrocarbon is substituted. Examples of substituted aromatic hydrocarbons include, but are not limited to, alkyl-substituted benzene and / or alkyl-substituted naphthalene. Examples of alkyl-substituted benzene include, but are not limited to, xylene(s), toluene, propylbenzene, or combinations thereof. In some embodiments, the organic solvent includes xylene(s). In some embodiments, the aromatic hydrocarbon is, without limitation, a mixture of a substituted aromatic hydrocarbon and an unsubstituted aromatic hydrocarbon, such as a mixture of naphthene and alkyl-substituted naphthalene.
[0069] In some embodiments, the aromatic solvent is a mixture of hydrocarbons. For example, in some embodiments, the aromatic solvent is Aromatic 100 (a hydrocarbon combination obtained by distillation of an aromatic stream mainly composed of aromatic hydrocarbons C8 - C10, a naphtha-containing solvent (CAS Registry Number 64742-95-6)), or Aromatic 200 (based on the total weight of the Aromatic 200 composition, aromatic hydrocarbons (C 11 -C 14 ) present at 50 - 85 wt%, naphthalene (CAS Registry Number 91-20-3) present at 5 - 20 wt%, aromatic hydrocarbons without naphthalene (C 10 ) present at 5 - 15 wt%, and a solvent containing a mixture of aromatic hydrocarbons (C 15 -C 16 ) present at 5 - 15 wt%). In some embodiments, the aromatic hydrocarbon is a mixture of Aromatic 100 and Aromatic 200.
[0070] In some embodiments, the organic solvent is selected from the group consisting of sulfones, sulfoxides, amide-containing solvents, or combinations thereof. In some embodiments, the organic solvent is selected from the group consisting of DMSO, DMF, methylated seed oil, dimethyl sulfoxide, DMPU, NMP, or combinations thereof. In some embodiments, the organic solvent is a single solvent from the aforementioned solvents. In some embodiments, the organic solvent contains one or more of the aforementioned organic solvents. The amount of organic solvent in the urease inhibitor composition may vary. For example, in some embodiments, the amount of organic solvent is in the range of about 0.001% to about 99% by weight, about 0.01% to about 90% by weight, about 0.1% to about 85% by weight, about 1% to about 80% by weight, about 10% to about 75% by weight, about 15% to about 70% by weight, about 20% to about 65% by weight, about 25% to about 60% by weight, about 30% to about 55% by weight, about 35% to about 50% by weight, or about 40% to about 45% by weight, based on the total weight of the urease inhibitor composition. In some embodiments, the amount of organic solvent present in the urease inhibitor composition is less than about 90% by weight, about 85% by weight, about 80% by weight, about 75% by weight, about 70% by weight, about 65% by weight, about 50% by weight, about 45% by weight, about 40% by weight, about 35% by weight, about 30% by weight, about 25% by weight, about 20% by weight, about 15% by weight, about 10% by weight, about 5% by weight, or less than about 1% by weight, based on the total weight of the urease inhibitor composition.
[0071] formulation The disclosed urease inhibitor compositions may be used in their unmodified original form (e.g., neat), or may be formulated into formulations comprising one or more auxiliary agents selected from bulking agents, carriers, solvents, surfactants, stabilizers, anti-foaming agents, anti-freezing agents, preservatives, antioxidants, viscosity modifiers, suspending agents, light absorbers, corrosion inhibitors, fragrances, pH adjusters, flow enhancers, lubricants, plasticizers, complexing agents, colorants, thickeners, solid adhesives, fillers, wetting agents, dispersants, lubricants, anti-caking agents, deformers, and diluents. Such auxiliary agents are known and commercially available in the art. Their use in the formulation of the disclosed urease inhibitor compositions will be obvious to those skilled in the art.
[0072] The amount of urease inhibitor composition present in the formulations disclosed herein may vary. In some embodiments, the urease inhibitor composition is present in amounts ranging from about 0.1% to about 99.9% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, about 30% to about 70% by weight, or about 40% to about 60% by weight, based on the total weight of the formulation. In some embodiments, the urease inhibitor composition is present in amounts ranging from about 0.1% to about 75% by weight, about 1% to about 70% by weight, about 10% to about 60% by weight, about 20% to about 50% by weight, or about 25% to about 40% by weight, based on the total weight of the formulation. In some embodiments, the urease inhibitor composition is present in amounts ranging from about 10% to about 99.9% by weight, about 20% to about 95% by weight, about 30% to about 90% by weight, about 35% to about 80% by weight, about 40% to about 75% by weight, or about 50% to about 70% by weight, based on the total weight of the formulation.
[0073] In some embodiments, the formulation contains one or more excipients selected from carriers and / or solvents. Such formulations are said to be in liquid form and do not contain tBHQ. Exemplary carriers and / or solvents that can be used in liquid urease inhibitor formulations include water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A,A-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,11-Trichloroethane, 2-Heptanone, Alpha-Pinene, d-Limonene, Ethyl Lactate, Ethylene Glycol, Ethylene Glycol Butyl Ether, Ethylene Glycol Methyl Ether, Gamma-Butyrolactone, Glycerol, Glycerol Acetate, Glycerol Diacetate, Glycerol Triacetate, Hexadecane, Hexylene Glycol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Isopropylbenzene, Isopropyl Myristate, Lactic Acid, Laurylamine, α-Linolenic Acid, γ-Linolenic Acid, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Linoleate, Methyl Octanoate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octyl Acetate This includes, but is not limited to, amines, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, and A / -methyl-2-pyrrolidone.
[0074] The amount of liquid carrier(s) and / or solvent(s) present in the liquid formulation may vary. In some embodiments, the liquid carrier(s) and / or solvent(s) are present in amounts ranging from about 0.1% to about 99.9% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, about 30% to about 70% by weight, or about 40% to about 60% by weight, based on the total weight of the liquid formulation. In some embodiments, the carrier(s) and / or solvent(s) are present in amounts ranging from about 0.1% to about 75% by weight, about 1% to about 70% by weight, about 10% to about 60% by weight, about 20% to about 50% by weight, or about 25% to about 40% by weight, based on the total weight of the formulation. In some embodiments, the carrier(s) and / or solvent(s) are present in amounts ranging from about 10% to about 99.9% by weight, about 20% to about 95% by weight, about 30% to about 90% by weight, about 35% to about 80% by weight, about 40% to about 75% by weight, or about 50% to about 70% by weight, based on the total weight of the formulation.
[0075] In some embodiments, the formulation contains one or more adjuvants selected from carriers used in solid urease inhibitor formulations. Exemplary solid carriers include, but are not limited to, talc, titanium dioxide, pyroferrite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.
[0076] The amount of solid carrier(s) present in a solid urease inhibitor formulation may vary. In some embodiments, the solid carrier(s) may be present in amounts ranging from about 0.1% to about 99.9% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, about 30% to about 70% by weight, or about 40% to about 60% by weight, based on the total weight of the solid urease inhibitor formulation. In some embodiments, the solid carrier(s) may be present in amounts ranging from about 0.1% to about 75% by weight, about 1% to about 70% by weight, about 10% to about 60% by weight, about 20% to about 50% by weight, or about 25% to about 40% by weight, based on the total weight of the urease inhibitor formulation. In some embodiments, the solid carrier(s) are present in amounts ranging from about 10% to about 99.9% by weight, about 20% to about 95% by weight, about 30% to about 90% by weight, about 35% to about 80% by weight, about 40% to about 75% by weight, or about 50% to about 70% by weight, based on the total weight of the urease inhibitor formulation.
[0077] In some embodiments, the formulation contains a surfactant (surfactant). The surfactant is designed to enhance the dispersion / emulsification, absorption, diffusion, and / or adhesion properties of the liquid urease inhibitor formulation, such as a spray mixture. Useful surfactants are ionic or nonionic emulsifiers and / or foaming agents, dispersants, or wetting agents, or mixtures thereof. These non-limiting examples include salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinate esters, taurine derivatives (preferably alkyltaurates), phosphate esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of compounds containing sulfates, sulfonates, and phosphates, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, protein hydrolysates, lignosulfite wastewater, and methylcellulose. The presence of a surfactant may be particularly preferred if one of the active ingredients and / or one of the inert carriers is insoluble in water and application is carried out in water. The proportion of the surfactant is about 5% to about 40% by weight of the composition. In some embodiments, the proportion of the surfactant is about 10% to about 30% by weight of the composition, or about 15% to about 25% by weight. In some embodiments, the proportion of the surfactant is less than about 40% by weight, less than about 30% by weight, less than about 25% by weight, less than about 20% by weight, less than about 10% by weight, or less than about 5% by weight of the composition. In some embodiments, the proportion of the surfactant is more than about 5% by weight, more than about 10% by weight, more than about 20% by weight, more than about 25% by weight, or more than about 30% by weight of the urease inhibitor composition.
[0078] The formulation may further contain colorants and dyes. Dyes include inorganic pigments, such as iron oxide, titanium dioxide, and Prussian blue, as well as organic dyes, such as alizarin dyes, azo dyes, and metal phthalocyanine dyes, and micronutrients, such as salts of sulfur, calcium, magnesium, iron, manganese, boron, copper, cobalt, molybdenum, and zinc.
[0079] The formulation may further contain a carrier medium or vehicle, the medium or vehicle being water. Ion-exchanged water (deionized water), pure water, ultrapure water, and distilled water can be used as water. To reduce the amount of unwanted components present in the water, the purity of the water can be increased by operations such as removal of impurity ions with ion exchange resins, removal of contaminants with filters, and / or distillation.
[0080] Furthermore, those skilled in the art will also recognize, based on the properties listed above and additional properties obvious to those skilled in the art, the types and combinations of adjuvants and / or carriers required to optimize urease inhibitor formulations.
