Soil conditioning dispersible particles

Abstract

Soil conditioning dispersible particles are disclosed that include at least one metal oxide domain and at least one nutrient domain. The at least one metal oxide domain and the at least one nutrient domain are present in the soil conditioning dispersible particle as different domains aggregated together. The soil conditioning dispersible particles are free of phosphorus. The invention further discloses soil conditioning dispersible particles. Wherein the at least one metal oxide domain comprises at least one metal oxide selected from the group consisting of alumina, alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, bauxite, alumina trihydrate, alumina monohydrate, boehmite, pseudo-boehmite, gibbsite, diaspore, and combinations thereof, and at least one nutrient domain includes a nutrient selected from the group consisting of bioavailable substances: molybdenum, selenium, zinc, copper, cobalt, iron, nickel, manganese, vanadium, calcium, potassium, sulfur, chlorine, silicon, magnesium, sodium, nitrogen, boron, and combinations thereof.

Description

[0001] Related Applications

[0002] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 62 / 350,176, filed on June 8, 2022, entitled “Soil Regulation Dispersible Granules,” which is incorporated herein by reference in its entirety. Technical Field

[0003] The present application relates to soil conditioning dispersible granules. In particular, the present application relates to soil conditioning dispersible granules having metal oxides and nutrients and being free of phosphorus. Background Art

[0004] In agricultural systems, ensuring that crops receive an adequate supply of plant nutrients is critical to maximizing yields. However, soil systems are imperfect in providing nutrients to plants through their root systems, and many plant nutrients cannot be absorbed by plants because they are bound to soil particles, carried away by surface runoff, or leached into groundwater courses. To combat undesirable nutrient-soil outcomes, agronomists typically work to increase the cation and anion exchange capacity of soils to ensure a dynamic ionic environment.

[0005] Sulfur is an essential plant nutrient that is almost entirely consumed by plant roots as sulfate (SO4 2- ) in soils with sufficient organic matter. Although sulfur is generally abundant in soils with sufficient organic matter, many common soil conditions ensure that only a small fraction of sulfur is available in soluble, plant-available forms. In general, sulfur cycles between organic and inorganic forms through the processes of activation, fixation, mineralization, oxidation, and reduction. Of the two forms, inorganic sulfur is the more mobile, with sulfate (SO4 2- ) is the most mobile ion. The mobility of sulfate in soil is limited by adsorption processes, where adsorption and desorption are mainly controlled by the sulfate concentration in the soil solution, the soil pH, the colloidal surface properties, and the presence of other anions in the solution. Isotopic studies have shown that sulfate ions in soil solution are in kinetic equilibrium with sulfate ions adsorbed on the soil solid phase. The adsorption of sulfate is pH-dependent, with maximum adsorption achieved at pH 3 and rapidly decreasing with increasing pH, becoming negligible at pH values ​​above 6.5. In addition, sulfate is considered to be weakly adsorbed to soils, and anions such as OH - and H2PO4 – Easier to adsorb than sulfate.

[0006] In recent decades, sulfur deficiency has been considered a limiting factor in crop production worldwide. The reduction of sulfur dioxide emissions and the routine use of high-analysis low-sulfur fertilizers are one of the reasons for sulfur deficiency observed in crops. In order to manage sulfur deficiency, several inorganic sulfur fertilizers (e.g., ammonium sulfate, ammonium thiosulfate, potassium sulfate, magnesium sulfate, etc.) are applied to agricultural soils. Sulfate in sulfur fertilizers has the advantage of being absorbed by plant roots immediately after dissolution. However, most of the relatively large doses of sulfate released into the soil solution in a short period of time are leached into the soil profile outside the plant root zone. Many current sulfur fertilizer formulations are designed to create a slow-release sulfur system. These systems generally involve controlling the dissolution kinetics of sulfur by changing the chemical form of sulfur or by using a particle coating to delay sulfur from entering the soil solution phase. Although these measures prevent the immediate increase in sulfur effectiveness occasionally observed when using standard sulfur fertilizers, these measures cannot provide sulfur to the soil solution phase during periods of high crop demand, nor can they store sulfur during periods of low crop demand. The best sulfur-buffered agricultural soil will match sulfur effectiveness with crop demand through rhizosphere-responsive sulfur adsorption behavior.