[0081] The disclosed formulations may be in liquid or solid form. Examples of liquid and solid formulations include, but are not limited to, soluble liquids (SF), emulsifying concentrates (EC), wettable powders (WP), dry flowable (DF) powders, flowable powders (F), water-soluble powders (SP), ultra-low volume concentrates (ULV), suspension concentrates (SC), aqueous suspensions (AS), microcapsule suspensions (ME or MT), or capsule suspensions (CS). In some embodiments, the urease inhibitor composition is in the form of a soluble salt that is water-soluble and requires little or no agitation to remain in solution. These types of formulations often refer to solutions (S), soluble concentrates (SC), liquids (L), and water-soluble concentrates (WSC). In some embodiments, these types of formulations (e.g., S) are "ready to use". In some embodiments, the formulations are formulations mixed in a tank or pre-mixed formulations. In some embodiments, these types of formulations (e.g., SC, WSC) are diluted with water before use.
[0082] In some embodiments, any of the above formulations (or urease inhibitor compositions) may be used in a method for coating solid urea-containing fertilizers, as will be described in more detail below. In other embodiments, any of the above formulations (or urease inhibitor compositions) may be used in a method for producing solid urea-containing fertilizers, as will be described in more detail below.
[0083] agricultural products Any of the urease inhibitor compositions or formulations described may be combined with one or more other components selected from the group consisting of fertilizers, agricultural active compounds, seeds, compounds having urease inhibitory activity, compounds having nitrification inhibitory activity, pesticides, herbicides, insecticides, fungicides, and acaricides.
[0084] fertilizer In some embodiments, the agricultural product described is a combination of the urease inhibitor composition or formulation described (generally referred to as the "urease inhibitor component") and a fertilizer. In some embodiments, the urease inhibitor component is a urease inhibitor composition comprising an antioxidant. In such embodiments, the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. In some embodiments, the urease inhibitor component is a urease inhibitor composition comprising an antioxidant and a chaotropic agent. Thus, the urease inhibitor component is an antioxidant or the urease inhibitor composition described herein.
[0085] In some embodiments, the urease inhibitor component is in liquid form. In such embodiments, the liquid urease inhibitor component does not contain any organic solvents when the inhibitor component is tBHQ. Therefore, in embodiments where the inhibitor component includes tBHQ and an organic solvent, a chaotropic agent must be present. These liquid urease inhibitor components can be combined with one or more fertilizers in liquid form. For example, in some embodiments, the urease inhibitor components described can be prepared in the form of a dispersion and / or solution in a liquid fertilizer, such as UAN, urea 20, or water. In addition, these liquid urease inhibitor components can also be applied as a surface coating to a fertilizer product in solid form. In the case of such agricultural products, the urease inhibitor components described are applied to the surface of the fertilizer in solid form as a liquid, dispersion, or powder.
[0086] In the case of agricultural products in which a urease inhibitor component is used as a coating, the urease inhibitor component may constitute about 0.005% to about 15% by weight of the coated fertilizer product, or about 0.01% to about 10% by weight, about 0.05% to about 5% by weight, about 0.05% to about 2% by weight, or about 0.5% to about 1% by weight of the agricultural product (e.g., the coated fertilizer product).
[0087] In some embodiments, the urease inhibitor component described is already incorporated into the solid form of the fertilizer. In the case of such agricultural products, the urease inhibitor component described is physically incorporated into the solid form of the fertilizer during the production process of the solid fertilizer (e.g., pre-injected).
[0088] In agricultural products in which urease inhibitor components are incorporated into the fertilizer product, the amount of urease inhibitor components present in the fertilizer product may vary. In some embodiments, the urease inhibitor components are present in the agricultural product (e.g., fertilizer product) in amounts of about 0.001% to about 15% by weight, about 0.001% to about 10%, about 0.001% to about 5%, about 0.01% to about 5%, about 0.01% to about 2.5%, about 0.1% to about 2.5%, about 0.1% to about 2%, about 0.1% to about 1.5%, about 0.5% to about 1.5%, or about 0.75% to about 1.25%, based on the total weight of the agricultural product. In some embodiments, the urease inhibitor components are present in the fertilizer product in amounts of about 1%, based on the total weight of the agricultural product.
[0089] The fertilizers used for these agricultural products are not particularly limited and can be any solid fertilizer suitable for application to fields and / or crops. Such solid fertilizers can be any granular fertilizer to which the urease inhibitor components described can be applied as a solution, liquid dispersion, or powder. In some embodiments, such fertilizers may be selected from the group consisting of starter fertilizers, phosphate fertilizers, nitrogen-containing fertilizers, phosphorus-containing fertilizers, potassium-containing fertilizers, calcium-containing fertilizers, magnesium-containing fertilizers, boron-containing fertilizers, chlorine-containing fertilizers, zinc-containing fertilizers, manganese-containing fertilizers, copper-containing fertilizers, urea and ammonium nitrite-containing fertilizers, and / or fertilizers containing molybdenum materials. In some embodiments, the fertilizer is or contains urea and / or ammonia, and includes, for example, anhydrous ammonia fertilizers. In some embodiments, the fertilizer contains nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, or micronutrients available to the plant. In some embodiments, the fertilizer is solid, granular, a fluid suspension, a gas, or a solution-type fertilizer. In some embodiments, the fertilizer contains micronutrients. Micronutrients are essential elements that plants require in small amounts. In some embodiments, the fertilizer contains metal ions selected from the group consisting of Fe, Mn, Mg, Zn, Cu, Ni, Co, Mo, V, and Ca. In some embodiments, the fertilizer contains gypsum, a member of the kieselite group, potassium products, potassium magnesium sulfate, elemental sulfur, or magnesium potassium sulfate. Such fertilizers may be granular, liquid, gaseous, or mixtures (e.g., a suspension of solid fertilizer particles in a liquid material). For example, in some embodiments, the fertilizer is a urea-containing fertilizer in solid form. In some embodiments, a fertilizer coated with the urease inhibitor component described is a solid urea-containing fertilizer. In some embodiments, a fertilizer in which the urease inhibitor component described is incorporated is a solid urea-containing fertilizer.
[0090] In some embodiments, the solid fertilizer (e.g., urea-containing fertilizer) is in the form of granules or prills. In some embodiments, the shape of the granules or prills is round (e.g., spherical or oval), but should not be limited thereto. Additional shapes include cubes, rectangular prisms, and / or irregular shapes.
[0091] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granular / prill having an average mesh size in the range of about 1 to about 100 (e.g., 1 / 100), about 10 to about 100 (e.g., 10 / 100), or about 16 to about 100 (e.g., 16 / 100) US mesh. In other embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granular / prill having an average mesh size in the range of about 4 to about 30 (e.g., 4 / 30), about 5 to about 24 (e.g., 5 / 24), or about 6 to about 16 (e.g., 6 / 16) US mesh.
[0092] In some embodiments, the median particle size (d) of the granules / pills of the fertilizer (e.g., urea-containing fertilizer) is 50 The median particle size (d) of the granules / pills of the fertilizer (e.g., urea-containing fertilizer) is in the range of approximately 0.1 to 3.5 mm, approximately 0.5 to approximately 2.5 mm, or approximately 0.9 to approximately 1 mm (or approximately 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 mm). In some embodiments, the median particle size (d) of the granules / pills of the fertilizer (e.g., urea-containing fertilizer) is... 50 ) are approximately 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm, 1.5 mm, or less than 1.0 mm.
[0093] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granular / prill having particle sizes in the range of about 10 to about 500, about 50 to about 450, about 75 to about 400, about 80 to about 250, or about 90 to about 230 SGN.
[0094] In some embodiments, the granular / prill fertilizer (e.g., urea-containing fertilizer) contains granular / prill having a UI (indicating uniformity of granule size) in the range of approximately 30-40, 30-50, 35-45, 40-60, 40-50, or 50-60.
[0095] In some embodiments, granular / prilline fertilizers (e.g., urea-containing fertilizers) are approximately 10-150 lbs / ft 3 , 30-100 lbs / ft 3 Approximately 45-85 lbs / ft 3 , or approximately 45-60 lbs / ft 3 It contains granules / prils having a particle density within the range.
[0096] In some embodiments, granular / prilline fertilizers (e.g., urea-containing fertilizers) are approximately 10-150 lbs / ft 3 , 30-100 lbs / ft 3 Approximately 45-75 lbs / ft 3 , about 50~70lbs / ft 3 , or approximately 60-70 lbs / ft 3 It has a bulk density. In some embodiments, the bulk density is a "sparsely packed" bulk density.
[0097] In some embodiments, the urease inhibitor components described may be applied together with the application of fertilizer. The urease inhibitor components may be applied before, after, or simultaneously with the application of fertilizer. Such liquid urease inhibitor components, including tBHQ in combination with an organic solvent, must also contain the chaotropic agent described herein.
[0098] Fertilizer products containing urease inhibitor compositions can be applied in any manner that benefits the crop of interest. In some embodiments, the product is applied to the growing medium in strips or rows. In some embodiments, the product is applied to the growing medium or to the entire growing medium before sowing or transplanting the desired crop plant. In some embodiments, the product is applied to the root zone of the growing plant.
[0099] Plants and / or crops include plants, such as cereals, tree fruits, shrubs, grains, legumes, and combinations thereof. Exemplary crops include rye, oats, maize, rice, sorghum, rye, rapeseed, rice, soybeans, sugar beets, sugarcane, turf, tree fruits, palm trees, coconut trees, or other nuts, grapes, shrubs, fruit plants, and beets, fodder beets, pomes, drupes, apples, pears, plums, peaches, almonds, cherries, and berries, such as strawberries, raspberries, and blackberries, as well as legumes such as beans, lentils, peas, soybeans, and peanuts, and oil plants, such as rapeseed, mustard, and sunflowers, and cucurbits, such as zucchini, cucumbers, and melons, and fiber plants, such as cotton, flax, hemp, and jute, and This includes, but is not limited to, citrus fruits such as oranges, lemons, grapefruits, and mandarins, as well as vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, sweet potatoes, yams, and bell peppers, and ornamental plants such as flowers, shrubs, broad-leaved trees, and evergreen plants such as conifers, cereals such as wheat, barley, oats, autumn wheat, spring wheat, autumn barley, spring barley, rye, grain rye, autumn durum wheat, spring durum wheat, autumn oats, spring oats, fodder grains, rye, timothy grass, fescue, timothy, seed-producing grasses, and meadows, and any combination thereof.
[0100] seed Several embodiments describe agricultural seeds coated with urease inhibitor components disclosed herein. The urease inhibitor components may be present in the seed product at levels of about 0.001% to about 10% by weight, about 0.004% to about 2% by weight, about 0.01% to about 1% by weight, or about 0.1% to about 1% by weight (or about 10% or less, about 9%, about 8%, about 7%, about 6%, about 5%, about 4%, about 3%, about 2%, about 1%, about 0.5%, about 0.1%, about 0.01%, or 0.001% or less) based on the total weight of the coated seed product. The seeds may be, but are not limited to, wheat, barley, oats, rye, rye, rice, maize, soybeans, cotton, or rapeseed.
[0101] others In some embodiments, urease inhibitors, nitrification inhibitors, pesticides, herbicides, insecticides, fungicides, and / or acaricides are combined with the urease inhibitor compositions disclosed herein. As used herein, “pesticide” refers to any agent having pesticide activity (e.g., herbicides, insecticides, and fungicides), preferably selected from the group consisting of insecticides, herbicides, and mixtures thereof, but usually excluding materials claimed to have plant fertilizer effects, such as sodium borate and zinc compounds, such as zinc oxide, zinc sulfate, and zinc chloride. For an unrestricted list of pesticides, see the “Farm Chemicals Handbook 2000, 2004” (Meister Publishing Co, Willoughby, OH), which is incorporated herein by reference in its entirety.
[0102] Examples of herbicides include acetochlor, alachlor, aminopyralide, atrazine, benoxacol, bromoxynil, carfentrazone, chlorsulfuron, clodinahop, clopyralide, dicamba, diclohop-methyl, dimethenamide, phenoxaprop, flucarbazone, flufenacet, flumethoslam, flumimicrolac, fluroxypyr, glufosinate-ammonium, glyphosate, halosulfuron-methyl, imazametabenz, imazamox, imazapyr, imazakine, imazetapyr, isoxaflutol, quinchlorac, MCPA, and MCPamine. This includes, but is not limited to, MCP esters, mephenoxam, mesotrione, metrachlor, s-metrachlor, metrivudine, metosulfuron methyl, nicosulfuron, paraquat, pendimethalin, picloram, primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl, limsulfuron, simazine, sulfosulfuron, thifensulfuron, topramezone, tralcoxidime, triallate, triasulfuron, tribenulon, triclopyr, trifluralin, 2,4-D, 2,4-D amines, and 2,4-D esters.
[0103] Examples of insecticides include 1,2-dichloropropane, 1,3-dichloropropene, abamectin, acephate, acequinosyl, acetamiprid, acetylone, acetoprole, acrinatrin, acrylonitrile, alanicarb, aldicarb, aldoxycarb, aldrin, arethrin, allosamidine, alixicarb, alpha-cypermethrin, alpha-ecdysone, amidithione, amidoflumeth, aminocarb, amiton, amitraz, anabasine, arsenic trioxide, atidathion, azadirachtin, azamethios, azinphosethyl, and azinphosmethyl Azobenzene, azocyclotin, azothoate, barium hexafluorosilicate, valthrin, bencrotiaz, bendiocarb, benfuracarb, benoxaphos, bensultap, benzoximate, benzyl benzoate, beta-cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin, binapacril, biorethrin, bioetanomethrin, biopermethrin, bistriflurone, borax, boric acid, bromufenbinphos, bromoDDT, bromocyclene, bromophos, bromophosethyl, bromopropylate, bufenca Lubu, buprofezin, butacarb, butathiophos, butocarboxime, butonate, butoxycarboxime, kazusaphos, calcium arsenate, calcium polysulfide, campechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, quinomethionate, chlorantraniliprole, chlorbenside, chlorbicyclene, chlordane, chlordecone, chlordimeform, chloretoxyphos, chlorfenapyr, chlorphenetol, chlorfensone, chlorfensulfide, chlorfensulfide, chlorfensulfide Lorfenbinphos, Chlorfluazurone, Chlormephos, Chlorobenzilate, Chloroform, Chloromebform, Chloromethirone, Chloropicrin, Chlopropylate, Chlorphoxime, Chlorprazophos, Chlorpyrifos, Chlorpyrifos-methyl, Chlorthiophos, Chlomafenozide, Synerin I, Synerin II, Cysmethrin, Chloetocarb, Clofentezine, Closantel, Clothianidin, Copper acetoarsenite, Copper arsenate, Copper naphthenate, Copper oleate, Coumaphos, Cumitoate, Crotamiton, Clotoxyphos, Cruentalen A and B,Culfomate, cryolite, cyanophenphos, cyanophos, cyanthoate, ciclethrin, cycloprothrin, cyenopyrafen, cyflumetofen, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin, cyromazine, cythioate, d-limonene, dazomet, DBCP, DCIP, DDT, decarbofuran, deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton-methyl, demeton-O, demeton-O methyl, demeton-S, demeton-S methyl, demeton-S methylsulfone Diafenthiuron, Dialiphos, Diamidaphos, Diazinon, Dicapton, Diclofenthion, Diclofluanide, Dichlorvos, Dicofor, Dicresyl, Diclotophos, Dicyclanil, Dieldrin, Dienochlor, Diflovidazine, Diflubenzuron, Dirol, Dimefluthrin, Dimefox, Dimethane, Dimethoate, Dimetrin, Dimethylvinphos, Dimethilane, Dynex, Dinobuton, Dinocup, Dinocup-4, Dinocup-6, Dinoctone, Dinopenton, Dinoprop, Dinosam, Dinosulfone, Dinotefuran, Dinoterbone Diophenolane, dioxabenzophos, dioxacarb, dioxathion, diphenylsulfone, disulfiram, disulfoton, diticlophos, DNOC, dofenapine, doramectin, ecdysterone, emamectin, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epophenonane, eprinomectin, esfenvalerate, etaphos, ethiofencarb, ethione, ethiprole, etoatemethyl, etoprophos, ethyl DDD, ethyl formate, ethylene dibromide, ethylene dichloride, Ethylene oxide, etofenprox, etoxazole, etrimphos, EXD, famfur, phenamiphos, phenazaflor, phenazaquin, fenbutasin oxide, fenchlorphos, phenetacarb, fenfluthrin, fenitrothion, phenobucarb, phenothiocarb, phenoxacrim, phenoxycarb, fenpyritrin, fenpropathrin, fenpyroximate, fenson, fensulfotion, fenthion, fenthion ethyl, fentriphanil, fenvalerate, fipronil, flonicamide, fluacrypyrim,Fluazuron, flubendiamide, flubendimine, flucoflon, flucycloxlon, flucitrinate, fluenate, flufenetil, flufenelim, flufenoxlon, flufenprox, flumetrin, fluolbenside, fluvalinate, honofos, formmethanate, formothion, formparanate, fosmethilane, fosspire, fosthiazate, fosthiethane, fosthiethane, flatiocarb, fretrin, furfural, gamma-halothrin, gamma-HCH, halfenprox, halophenozide, HCH, HEOD, heptachlor, Ptenofos, Heterophos, Hexaflumurone, Hexythiazox, HHDN, Hydramethylnon, Hydrocyanide, Hydroprene, Hikincarb, Imisiafos, Imidacloprid, Imiprothrin, Indoxacarb, Iodomethane, IPSP, Isamidophos, Isazofos, Isobenzane, Isocarbophos, Isodrine, Isofenphos, Isoprocarb, Isoprothiolane, Isothioate, Isoxathion, Ivermectin, Jasmolin I, Jasmolin II, Iodofenphos, Juvenile Hormone I, Juvenile Hormone II, Juvenile Hormone III, Kereban Quinoprene, lambda cyhalotrin, lead arsenate, lepimectin, leptophos, lindane, lilimphos, lufenulon, ritidathion, malathion, malonoben, majidox, mecarbam, mecarbhon, menazone, mephosphoran, mercurous chloride, mesulfen, mesulfenphos, metaflumizone, metam, methacryphos, methamidophos, methidathion, methiocarb, metoclotophos, methomyl, methoprene, methoxychlor, methoxyphenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metoluca Lube, Methoxadiazone, Mevinfos, Mexacarbate, Milbemectin, Milbemycin oxime, Mipahox, Milex, MNAF, Monoclotophos, Morphothion, Moxidectin, Naphthalophos, Nared, Naphthalene, Nicotine, Niflulidide, Nikkomycin, Nitenpyram, Nichiazine, Nitrilacarb, Novalon, Noviflumuron, Omethoate, Oxamyl, Oxidemetonmethyl, Oxideprophos, Oxydisulfone, Paradichlorobenzene, Parathion, Parathionmethyl, Penflurone, Pentachlorophenol,Permethrin, Fencapton, Phenothrin, Fenthoate, Phorate, Fosalon, Phosphane, Phosmet, Fosnichlor, Phosphamidone, Phosphine, Phosphocarb, Foxim, Foximmethyl, Pyrimethraphos, Pyrimicarb, Pyrimiphosethyl, Pyrimiphosmethyl, Potassium arsenite, Potassium thiocyanate, pp'DDT, Prallethrin, Precosen I, Precosen II, Precosen III, Primidophos, Proclonol, Profenophos, Profluthrin, Promacil, Promecarb, Propaphos, Propargit, Propetamphos, Pro Poxul, Protidathion, Prothiofos, Protoate, Protifenbut, Pyraclofos, Pyrafluprole, Pyrazofos, Pyrethmetrin, Pyrethrin I, Pyrethrin II, Pyridaben, Pyridaryl, Pyridafenthion, Pyrifluquinazon, Pyrimidifen, Pyrimitate, Pyriprole, Pyriproxyfen, Cassia, Quinalfos, Quinalfos, Quinalfos-methyl, Quinotion, Rahoxanide, Resmethrin, Rotenone, Lianya, Sabajira, Shuradan, Selamectin, Silafluofen, Sodium arsenite, Sodium fluoride, Hexaflu Sodium orosilicate, sodium thiocyanate, sofamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramato, sulcoflon, sulfiram, sulfuramide, sulfotep, sulfur, sulfuryl fluoride, sulprophos, taufluvalinate, tadimucarb, TDE, tebufenozide, tebufenpyrad, tebupyrimphos, teflubenzuron, tefluthrin, temephos, TEPP, terarethrin, terbuphos, tetrachloroethane, tetrachlorvinphos, tetradiphon, tetramethrin, tetranactin, tetra Sul, Thetacypermethrin, Thiacloprid, Thiamethoxam, Cyclophos, Thiocarboxim, Thiocyclam, Thiodicarb, Thiofanox, Thiometon, Thionadin, Thioquinox, Thiosultap, Thuringensin, Tolfenpyrad, Tralomethrin, Transfluthrin, Transpermethrin, Triaten, Triazamate, Triazophos, Trichlorfon, Trichlormetaphos-3, Trichloronate, Triphenophos, Triflumulon, Trimetacarb, Triprene, Bamidthione, Bamidthione, Vaniliprole, XMC,This includes, but is not limited to, xylcarb, zetacypermethrin, and zolaprofos.