[0007] A relatively new commercial soil amendment, activated alumina, regulates available P levels in soils through a pH-dependent and concentration-dependent adsorption mechanism. However, this adsorption-based buffering capacity has not been considered or applied to the management of other anionic plant nutrients. Summary of the invention

[0008] In an exemplary embodiment, the soil conditioning dispersible particle includes at least one metal oxide domain and at least one nutrient domain. The at least one metal oxide domain and the at least one nutrient domain are present in the soil conditioning dispersible particle as distinct domains aggregated together. The soil conditioning dispersible particle does not contain phosphorus.

[0009] In another exemplary embodiment, the soil conditioning dispersible particle includes at least one metal oxide domain and at least one nutrient domain. The at least one metal oxide domain includes at least one metal oxide selected from the group consisting of: alumina, alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, bauxite, trihydrated alumina, monohydrated alumina, boehmite, pseudoboehmite, gibbsite, diaspore, and combinations thereof. The at least one nutrient domain includes nutrients selected from the group consisting of the following bioavailable substances: molybdenum, selenium, zinc, copper, cobalt, iron, nickel, manganese, vanadium, calcium, potassium, sulfur, chlorine, silicon, magnesium, sodium, nitrogen, boron, and combinations thereof. The at least one metal oxide domain and the at least one nutrient domain are present in the soil conditioning dispersible particle as distinct domains clustered together. The soil conditioning dispersible particle does not contain phosphorus. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] These and other features, aspects and advantages of the present subject matter will become better understood when the following detailed description is read with reference to the accompanying drawings, in which:

[0011] Figure 1 is a schematic cross-sectional view of bonded dispersible particles according to an embodiment of the present disclosure.

[0012] FIG. 2 is a graphical comparison of corn yields (bushels per acre) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments in 2021 at different aluminum oxide levels (lbs per acre).

[0013] 3 is a graphical comparison of corn and soybean yields (bushels per acre) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments in 2022 at different aluminum oxide levels (lbs per acre).

[0014] 4 is a graphical comparison of corn ear leaf sulfur concentration (%) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments at different aluminum oxide levels (lbs / acre) in 2021.

[0015] 5 is a graphical comparison of corn and soybean ear-level leaf sulfur concentrations (%) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments at various 2022 aluminum oxide levels (lbs / acre).

[0016] 6 is a graphical comparison of leaf aluminum concentrations (%) at the cob level for 2021 corn at different aluminum oxide levels (lbs / acre) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments.

[0017] 7 is a graphical comparison of corn and soybean ear leaf aluminum concentrations (%) for (A) poultry litter treatments; (B) granular MAP treatments; and (C) powdered MAP treatments at different aluminum oxide levels (lbs / acre) in 2022.

[0018] 8 is a graphical comparison of soil sulfur concentrations (ppm) at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth at different aluminum oxide levels (lbs / acre) in 2021.

[0019] 9 is a graphical comparison of soil sulfur concentrations (ppm) at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth for different aluminum oxide levels (lbs / acre) in 2022.

[0020] 10 is a graphical comparison of soil aluminum concentrations (ppm) at different aluminum oxide levels (lbs / acre) in 2021 at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth.

[0021] 11 is a graphical comparison of soil aluminum concentrations (ppm) at different aluminum oxide levels (lbs / acre) in 2022 at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth.

[0022] 12 is a graphical comparison of soil Mehlich-3-aluminum concentrations (ppm) at different aluminum oxide levels (lbs / acre) in 2021 at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth.

[0023] 13 is a graphical comparison of soil Mehlich-3-aluminum concentrations (ppm) at different aluminum oxide levels (lbs / acre) in 2022 at (A) 0-3 inches soil depth; (B) 3-6 inches soil depth; and (C) 6-12 inches soil depth.

[0024] Fig.14 is a graphical comparison of sulfur released into a distilled water reservoir over time from ammonium sulfate granules versus co-granulated aluminum oxide and ammonium sulfate granules.

[0025] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same parts. DETAILED DESCRIPTION

[0026] Disclosed herein are dispersible particles of soil conditioning without phosphorus with metal oxide and nutrients.Compared with particles lacking one or more features of the disclosure, embodiments of the disclosure have higher production efficiency, larger particle crushing strength, less metal oxide: the particle intergranular variability of nutrient weight ratio, interaction between metal oxide and nutrient domain of improvement, improved metal oxide surface area and activity, moisture content of reduction, higher hygroscopic stability or its combination.These dispersible particles of soil conditioning can adsorb and desorb anionic plant nutrients, such as sulphur, molybdenum, nitrogen, boron and chlorine, and reduce their release rate.Supplying anionic nutrients uninterruptedly can improve the overall health of plants, and reducing plants is the needs of these nutrients distribution energy.The energy demand reduced prompts redundant energy to be applied to other plant needs, improves other plant characteristics and behaviors, such as cationic nutrients absorption.