[0104] Examples of fungicides include acibenzoral, acyl amino acid fungicides, acipetax, algimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylphos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, venalaxyl, venalaxyl-M, benodanil, benomyl, benquinox, bentallon, bentiavaricarb, benzalkonium chloride, benzamacryl, benzamide fungicides, and benzamorph. Benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazol carbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazine, binapacril, biphenyl, vitertanol, bithionol, bixafen, blasticidine-S, Bordeaux mixture, boric acid, boscalid, cross-linked diphenyl fungicides, bromconazole, bupirimate, Burgundy mixture, butthiobate, sec-butylamine, calcium polysulfide, captahole, captan, carbamate fungicides Fungal agents, carbamorphs, carbanilate fungicides, carbendazim, carboxyne, carpropamide, carvon, Cheshant mixture, quinomethionate, clobentiazon, chloraniformethane, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroform, chlorneb, chloropicrin, chlorothalonil, chlorquinox, clozolinate, cyclopirox, crimbazole, clotrimazole, conazole fungicides, conazole fungicides (imidazole), conazole fungicides (triazole), copper(II) acetate, copper carbonate (II) (basic), copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper(II) sulfate, copper sulfate (basic), copper zinc chromate, cresol, cufraneb, cuprobum, cuprous oxide, cyazofamide, cyclafamide, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamide, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin, dehydroacetic acid, dicarboximide fungicides, diclofluanide, diclon, dichlorofen, dichlorophenyl,Diclozolin, diclobutrazol, diclocimet, diclomezin, dichloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetrim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinitrophenol fungicides, dinobuton, dinocup, dinocup-4, dinocup-6, dinoctone, dinopenton, dinosulfone, dinotervone, diphenylamine, dipyrithione, disulfiram, ditalimphos, dithianone, dithiocarbamate fungicides, DNOC, dode Morph, Dodzine, Dozin, Donatodine, Drazoxolone, Edifenphos, Epoxyconazole, Etaconazole, Etem, Etaboxam, Ethyrimol, Ethoxyquin, Ethylene oxide, Ethylmercury 2,3-dihydroxypropyl mercaptide, Ethyl ethyl mercury, Ethylmercury bromide, Ethylmercury chloride, Ethylmercury phosphate, Etridiazole, Famoxadone, Phenamidon, Phenaminosulf, Phenapanil, Phenarimol, Fenbuconazole, Fenflam, Fenhexamide, Fenitropan, Phenoxanil, Fenpiclonil, Fenpro Pidine, fenpropimorph, fentin, falbam, ferimzon, fluazinam, fluconazole, fludioxonil, flumetoveil, flumorph, fluopicolide, fluoroimide, fluotorimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafole, fluxapiroxad, forpet, formaldehyde, fosetil, fuberidazole, fluraxil, flametopyr, flamido-type fungicides, flanilide-type fungicides, flucarbanil, fluconsol, fluconsol-s S, furfural, flumecyclox, flofanate, gliodin, griseofulvin, guazatin, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorofen, hexaconazole, hexylthiophos, hydragafen, himexazole, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ibuconazole, iprobenphos, iprodione, iprovalicarb, isopropyl alcohol, isoprothiolane, isobalezion, isopyrazam,Kasugamycin, Ketoconazole, Kresoxim-methyl, Lime sulfur mixture (lime sulfur), Mancopper, Mancozeb, Maneb, Mebenil, Mecarbinzide, Mepanipyrim, Mepronil, Mercuric chloride (discontinued), Mercury oxide (discontinued), Mercurous chloride (discontinued), Metalaxyl, Metalaxyl-M (also known as Mephenoxam), Metam, Metazoxolone, Metconazole, Metasulfocarb, Metofloxam, Methyl bromide, Methyl isothiocyanate, Methylmercury benzoate, Dicyandiamide methylmercury, Pentachlorophenoxide methylmercury, Methylam, Metominos Trobin, Metraphenone, Methosulfobacs, Milneb, Morpholine fungicides, Mycrobutanil, Mycrozolin, N-(ethylmercury)-p-toluenesulfonanilide, Nabam, Natamycin, Nystatin, β-nitrostyrene, Nitrotal-isopropyl, Nualimol, OCH, Octylinone, Ofrace, Oprodione, Organomercury fungicides, Organophosphate fungicides, Organotin fungicides (discontinued), Orthophenylphenol, Orysastrobin, Oxadixyl, Oxatiin fungicides, Oxazole fungicides, Oxine copper, Oxpocona Zole, oxycarboxyne, pefurazoate, penconazole, pencyclon, pentachlorophenol, penthiopyrad, phenylmercury urea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivatives of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phenylsulfamide fungicides, phosdiphen, phosphite, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamate, high molecular weight dithiocarbamate fungicides, polyoxin, polyoxolim, polysulfide fungicides, potassium azide, Potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazide, prothiocarb, prothioconazole, pyracarboride, pyraclostrobin, pyrazole fungicides, pyrazofos, pyridine fungicides, pyridinitrile, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, pyroxicrol, piroxiflu, pyrrole fungicides, quinacetol, quinazamide, quinconazole, quinoline fungicides, quinomethionate, quinone fungicides,Quinoxaline fungicides, quinoxifen, quintozen, ravenzazole, salicylanilide, silthiofame, silver, simeconazole, sodium azide, sodium bicarbonate[2][3], sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, strobilurin fungicides, sulfonanilide fungicides, sulfur, sulfuryl fluoride, sultropen, TCMTB, tebuconazole, tecrophthalam, technazen, tecolam, tetraconazole, thiabendazole, thiadifluor, thiazole fungicides, thiofen, tifluzamide, thymol, triforine, thiocarbamate fungicides, thiochlorfenfim, thiomersal, thiophanate, thiophanate-methyl, thiofe This includes, but is not limited to, nitramide fungicides such as thioquinox, thyram, thiadinyl, thioxymide, tivedo, tolclophos-methyl, tolnaphthate, tolfluanide, tolylmercury acetate, triadimephon, triadimenol, triamiphos, trialimol, triazbutyl, triazine fungicides, triazole fungicides such as triazoxide, tributyltin oxide, triclamide, triciclamide, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, uniconazole-P, urea fungicides such as validamycin, valinamide fungicides such as vinclozoline, voriconazole, zarilamide, zinc naphthenate, zineb, ziram, and / or zoxamide.
[0105] In some embodiments, the subject matter compositions of the present disclosure are pesticide / urease inhibitor composition-containing products comprising a pesticide and tert-butylhydroquinone (and optionally additional components). In some embodiments, the pesticide is a herbicide, an insecticide, or a combination thereof.
[0106] The amount of urease inhibitor composition in a product containing a pesticide / urease inhibitor composition may vary. In some embodiments, the amount of urease inhibitor composition is present at a level of about 0.05% to about 10% by weight (more preferably about 0.1% to about 4% by weight, most preferably about 0.2% to about 2% by weight) based on the total weight of the product containing the pesticide / urease inhibitor composition, which is considered to be 100% by weight.
[0107] Exemplary classifications of acaricides include plant-based mite control agents, cross-linked diphenyl mite control agents, carbamate mite control agents, oxime carbamate mite control agents, carbadic acid mite control agents, dinitrophenol mite control agents, formamidine mite control agents, isoxalin mite control agents, macrocyclic lactonid mite control agents, avermectin mite control agents, milbemycin mite control agents, milbemycin mite control agents, mite growth regulators, organochlorine mite control agents, organophosphate mite control agents, organothiophosphate mite control agents, phosphonic acid mite control agents, and phosphoaluminum This includes, but is not limited to, thiolate mite control agents, organotid mite control agents, phenylsulfonamide mite control agents, pyrazole carboxamide mite control agents, pyrethroid ether mite control agents, quaternary ammonium mite control agents, euryrotoid ester mite control agents, pyrrole mite control agents, quinoxaline mite control agents, methoxyacrylate strobilurin mite control agents, teronate mite control agents, thiasolizin mite control agents, thiocarbamate mite control agents, thiourea mite control agents, and unclassified mite control agents. Examples of acaricides in these classifications include plant-based mite control agents (carvacrol, sanguinalin), cross-linked diphenyl mite control agents (azobenzene, benzoximate, benzyl, benzoic acid, bromopropylate, chlorbenside, chlorphenetol, chlorfensone, chlorfensulfide, chlorobenzylate, chloropropylate, cyflumetofen, DDT, dicofol, diphenyl, sulfone, dofenapine, fensone, fentriphanil, fluolbenside, genitol, hexachlorophene, fenproxide, proclonal, tetradiphon, tetrasul), and carbamate mite control agents (benomide). (L, carbanolate, carbaryl, carbofuran, methiocarb, metholcarb, promacil, propoxul), oximecarbamate mite control agents (aldicarb, butocarboxime, oxamyl, thiocarboxime, thiophanox), carbazet mite control agents (bifenazate), dinitrophenol mite control agents (binapacrill, Ginex, Zinobuton, Zinocup, Zinocup-4, Zinocup-6, Dinoctone, Dinopenton, Dinosulfone, Dinotervon, DNOC), formamidine mite control agents (amitraz, chlorodimeform, chloromebform, formmethanate, formparanate,Medimeform, semiamitraz), isoxazoline mite control agents (afoxolaner, fluralaner, lotilaner, sarolaner), macrocyclic lactundan mite control agent (tetranactin), avermectin mite control agents (abamectin, doramectin, eprinomectin, ivermectin, selamectin), milbemycin mite control agents (milbemectin, milbemycin, oxime, moxidectin), mite growth regulators (clofentezine, ciromazine, diflovidazine, dofenapine, fluazuron, flubendimine, flucycloxuron, flufenoxuron, Hexythiazox), organochlorine mite control agents (bromocyclene, campechlor, DDT, dienochlor, endosulfan, lindane), organophosphate mite control agents (chlorfenvinphos, clotoxyphos, dichlorvos, heptenophos, mevinphos, monoclotophos, nared, TEPP, tetrachlorvinphos), organothiophosphate mite control agents (amidithion, amiton, azinphos-ethyl, azinphos-methyl, azothoate, benoxaphos, bromophos, bromophos-ethyl, carbophenothion, chlorpyrifos, chlorthiophos, coumaphos, shea Endoate, Demeton, Demeton-O, Demeton-S, Demeton-Methyl, Demeton-O-Methyl, Demeton-S-Methyl, Demeton-S-Methylsulfone, Dialiphos, Diazinon, Dimethoate, Dioxathion, Disulfon, Endothion, Ethion, Ethoate-Methyl, Formothion, Malathion, Mecarbam, Methacryphos, Omethoate, Oxydeprophos, Oxydisulfon, Parathion, Fencapton, Phorate, Fosalon, Fosmet, Fostin, Foxim, Pyrimifos-Methyl, Protidathion, Protoate, Pyrimite (T, Kinalphos, Kinthiophos, Sofamide, Sulfotep, Thiometon, Triazophos, Triphenophos, Bamidthione), Phosphonic acid mite control agents (Trichlorfon), Phosphoramidothioate mite control agents (Isocarbofos, Methamidophos, Propetamphos), Phosphorodiamide mite control agents (Dimehox, Mipahox, Shuradan), Organostalt mite control agents (Azocyclotin, Cyhexatine, Fenbutine, Oxide, Phostine), Phenylsulfamide mite control agent (Diclofluanide), Phthalimide mite control agents (Dialiphos, Phosmet),Pyrazole mite control agents (cyenopyrafen, fenpiroximate), phenylpyrazole mite control agents (acetol, fipronil, vaniliprole), pyrazole carboxamide mite control agents (piflubmid, tebufenpyrad), pyrethroid ester mite control agents (acrinatrin, bifenthrin, broflusrinate, cyhalothrin, cypermethrin, alpha-cypermethrin, fenpropathrin, fenvalerate, flusitrin) (Lineate, flumethrin, fluvalinate, tau-fluvalinate, permethrin), pyrethroid ether mite control agent (halfenprox), pyrimidinamine mite control agent (pyrimidifen), pyrrole mite control agent (chlorfenapyr), quaternary ammonium mite control agent (sanguinalin), quinoxalin mite control agent (kinomethionate, thioquinox), methoxyacrylate strobilin mite control agent (bifujunji, fluacrypirin) Mite control agents (fluphenoxystrobin, pyriminostrobin), sulfite ester mite control agents (aramite, propargit), tetronic acid mite control agents (spirodiclofen), tetrazolidine mite control agents (clofentezine, diflovidazine), thiazolidinedione mite control agents (flubendimine, hexythiazox), thiocarbamate mite control agents (phenothiocarb), thiourea mite control agents (chloromethiurone, diafenthiurone), unclassified mite control agents (This includes, but is not limited to, asequinosyl, acinonapir, amidoflumet, arsenic, oxide, clenpyrin, closantel, crotamiton, cycloplate, simiasol, disulfiram, etoxazole, phenazaflor, phenazaquin, fluenetil, mesulfen, MNAF, niflulidide, nikkomycin, pyridaben, sulfiram, sulfuramide, sulfur, thuringensine, triatene).
[0108] In some embodiments, the acaricides also include abamectin, acephate, acequinosyl, acetamiprid, aldicarb, arethrin, aluminum phosphide, aminocarb, amitraz, azadirachtin, azinphos-ethyl, azinphos-methyl, Bacillus thuringiensis, benziocarb, beta-cyfluthrin, bifenazate, bifenthrin, bomil, buprofezin, calcium cyanide, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, chlorfenbinphos, chlorobenzylate, chloropicrin, chlorpyrifos, Clofentezin, Chlorfenapyr, Clothianidin, Coumaphos, Clotoxyphos, Clotoxyphos + Dichlorvos, Cryolite, Cyfluthrin, Cyromazine, Cypermethrin, DEET, Deltamethrin, Demeton, Diazinon, Diclofenthion, Dichloropropene, Dichlorvos, Dicofor, Diclotophos, Dierdrin, Dienochlor, Diflubenzuron, Dical (fungicide + acaricide), Dimethoate, Dinocap, Dinotefuran, Dioxathion, Disulfon, Emamectin Benzoate, Endosulfan, Endrin, Esfen Valerate, Ethion, Etoprop, Ethylenedibromide, Ethylenedichloride, Ethoxazole, Famfur, Fenitrothion, Phenoxycarb, Fenpropatrin, Fenpyroximate, Fensulfothin, Fenthion, Fenvalerate, Flonicamide, Flucitrinate, Fluvalinate, Honofos, Formetanate hydrochloride, Gamma-cyhalotrin, Halofenozide, Hexakis, Hexythiazox, Hydramethylnon, Slaked lime, Indoxacarb, Imidacloprid, Kerosene, Quinoprene, Lambda-cyhalotrin, Lead arsenate, Phosphorus Den, Malathion, Mephosphorane, Metaldehyde, Metam-sodium, Metamidophos, Methidathion, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyphenozide, Methyl bromide, Methylparathion, Mevinphos, Mexacarbate, Emulsified spores, Nared, Naphthalene, Nicotine sulfate, Novalon, Oxamyl, Oxidemeton-methyl, Oxythioquinox, Para-dichlorobenzene, Parathion, PCP, Permethrin, Petroleum, Phorate, Phosalon, Phosphane, Phosmet, Phosphamidone, Foxim, Piperonyl butoxide,The following may be selected: pyrimicarb, pyrimiphos-methyl, profenofos, propargit, propetamfos, propoxul, pyrethroid-synthetic: see below, allethrin, permethrin, fenvalerate, resmethrin, pyromancy, pyridaben, pyriproxyfen, resmethrin, rotenone, s-methoprene, soap, insecticide, sodium fluoride, spinosad, spiromesifen, sulfotep, sulprofos, temefos, terbufos, tetrachlorvinfos, tetrachlorvinfos + dichlorvos, tetradiphon, thiamethoxam, thiodicarb, toxafen, tralomethrin, trimetacarb, and tebufenozide.
[0109] method In some embodiments, the urease inhibitor composition is used directly. In other embodiments, the urease inhibitor composition is formulated in a manner that facilitates its use in the context of productive agriculture. For example, in some embodiments, the urease inhibitor composition is used in agricultural products together with fertilizers (e.g., urea-containing fertilizers). The urease inhibitor composition used in these methods contains an antioxidant (e.g., tert-butylhydroquinone) alone or in combination with the chaotropic agent described above. The urease inhibitor composition alone or formulated as an agricultural product (e.g., urea-containing fertilizer) can be used in the following ways: A. Methods for improving plant growth and / or plant health, and / or soil fertility. B. Methods for inhibiting urease enzyme activity C. Methods for inhibiting ammonia release or generation D. Methods for improving soil conditions E. Method for preparing a urease inhibitor composition F. Method for preparing agricultural products containing fertilizer
[0110] A. Methods for improving plant growth include contacting the soil with the urease inhibitor compositions disclosed herein. In some embodiments, the urease inhibitor composition is applied to the soil before the emergence of sown crops. In some embodiments, the urease inhibitor composition is applied to the soil adjacent to the plants and / or to the base of the plants and / or to the root zone of the plants. In some embodiments, the urease inhibitor composition is formulated as an agricultural product together with a fertilizer (e.g., a urea-containing fertilizer) and applied in the same manner as described above for the urease inhibitor composition.