[0027] Certain anions exhibit pH-dependent adsorption and desorption behavior toward metal oxides. Co-addition of metal oxides in fertilizers can improve crop access to anionic plant nutrients, thereby reducing plant stress and reducing the energy allocation required for nutrient acquisition. In turn, these benefits to crops enable improved uptake of cationic nutrients as increased plant energy reserves may be diverted toward these activities. On a per-acre basis, fertilizer requirements could be reduced, improving the sustainability profile of agricultural activities. With reduced fertilizer use, runoff and leaching could be reduced, global fertilizer supplies could be extended, and the life of fertilizer mines could be extended.

[0028] As used herein, "about" means a deviation of up to 10% from the value so modified. All values ​​modified with "about" are also intended to convey the unmodified value as an alternative, thus, for example, "about 10 μm" discloses a range of 9-11 μm as well as specifically 10 μm.

[0029] As used herein, "free of phosphorus" means that phosphorus is absent except for trace incidental impurities at concentrations too low to have any substantial effect on the properties or behavior of the soil conditioning dispersible particles. The maximum level of such trace incidental impurities of phosphorus is a P2O5 level of less than 1.0 weight percent.

[0030] As used herein, "bonded" dispersible particles differ from typical "agglomerated" dispersible particles in that "agglomerated" refers to particles formed by mechanically agglomerating at least two types of preformed particles together, while "bonded" refers to particles formed by agglomerating one type of preformed particles with a second material domain formed simultaneously. The structural differences between bonded dispersible particles and agglomerated dispersible particles include, but are not limited to, particle crushing strength, abrasion resistance, moisture content, hygroscopic stability, inter-particle variability of metal oxide: nutrient weight ratio, contact surface area between metal oxide and nutrient domain resulting in tighter bonding, metal oxide surface area, binder incorporation, degree of mixed domains, or a combination thereof.

[0031] refer to Figure 1 In one embodiment, the soil conditioning dispersible granule 1 includes at least one metal oxide domain 2 and at least one nutrient domain 3. The at least one metal oxide domain 2 and the at least one nutrient domain 3 are present in the soil conditioning dispersible granule 1 as distinct domains that are aggregated together. The soil conditioning dispersible granule 1 does not contain phosphorus. Relative to an otherwise identical comparative soil conditioning composition having mixed (but not co-granulated) metal oxide particles and nutrient particles, the adsorption ratio of anionic plant nutrients on the metal oxide of the soil conditioning dispersible granule 1 can be increased due to the improved soil placement proximity of the metal oxide and the nutrient in the soil conditioning dispersible granule 1 compared to the comparative soil conditioning composition.

[0032] The presence of at least one metal oxide domain 2 and at least one nutrient domain 3 in the soil conditioning dispersible granule 1 can slow down the release of at least one nutrient from the soil conditioning dispersible granule 1. In one embodiment, aluminum oxide as the at least one metal oxide domain 2 reduces the release rate of sulfur as ammonium sulfate as the at least one nutrient domain 3 from the soil conditioning dispersible granule 1.

[0033] The soil conditioning dispersible particles 1 may be agglomerated dispersible particles or bonded dispersible particles ( Figure 1 ). The bonded dispersible particles may have a reduced inter-particle variability in the metal oxide:nutrient weight ratio compared to the agglomerated dispersible particles, or the inter-particle variability in the metal oxide:nutrient weight ratio is reduced by 5%, or by 10%, or by 15%, or by 20%, or by 25%. In one embodiment, the bonded dispersible particles have an inter-particle variability in the metal oxide:nutrient weight ratio of ±40%, or ±35%, or ±30%, or ±25%, or ±20%, or ±15%. As used herein, the inter-particle variability is measured relative to the smaller components of the metal oxide and the nutrient, as measured by the average value of the entire bonded dispersible particles, so that if the average metal oxide:nutrient weight ratio is 50:50, the inter-particle variability is ±40%, and the metal oxide:nutrient weight ratio can be in the range of 30:70 to 70:30. As a further explanation, if the metal oxide:nutrient weight ratio averages 25:75 and the intergranularity is ±40%, then the metal oxide:phosphate weight ratio may range from 15:85 to 35:65.