[0111] Methods for improving plant growth can also be achieved by applying the urease inhibitor compositions disclosed herein to seeds as a seed coating in the form of a liquid dispersion that forms a dry residue upon drying. In some embodiments, the urease inhibitor compositions disclosed herein are in solid form (e.g., powder) and are applied to seeds so that the powder adheres to the surface of the seeds. In these embodiments, the seed coating provides an antioxidant (e.g., tert-butylhydroquinone) very close to the seeds when sowing, so that the antioxidant can exert its beneficial effects in the environment where it is most needed. That is, the antioxidant (e.g., tert-butylhydroquinone) provides an environment that helps improve plant growth in areas where the effect can be localized around the plant in which it is desired. In the case of seeds, a coating containing an antioxidant (e.g., tert-butylhydroquinone) increases the chances of seed germination, subsequent plant growth, and increased nutrient availability in the plant.
[0112] B. A method for inhibiting / reducing urease enzyme activity, comprising applying a urease inhibitor composition disclosed herein to soil. In some embodiments, the urease inhibitor composition is applied to soil before the emergence of sown crops. In some embodiments, the urease inhibitor composition is applied to soil adjacent to plants and / or to the base of plants and / or to the root zone of plants. In some embodiments, urease enzyme activity is inhibited / reduced by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least about 95%.
[0113] C. Methods for inhibiting / reducing ammonia release or generation in an affected area include applying a urease inhibitor composition disclosed herein to the affected area. In some embodiments, application of a urease inhibitor to an affected area inhibits / reduces ammonia release in the affected area by at least about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least 95%. The affected area may be soil adjacent to plants, fields, pastures, livestock or poultry housing, pet bedding, manure collection zones, upright walls forming enclosures, or roofs substantially covering an area, in which case the urease inhibitor may be applied directly to the manure in the collection zone. The urease inhibitor component is preferably applied in the form of an aqueous dispersion having a pH of about 1 to about 5, at a level of about 0.005 to about 3 gallons per ton of manure.
[0114] D. A method for improving soil conditions selected from the group consisting of nitrification processes, urease activity, and combinations thereof, comprising the step of applying an effective amount of the urease inhibitor composition described herein or an effective amount of the agricultural product disclosed herein to the soil. The urease inhibitor composition or agricultural product disclosed herein is generally applied at levels of about 0.01% to about 10% by weight, about 0.1% to about 10% by weight, about 1% to about 10% by weight, or about 1% to about 5% by weight, based on the total weight of the urease inhibitor composition or agricultural product.
[0115] E. A method for preparing a urease inhibitor composition in liquid form involves contacting an antioxidant, a chaotropic agent, and / or one or more organic solvents disclosed herein to form a mixture. In some embodiments, the mixture is a solution (i.e., the antioxidant and chaotropic agent, if present, are completely dissolved). In some embodiments, the mixture is a dispersion (i.e., the antioxidant and chaotropic agent, if present, are not completely dissolved).
[0116] A method for preparing a urease inhibitor composition in solid form involves grinding and / or pulverizing, if present, the antioxidants and chaotropic agents disclosed herein in solid form to produce powders. In some embodiments, the antioxidants and chaotropic agents, if present, are mixed before the grinding and / or pulverizing step. In such embodiments, the antioxidants and chaotropic agents, if present, are ground and / or pulverized simultaneously. In some embodiments, the antioxidants and chaotropic agents, if present, are ground and / or pulverized separately to obtain separate powders, which are then mixed to obtain a urease inhibitor composition. Those skilled in the art will generally be familiar with various grinding and pulverizing techniques. For example, in some embodiments, the method utilizes stainless steel beads as the grinding technique.
[0117] The amounts of antioxidants and chaotropic agents used in these preparation methods may vary. In some embodiments, the amounts of antioxidants and chaotropic agents used in the disclosed methods are in the range of molar ratios of antioxidants to chaotropic agents of approximately 1:1000 to approximately 1000:1, approximately 1:500 to approximately 500:1, approximately 1:250 to approximately 250:1, approximately 1:150 to approximately 150:1, approximately 1:100 to approximately 100:1, approximately 1:75 to approximately 75:1, approximately 1:50 to approximately 50:1, approximately 1:25 to approximately 25:1, approximately 1:15 to approximately 15:1, approximately 1:10 to approximately 10:1, approximately 1:8 to approximately 8:1, approximately 1:5 to approximately 5:1, approximately 1:3 to approximately 3:1, or approximately 1:2 to approximately 2:1. In some embodiments, the antioxidant and the chaotropic agent are used in a 1:1 molar ratio.
[0118] F. A method for preparing an agricultural product comprises contacting the agricultural product with the urease inhibitor composition described. In some embodiments, the urease inhibitor is in the form of a solution / liquid or dispersion and is sprayed onto the outer surface of a solid agricultural product (e.g., fertilizer or seeds). In some embodiments, the urease inhibitor composition is mixed with a solid, liquid, or gaseous fertilizer containing urea, and in particular with solid fertilizers, in the latter case, the urease inhibitor composition is applied to the surface of the (urea-containing) fertilizer as an aqueous dispersion and subsequently dried, so that the urease inhibitor composition is present on the solid fertilizer as a dried residue. In some embodiments, the urease inhibitor composition is in solid form, e.g., powder. In such embodiments, the solid urease inhibitor is applied to the outer surface of a solid agricultural product so that the urease inhibitor composition adheres to its surface.
[0119] A method for preparing an agricultural product containing a fertilizer in powder form involves grinding and / or pulverizing a urease inhibitor composition disclosed herein in solid form and a fertilizer in solid form (e.g., a urea-containing fertilizer) to produce a powder. In some embodiments, the urease inhibitor composition and fertilizer are mixed before the grinding and / or pulverizing step. In such embodiments, the urease inhibitor composition and fertilizer are ground and / or pulverized simultaneously. In some embodiments, the urease inhibitor composition and fertilizer are ground and / or pulverized separately to obtain separate powders, which are then mixed together to obtain an agricultural product. Those skilled in the art will generally be familiar with various grinding and pulverizing techniques. For example, in some embodiments, the method utilizes stainless steel beads as the grinding technique.
[0120] The amounts of urease inhibitory composition and fertilizer used in these preparation methods may vary. In some embodiments, the amounts of urease inhibitory composition and fertilizer used in the disclosed methods are in the range of weight ratios of urease inhibitory composition to fertilizer of about 1:1000 to about 1000:1, about 1:750 to about 750:1, about 1:500 to about 500:1, about 1:250 to about 250:1, about 1:150 to about 150:1, about 125:1 to about 1:125, about 1:100 to about 100:1, or about 1:75 to about 75:1. In some embodiments, the urease inhibitory composition and fertilizer are used in a molar ratio of 1:99.
[0121] Methods for preparing agricultural products containing fertilizers in the form of granules or prills, wherein the urease inhibitor composition described herein is incorporated into such granules or prills. In these methods, the disclosed urease inhibitor composition or formulation can be used as an additional component in the production process of such fertilizers. For example, common fertilizers in the form of granules or prills are urea-containing fertilizers. The production process of urea-containing granules or urea-containing prills is generally known in the art and generally employs a urea molten or urea aqueous solution.
[0122] The urea source for preparing a urea molten product or an aqueous urea solution may include any suitable urea source. In some embodiments, the urea source is urea that remains molten (not cooled and remelted) after synthesis. In some embodiments, the urea source is urea in solid form and includes, but is not limited to, granulated urea or prilylated urea, i.e., remelted and dehydrated urea. In some embodiments, urea is produced from ammonia and carbon dioxide, for example, in an industrial urea production plant. Those skilled in the art will recognize other urea sources for the method of the present invention.
[0123] The amount of urea in urea-containing granular fertilizer can range from about 1% to about 99% by weight relative to the total weight of the agricultural product (urea-containing granules pre-injected with a urease inhibitor). The amount of urea present in the agricultural product can be about 1% to about 99% by weight, about 10% to about 99% by weight, about 20% to about 99% by weight, about 30% to about 99% by weight, about 40% to about 99% by weight, about 50% to about 99% by weight, about 60% to about 99% by weight, about 70% to about 99% by weight, about 80% to about 99% by weight, or about 90% to about 99% by weight, based on the total weight of the agricultural product. In some embodiments, the amount of urea is at least about 60% by weight, about 70% by weight, about 80% by weight, about 90% by weight, about 91% by weight, about 92% by weight, about 93% by weight, about 94% by weight, about 95% by weight, about 96% by weight, about 97% by weight, about 98% by weight, or about 99% by weight, based on the total weight of the agricultural product.
[0124] In some embodiments, the urea molten product may initially contain up to about 70% by weight, about 75% by weight, about 80% by weight, about 85% by weight, or about 80% by weight of urea in water, either from the urea source used or by the addition of UF85 or the like. Such an aqueous urea molten product may be further concentrated by vacuum concentration or evaporation at atmospheric pressure to obtain a concentrated urea molten product. In some embodiments, the obtained urea molten product contains water at a reduced concentration based on the total weight of the urea molten product, such as less than about 9%, 8%, 7%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, or less than 1% (e.g., about 0.5%, 0.4%, 0.3%, 0.2%, or 0.1%).
[0125] In some embodiments, the disclosed method provides an agricultural product in which the water concentration is up to about 1% by weight based on the total weight of the agricultural product.
[0126] Accordingly, in some embodiments, a method for preparing agricultural products such as urea-containing fertilizers in the form of granules or prills in which the urease inhibitor composition described herein is incorporated therein comprises: obtaining a urea molten material; contacting the urea molten material with a urease inhibitor composition or formulation disclosed herein to produce a mixture of the urea molten material and the urease inhibitor; and forming the mixture of the urea molten material and the urease inhibitor into granules and / or prills.
[0127] In some embodiments, the contact step of the method includes mixing the urease inhibitor with the urea molten material. Thorough mixing of both components should be performed to facilitate the uniform distribution of the urease inhibitor composition or formulation throughout the urea molten material. Uniform distribution of the urease inhibitor in the granular fertilizer compositions of the present invention enhances the performance of these compositions with respect to their ability to promote plant growth and inhibit urease enzyme activity. Therefore, in some embodiments, the urease inhibitor composition is added to the urea molten material before the molding step, which is performed in either a granulator or a pre-ringing tower (or vice versa).
[0128] In order to ensure a uniform distribution of the urease inhibitor composition in the mixture of urea molten material and urease inhibitor produced in the contact step, sufficient time must be given to allow both components (i.e., urea molten material and urease inhibitor composition) to dissolve. Therefore, in some embodiments, a convenient time for adding the urease inhibitor composition or formulation disclosed herein to the urea molten material in a urea production plant would be before or during the evaporation step used to reduce the water content of the urea molten material. In some embodiments, the urease inhibitor of the formulation disclosed herein is introduced into the urea molten material immediately before the granulation or priling step, and is retained in the molten material for a time sufficient to allow for the distribution of the urease inhibitor into the molten material.
[0129] In some embodiments, the retention time of the urea molten material from the time of urease inhibitor addition to the granulation step is less than 5 minutes, or even less than 1 minute. In some embodiments, the retention time is only about 50 seconds, or 40 seconds, or 30 seconds, or 29 seconds, or 28 seconds, or 27 seconds, or 26 seconds, or 25 seconds, or 24 seconds, or 23 seconds, or 22 seconds, or 21 seconds, or 20 seconds, or 19 seconds, or 18 seconds, or 17 seconds, or 16 seconds, or 15 seconds, or 14 seconds, or 13 seconds, or 12 seconds, or 11 seconds, or 10 seconds, or 9 seconds, or 8 seconds, or 7 seconds, or 6 seconds, or 5 seconds, or 4 seconds, or 3 seconds, or 2 seconds, or 1 second. Longer retention times may result in partial degradation of the urease inhibitor, increased biuret concentration, and / or reduced efficacy of the agricultural product.
[0130] In some embodiments, the urease inhibitor composition or formulation is added to the urea molten material at varying flow rates. In some embodiments, the urease inhibitor composition or formulation is added at flow rates of approximately 5 lbs / hour to approximately 2500 lbs / hour, approximately 10 lbs / hour to approximately 2500 lbs / hour, approximately 20 lbs / hour to approximately 220 lbs / hour, approximately 50 lbs / hour to approximately 200 lbs / hour, or approximately 75 lbs / hour to approximately 150 lbs / hour.
[0131] In some embodiments, the urease inhibitor composition or formulation disclosed herein is brought into contact with a urea molten material, and then any excess water present in the urease inhibitor-urea molten material composition is evaporated.
[0132] When forming granules or prills, the urease inhibitor-urea molten composition is cooled in a granulator or prilling tower. Generally, the granulation process takes place in a granulator, where a rotating high-speed airflow needs to be formed in a central coagulation tube. The particles are picked up at the bottom of the tube and accelerated by the airflow. These particles come into contact with fluid droplets produced from spray nozzles at the bottom of the tube. Because of the high relative velocity of the particles, air, and fluid droplets, wetting is efficient and drying begins almost immediately. During granulation, the urease inhibitor-urea molten composition is sprayed onto circulating, reusable prills (or seed particles such as solid urea or solid urease inhibitor), while simultaneously, air passes through the granulator, solidifying the urease inhibitor-urea molten composition deposited on the seed material. In some cases, the urease inhibitor-urea molten composition is prepared before spraying. This can improve the storability and handling of granular agricultural products. There are two types of granulators: drum granulators and pan granulators. In drum granulators, solid material is layered onto seed granules placed in a rotating drum granulator / cooler with a diameter of approximately 4.3 meters (14 feet). Pan granulators are also a type of agitated (tumble grow / non-pressurized / wet granulation) flocculant used in various industries to form products through a layering process and pelletize fine particles into round granules.
[0133] During the prilling process in the prilling tower, the concentrated urease inhibitor-urea molten composition is supplied to a perforated rotating bucket / shower-type spray head located at the top of the prilling tower. The bucket rotates at high speed, spraying the urease inhibitor-urea molten composition in the form of droplets. The liquid droplets solidify and cool as they free-fall within the tower against the forced or natural updraft of ambient air. The product is discharged from the bottom of the tower onto a conveyor belt. Cooling to ambient temperature and screening may be used before transferring the product to storage. There are two different types of prilling towers: fluidized bed and non-fluidized bed. A major difference is that producing agricultural-grade prill in a non-fluidized bed prilling tower may require a separate solids cooling operation.
[0134] The methods disclosed herein are not limited to the aforementioned methods for preparing solid fertilizer granules or prills, and those skilled in the art will generally be familiar with any variations of the methods disclosed herein, in which the disclosed urease inhibitor composition or formulation may be used as an additive for preparing the disclosed urea-containing granules or urea-containing prills that have been pre-injected with the disclosed urease inhibitor composition.
[0135] In other words, please understand that this disclosure is not limited to the specific embodiments described and is naturally subject to change. Also, please understand that the terms used herein are intended solely to describe specific embodiments and are not intended to limit them. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this disclosure pertains.
[0136] As will be apparent to those skilled in the art who have read this disclosure, each individual embodiment described and illustrated herein has separate components and features that can be easily separated from or combined with any of the features of several other embodiments without departing from the scope or spirit of this disclosure. Any of the listed methods may be performed in the order listed or in any other logically possible order.
[0137] Unless otherwise indicated, this disclosure is not limited to specific materials, reagents, reactants, or production processes, and should therefore be understood to be subject to change. Furthermore, the terms used herein are intended solely to describe specific embodiments and are not intended to limit them. Also, in this disclosure, each step may be performed in a different order, wherever logically possible.
[0138] Specific embodiments of the subject matter described herein include: 1. Antioxidants and, Chaotropic agents and A composition containing the following: 2. The composition according to Embodiment 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, dozin, guanidinium chloride, guanidinium thiocyanate, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, and combinations thereof. 3. The composition according to Embodiment 1 or Embodiment 2, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, monoethanolamine borate, thiourea, and guanidinam chloride. 4. The composition according to any one of the embodiments, wherein the antioxidant and the chaotropic agent are present in a molar ratio of about 1:2 to about 2:1. 5. Contains an antioxidant selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. The composition inhibits urease enzyme activity. 6. The composition according to any one of Embodiments 1 to 4, wherein the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. 7. The composition according to any one of the embodiments, wherein the antioxidant is tert-butylhydroquinone (tBHQ). 8. The composition according to any one of the embodiments, wherein the composition is in solid form. 9. The composition according to Embodiment 8, wherein the composition is in the form of a powder. 10. The composition according to any one of Embodiments 1 to 7, wherein the composition is in liquid form. 11. The composition according to Embodiment 10, wherein the composition further comprises an organic solvent. 12. The composition according to Embodiment 11, wherein the organic solvent is selected from the group consisting of dimethyl sulfoxide, sulfolane, DMF, DMPU, NMP, and combinations thereof. 13. The composition according to any one of the embodiments, wherein the composition is used in a method or process for preparing a urea-containing powder, granules, prill, or liquid formulation. 14. The composition according to any one of the embodiments, wherein the composition inhibits urease enzyme activity. 15. Granules or prill containing urea, It contains a urease inhibitor component, The urease inhibitor component is an antioxidant, or the composition described in any one of embodiments 1 to 4 and 6 to 14. The antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof, in the form of an agricultural chemical product. 16. The agricultural product according to Embodiment 15, wherein the urease inhibitor component is in liquid form. 17. The agricultural product according to Embodiment 16, wherein the urease inhibitor component is tBHQ and contains no organic solvent. 18. The agricultural product according to any one of embodiments 15 to 17, wherein the urease inhibitor component is sprayed onto the surface of the granules or prill. 19. The agricultural product according to Embodiment 15, wherein the urease inhibitor component is in solid form and adheres to the surface of the granules or prill. 20. The agricultural product according to any one of the embodiments, wherein the urease inhibitor component is present in an amount of about 0.001% to about 10% by weight, based on the total weight of the agricultural product. 21. The agricultural product according to Embodiment 15, wherein the urease inhibitor component is pre-injected into the granules or prill. 22. The agricultural product according to Embodiment 21, wherein the weight ratio of urea to urease inhibitor components present in the granules or prill is about 1:10 to about 10:1. 23. Contacting the antioxidant with the chaotropic agent, A method for producing the composition according to any one of embodiments 1 to 4 and 6 to 14, including the above. 24. The method according to Embodiment 23, wherein the contact step includes crushing, grinding, or a combination thereof. 25. The method according to Embodiment 23, wherein the contact step includes a solvent. 26. A method for producing urea-containing granules or urea-containing prill coated with the composition or formulation described in any one of the embodiments, To obtain urea-containing granules or urea-containing prill, A method comprising spraying the composition or formulation described in any one of the embodiments onto the surface of the urea-containing granules or urea-containing prill. 27. A method for producing granules or prills containing urea and one composition from Embodiments 1 to 16, To obtain a urea molten product, The urea molten material is brought into contact with one of the compositions from Embodiments 1 to 16 to obtain a mixture. A method comprising cooling the mixture to obtain the granules or prills. 28. The method according to Embodiment 27, wherein the method includes a pre-ring tower. 29. The method according to Embodiment 27, wherein the method includes a granulator. 30. A method for improving plant growth and / or health, comprising applying the composition or agricultural product described in any one of the embodiments described above to the soil. 31. The method according to Embodiment 30, wherein the composition described in any one of Embodiments 1 to 16 or the agricultural product described in any one of Embodiments 17 to 23 is applied to the soil before the emergence of the crop plant. 32. The method according to Embodiment 31, wherein the composition or agricultural product is applied to soil adjacent to a crop plant, the base of the crop plant, or the root zone of the crop plant. 33. The method according to Embodiment 31 or Embodiment 32, wherein the crop plant is selected from the group consisting of cereals, wheat, barley, oats, rye, rice, maize, soybeans, potatoes, vegetables, peanuts, cotton, oilseed crops, grapes, and fruit plants. 34. The method according to Embodiment 30, wherein the application step includes contacting the composition or agricultural product at a rate of about 5 lbs to about 30 lbs per acre. 35. The method according to Embodiment 30, wherein the composition or agricultural product is used in an amount ranging from about 25 to about 300 kg / ha. 36. A method for reducing atmospheric ammonia and / or nitrification, comprising applying the composition described in any one of the embodiments above to an area affected by ammonia generation and / or nitrification. 37. A method for suppressing soil conditions selected from the group consisting of nitrification process, urease activity, and combinations thereof, comprising applying an effective amount of the composition or agricultural product described in any one of the embodiments to the soil. [Examples]
[0139] Please understand that the following examples are provided for illustrative purposes only and are not limiting to any one of them.