[0034] The bonded dispersible particles can have a bonded dispersible particle crush strength greater than the agglomerated dispersible particles. In one embodiment, the bonded dispersible particles have a bonded dispersible particle crush strength of at least 3 lbf, or at least 3.5 lbf, or at least 4 lbf, or at least 4.5 lbf, or at least 5 lbf. The crush strength is measured by placing the particles on a steel surface and slowly applying more weight / pressure to the particles until the particles crack / break (IFDC S-115 procedure in the Fertilizer Physical Property Determination Handbook).

[0035] The at least one metal oxide domain 2 and the at least one nutrient domain 3 of the soil conditioning dispersible particle 1 can be uniformly or non-uniformly distributed in the soil conditioning dispersible particle 1 within the particle. The at least one metal oxide domain 2 and the at least one nutrient domain 3 of the soil conditioning dispersible particle 1 can be uniformly or non-uniformly distributed in the soil conditioning dispersible particle 1 between particles.

[0036] In one embodiment, each of the at least one metal oxide domain 2 is surrounded by at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99%, or completely surrounded by at least one nutrient domain 3. The degree of surrounding can be measured by energy dispersive x-ray spectroscopy combined with scanning electron microscopy.

[0037] Dispersible particles 1 may include at least one of a water-soluble binder, a suspending agent or an emulsifier. In one embodiment, dispersible particles 1 include 1-40% by weight, or 5-35% by weight, or 5-15% by weight, or 10-20% by weight, or 15-25% by weight, or 20-30% by weight, or 25-35% by weight, or any sub-range or combination thereof of a water-soluble binder. Suitable water-soluble binders include, but are not limited to, calcium lignin sulfonate, ammonium lignin sulfonate, or a combination thereof. Suitable suspending agents include, but are not limited to, polysaccharides, inorganic salts, carbomers, or a combination thereof. Suitable emulsifiers include, but are not limited to, plant derivatives such as acacia, tragacanth, agar, pectin, carrageenan or lecithin, animal derivatives such as gelatin, lanolin or cholesterol, semi-synthetic agents such as methylcellulose or carboxymethylcellulose, synthetic agents such as benzalkonium chloride, benzethonium chloride, alkaline soaps (including sodium oleate or potassium oleate), amine soaps (including triethanolamine stearate), detergents (including sodium lauryl sulfate, dioctyl sodium sulfosuccinate or docusate sodium), sorbitan esters, polyethylene oxide derivatives of sorbitan esters, glycerides, or combinations thereof.

[0038] The soil conditioning dispersible granule 1 may further include at least one additional domain present as a different domain. The at least one additional domain may include at least one pesticide domain, at least one biological additive domain, or a combination thereof. The at least one additional domain may aggregate with the at least one metal oxide domain 2 and the at least one nutrient domain 3 by mechanical or bonding agglomeration, may be coated on the soil conditioning dispersible granule 1, mixed with the soil conditioning dispersible granule 1, or a combination thereof.

[0039] At least one suitable pesticide domain includes but is not limited to herbicides, insecticides, fungicides, nematicides or combinations thereof. Suitable herbicides include but are not limited to sulfonylureas, HPPD inhibitors, chloroacetamides, PPO inhibitors, phenylureas, triazines or combinations thereof. Suitable insecticides include but are not limited to organophosphates, ureas, pyrethrins, neonicotinoids, spinosins, indoxacarb, diamides or combinations thereof. Suitable fungicides include but are not limited to strobilurines, pyrimidines, triazoles, dicarboximides or combinations thereof. Suitable nematicides include but are not limited to avermectins, carbamates, organophosphates or combinations thereof.

[0040] Suitable at least one biological additive domain includes but is not limited to at least one additive selected from the group consisting of humus, fulvic acid, live microorganisms, microbial metabolites, plant extracts, exogenous plant hormones and combinations thereof. Any suitable modification of the preparation containing humic acid or fulvic acid or any material derived from organic matter and containing multiple humic acid and / or fulvic acid species can be used. Microorganisms may include but are not limited to Rhodopseudomonas spp., Bacillus spp., Pseudomonas spp., Saccharomyces spp., Aspergillus spp., Candida spp., Streptococcus spp., Lactobacillus spp. or combinations thereof. Plant extracts may include, but are not limited to, plant hormones, quinols, plastoquinones, flavonoids, plant growth promoting metabolites, or combinations thereof. Exogenous plant hormones may include, but are not limited to, IDAA, gibberellins, abscisic acid, auxins, jasmonates, brassinosteroids, cytokinins, salicylic acid, or combinations thereof.

[0041] The dispersible particles 1 may further include mineral particles. The mineral particles may be mechanically or adhesively agglomerated in the dispersible particles 1, agglomerated with the dispersible particles 1, or mixed with the adhesively bonded dispersible particles 1.

[0042] In one embodiment, the dispersible granule 1 comprises 5-80 wt% metal oxide domains, 10-95 wt% nutrient domains, and optionally, 1-50 wt% water-soluble binder, or 30-40 wt% metal oxide domains, 30-40 wt% nutrient domains, and 20-40 wt% water-soluble binder, or 35 wt% metal oxide domains, 35 wt% nutrient domains, and 30 wt% water-soluble binder. In another embodiment, the bonded dispersible granule 1 comprises 5-70 wt% metal oxide domains, 10-70 wt% nutrient domains, up to 50 wt% water-soluble binder, and up to 20 wt% surfactant and emulsifier combination, or consists of 5-50 wt% metal oxide domains, 10-50 wt% nutrient domains, up to 50 wt% water-soluble binder, and up to 5 wt% surfactant and emulsifier combination.

[0043] The dispersible particles 1 can have any suitable size (measured by diameter based on the median value within the sample). Suitable sizes of the dispersible particles 1 can include, but are not limited to, about 0.4 mm to about 4.0 mm, or about 0.4 mm to about 1.2 mm, or about 0.9 mm to about 1.5 mm, or about 1.2 mm to about 1.8 mm, or about 1.5 mm to about 2.1 mm, or about 1.8 mm to about 2.4 mm, or about 2.1 mm to about 2.7 mm, or about 2.4 mm to about 3.0 mm, or about 2.7 mm to about 3.3 mm, or about 3.0 mm to about 3.6 mm, or about 3.3 mm to about 4.0 mm, or about 0.4 mm, or about 0.5 mm, or about 0.6 mm, or about 0.7 mm, or about 0.8 mm, or about 0.9 mm, or about 1.0 mm, or about 1.1 mm, or about 1. .2mm, or about 1.3mm, or about 1.4mm, or about 1.5mm, or about 1.6mm, or about 1.7mm, or about 1.8mm, or about 1.9mm, or about 2.0mm, or about 2.1mm, or about 2.2mm, or about 2.3mm, or about 2.4mm, or about 2.5mm, or about 2.6mm, or about 2.7mm, or about 2.8mm, or about 2.9mm, or about 3.0mm, or about 3.1mm, or about 3.2mm, or about 3.3mm, or about 3.4mm, or about 3.5mm, or about 3.6mm, or about 3.7mm, or about 3.8mm, or about 3.9mm, or about 4.0mm, or any subrange or combination thereof. In one non-limiting example, golf greens may use dispersible particles of about 0.5mm to about 0.8mm. In another non-limiting example, corn can use about 2.4 mm dispersible particles 1 by broadcast application. In a third non-limiting example, any crop applied with a strip tiller can use about 1.5 mm dispersible particles 1. In one embodiment, suitably, for example, for application as a suspension, the dispersible particles 1 are micronized and have a particle size of less than about 200 μm, or less than about 150 μm, or less than about 100 μm, or less than about 75 μm, or less than about 50 μm, or less than about 25 μm, or less than about 10 μm, or less than about 5 μm, or less than about 2 μm, or less than about 1 μm, or less than about 0.75 μm, or less than about 0.5 μm, or less than about 0.25 μm, or less than about 0.1 μm, or less than about 0.05 μm, or less than about 0.01 μm as measured by the maximum particle size.

[0044] The metal oxide of at least one metal oxide domain 2 may include an activated metal oxide. The metal oxide may be activated by calcination, acid treatment or a combination thereof.

[0045] The metal oxide of at least one metal oxide domain 2 can be any suitable metal oxide, including but not limited to alumina, α-alumina, β-alumina, γ-alumina, δ-alumina, bauxite, trihydrated alumina, monohydrated alumina, boehmite, pseudoboehmite, gibbsite, diaspore, iron oxide, hematite, hematite, magnetite, goethite, iron hydroxide, calcium oxide, calcium hydroxide, copper oxide, magnesium oxide, manganese oxide, manganese dioxide, nickel oxide, silicon dioxide and zinc oxide, or a combination thereof. As used herein, "metal oxide" is understood to include metal oxide hydrates and metal oxide hydroxides.