[0140] Example 1: Screening of urease inhibitor compositions We evaluated antioxidants in combination with chaotropic agents. The test samples were as follows:
[0141] Treatment 2 involved MgCl2 and tBHQ in a 1:1 molar ratio. Both chemicals were in powder form and were ground together by grinding with stainless steel beads. Process 3 - MEA borate and tBHQ in a 1:1 molar ratio. tBHQ powder was added to a MEA borate solution in a 1:1 molar ratio while stirring, and then ground using stainless steel beads. Treatment 4 involved guanidinium chloride and tBHQ in a 1:1 molar ratio. Both chemicals were in powder form and were ground together by grinding with stainless steel beads. Process 5 – Thiourea and tBHQ. Both chemicals were in powder form and were ground together by grinding with stainless steel beads.
[0142] Each of the above-mentioned samples was incorporated into the urea by grinding urea granules and the treatment samples together at a concentration of 1% by weight relative to the urea. The final product was in powder form containing 99% urea and 1% of each candidate treatment sample. This pre-incorporated urea powder was then used in a Dräger tube test. The results are shown below. [Table 2]
[0143] Treatment 2 was used as the positive control. This is the Agrotain product commercially available from Koch, containing NBPT as a urease inhibitor. Five replicate tests were performed for each sample. Treatment 1 was either a negative control or untreated bare ground.
[0144] The values in the table above represent NH3 equivalent emissions captured at specific times during the test. The unit of measurement is ppm. All four pulverized samples presented in this disclosure exceeded industry standards. Graphs of these results are shown in Figures 1A-1D. Results from various treatments, excluding Treatment 1, are found in Figures 2A-2D (i.e., the values for the control soil were subtracted from the control commercial product (Agrotain) and various treatments, and the differences were plotted).
[0145] Example 2: Screening of urease inhibitor-urea compositions The antioxidant tBHQ, combined with urea, was evaluated in a study. The test samples were as follows: 1) Treatment 7 is the untreated control (without urea). 2) Process 8 is pulverized urea. 3) Treatment 9 is an Agrotain control (Agrotain is a Koch product and is an industry-recognized NBPT-containing urease inhibitor product). 4) Treatment 10 is tBHQ (in DMSO-xylene; internal control). 5) Processing 11 0.5% pulverized urea-tBHQ 6) Processing 12 1% pulverized urea-tBHQ 7) Processing 13 1.5% pulverized urea-tBHQ 8) Processing 14 5% pulverized urea-tBHQ
[0146] The urea granules and the treated sample were ground together in an amount that resulted in the treated sample being present in the urea by weight percentage as shown above, thereby incorporating each of the samples into the urea. The final product was a mixture in powder form. Next, this pre-incorporated urea powder was used in a Dräger tube test. The results are shown in Figures 3A to 3E. [Table 3-1] [Table 3-2] [Table 3-3]
[0147] Graphs of these results are shown in Figures 3A to 3E. The results from various processes, excluding process 7, can be found in Figures 4A to 4E.
[0148] Example 3: Dräger Test Tube Protocol A Dräger tube protocol was developed, using soil samples from the NCSU Ag Research Facility in Oxford, North Carolina. Samples were prepared by co-dissolving them in a suitable solvent and rotating them in a sample turner at ambient temperature for 2–4 hours, after which they were allowed to stand over the weekend to ensure no turbidity and / or precipitation occurred. Typical sample sizes were 4–4.5 g in 12 mL cylindrical glass vials. These clear (sometimes light pink) solutions were added to urea prill at 3 qt / ton (L, for lower concentrations) and 6 qt / ton (H, for higher concentrations). The measurements were plotted as graphs. In the graphs, time was the independent variable, and NH3 was recorded on the y-axis (on the Dräger linear scale), typically yielding an "S" shaped graph. Samples were stored at ambient temperature for 6 months (or 12 months) to check for the occurrence of precipitation, thickening, or turbidity.
Claims
1. Antioxidants, Chaotropic agents and A composition containing the following:
2. The composition according to claim 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, sodium perchlorate, sodium bromide, sodium trifluoroacetate, sodium thiocyanate, sodium trichloroacetate, dozin, guanidinium chloride, guanidinium thiocyanate, lithium perchlorate, lithium acetate, monoethanolamine borate, phenol, sodium dodecyl sulfate, thiourea, urea, and combinations thereof.
3. The composition according to claim 1, wherein the chaotropic agent is selected from the group consisting of magnesium chloride, monoethanolamine borate, thiourea, and guanidinium chloride.
4. The composition according to claim 1 or 2, wherein the antioxidant and the chaotropic agent are present in a molar ratio of about 1:2 to about 2:
1.
5. The antioxidant comprises an antioxidant selected from the group consisting of trt-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof. The composition inhibits urease enzyme activity.
6. The composition according to claim 1 or 2, wherein the antioxidant is selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.
7. The composition according to any one of claims 1, 2, or 5, wherein the antioxidant is tert-butylhydroquinone (tBHQ).
8. The composition according to claim 1 or 5, wherein the composition is in solid form.
9. The composition according to claim 8, wherein the composition is in the form of a powder.
10. The composition according to claim 1 or 5, wherein the composition is in liquid form.
11. The composition according to claim 10, further comprising an organic solvent.
12. The composition according to claim 11, wherein the organic solvent is selected from the group consisting of dimethyl sulfoxide, sulfolane, DMF, DMPU, NMP, and combinations thereof.
13. The composition according to claim 1 or 5, wherein the composition is used in a method or process for preparing a urea-containing powder, granules, prill, or liquid formulation.
14. The composition according to claim 1 or 5, wherein the composition inhibits urease enzyme activity.
15. It comprises granules or prill containing urea and a urease inhibitor component, The urease inhibitor component is an antioxidant or the composition of claim 1. The antioxidant is an agricultural product selected from the group consisting of tert-butylhydroquinone (tBHQ), p-hydroxybenzyl alcohol (HBA), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, ascorbic acid, tocopherol, 2,4-di-tert-butylphenol (DBP), 2,6-di-tert-butyl-p-benzoquinone (BHT-Q), and combinations thereof.
16. The agricultural product according to claim 15, wherein the urease inhibitor component is in liquid form.
17. The agricultural product according to claim 16, wherein the urease inhibitor component is tBHQ and does not contain any organic solvent.
18. The agricultural product according to any one of claims 15 to 17, wherein the urease inhibitor component is sprayed onto the surface of the granules or prill.
19. The agricultural product according to claim 15, wherein the urease inhibitor component is in solid form and adheres to the surface of the granules or prill.
20. The agricultural product according to claim 15, wherein the urease inhibitor component is present in an amount of about 0.001% to about 10% by weight, based on the total weight of the agricultural product.
21. The agricultural product according to claim 15, wherein the urease inhibitor component is pre-injected into the granules or prill.
22. The agricultural product according to claim 21, wherein the weight ratio of urea to urease inhibitor components present in the granules or prill is about 1:10 to about 10:
1.
23. The antioxidant is brought into contact with the chaotropic agent. A method for producing the composition according to claim 1, which includes the composition described in claim 1.
24. The method according to claim 23, wherein the contact step includes crushing, grinding, or a combination thereof.
25. The method according to claim 23, wherein the contact step includes a solvent.
26. A method for producing urea-containing granules or urea-containing prill coated with the composition described in claim 1 or 5, To obtain urea-containing granules or urea-containing prill, A method comprising spraying the composition according to claim 1 or 5 onto the surface of the urea-containing granules or urea-containing prill.
27. A method for producing granules or prill containing urea and the composition of claim 1 or 5, To obtain a urea molten product, The urea molten material is brought into contact with the composition of claim 1 or 5 to obtain a mixture, A method comprising cooling the mixture to obtain the granules or prills.
28. The method according to claim 27, wherein the method includes a pre-ring tower.
29. The method according to claim 27, wherein the method includes a granulator.
30. A method for improving plant growth and / or health, comprising applying the composition according to claim 1 or 5 to the soil.
31. The method according to claim 30, wherein the composition is applied to the soil before the emergence of crop plants.
32. The method according to claim 31, wherein the composition is applied to soil adjacent to a crop plant, the base of the crop plant, or the root zone of the crop plant.
33. The method according to claim 31 or 32, wherein the crop plant is selected from the group consisting of cereals, wheat, barley, oats, rye, rice, corn, soybeans, potatoes, vegetables, peanuts, cotton, oilseed crops, grapes, and fruit trees.
34. The method according to claim 30, wherein the application step includes contacting the composition at a rate of about 5 lbs to about 30 lbs per acre.
35. The method according to claim 30, wherein the composition is used in an amount ranging from about 25 to about 300 kg / ha.
36. A method for reducing atmospheric ammonia and / or nitrification, comprising applying the composition according to claim 1 or 5 to an area affected by ammonia generation and / or nitrification.
37. A method for suppressing soil conditions selected from the group consisting of nitrification processes, urease activity, and combinations thereof, comprising applying an effective amount of the composition described in claim 1 or 5 to the soil.