[0046] The nutrients of the at least one nutrient domain 3 may be any suitable nutrients, including but not limited to one of the following bioavailable substances: molybdenum, selenium, zinc, copper, cobalt, iron, nickel, manganese, vanadium, calcium, potassium, sulfur, chlorine, silicon, magnesium, sodium, nitrogen, boron or a combination thereof. The bioavailable substances of the above nutrients include but are not limited to, MoO2 – 、SeO2 – 、Zn 2+ 、ZnCl – 、CuCO3、Co 2+ , Fe 2 + , Fe 3+ 、Ni 2+ 、NiCl + , Mn 2+ 、MnCl + 、HVO4 2– , Ca 2+ 、K+、SO4 2– , Cl – 、SiOH4、Mg 2+ 、Na + NH 4+ 、NO3 – , H3BO3 and B4O7 2– .

[0047] The weight ratio of metal oxide to nutrient in the soil conditioning dispersible granules can be any suitable weight ratio, including but not limited to a weight ratio of 10:1 to 1:10, or 8:1 to 1:8, or 7:1 to 1:7, or 6:1 to 1:6, or 5:1 to 1:5, or 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, or 3:1 to 1:1, or 1:1 to 1:3, or about 2:1, or about 1:1, or about 1:2, or any sub-range or combination of ranges thereof.

[0048] The metal oxide domains 2 may have any suitable size. In one embodiment, in order to maintain the adsorption capacity for nutrients and optimize the size of penetration through the soil profile by surface application, the preferred size of the metal oxide domains 2 is less than about 300 μm, or less than about 150 μm, or less than about 100 μm, or less than about 75 μm, or less than about 50 μm, or less than about 25 μm, or less, or any sub-range or combination thereof.

[0049] The soil conditioning dispersible granules 1 can be applied to the field as a soil conditioner together with plant nutrients, or co-granulated with one or more plant nutrients into a single composite granule and applied to the field. The soil conditioning dispersible granules 1 can be used as soil conditioners (buggers) for nutrients instead of soil improvers. The soil conditioning dispersible granules 1 can be used as soil improvers and granular fertilizer formulations, for example, in high-cost markets such as agriculture or forestry.

[0050] experiment

[0051] In the first study (Study 1), the potential of metal oxides to influence or regulate nutrients other than phosphorus was unexpectedly demonstrated. In the second study (Study 2), the combination of metal oxides with ammonium sulfate in a single particle was examined.

[0052] Study 1: Regulation of non-phosphorus nutrients by metal oxides

[0053] The effects of a single, no-till application of aluminum oxide on nutrient uptake in corn were tested in a split-plot experimental design at Penn State University over the next two years. A full factorial experiment (16 treatments total) was conducted with four poultry litter application rates (0, 2, 4, and 6 tons / acre) and four aluminum oxide application rates (0, 600, 1,200, and 2,400 pounds / acre), each replicated four times. Both poultry litter and aluminum oxide applications were applied once in the spring of 2021, but the effects on crop yield, soil properties, and crop nutrient uptake were measured in the fall of 2021 and 2022.

[0054] Two additional experiments were conducted simultaneously in which monoammonium phosphate ("MAP") was applied to plots in place of poultry litter, one with granular MAP and one with MAP powder. In these trials, corn was the 2021 investigation crop and soybeans were the 2022 rotation and field trial crop.

[0055] Soil sampling and analysis

[0056] At the beginning of the season, two soil samples were collected from each plot: one representing the top 0-6 inches of soil and the other representing the soil at a depth of 6-12 inches. At the end of each growing season, three soil samples were collected: one representing the soil at a depth of 0-3 inches, one representing the soil at a depth of 3-6 inches, and one representing the soil at a depth of 6-12 inches. Soil Mehlich 3-S was performed on all soil samples to measure the available sulfur concentration in the soil. In addition, total aluminum and available aluminum (Soil Mehlich-3-Al) concentrations were measured for all samples to determine if the alumina application increased the adverse effects of aluminum ion toxicity on the soil. The Soil Mehlich 3 test was performed by acid extraction of the soil at pH 2.5, which combined acetic acid (CH3COOH), ammonium nitrate (NH4NO3), ammonium fluoride (NH4F), nitric acid (HNO3), and ethylenediaminetetraacetic acid (EDTA). These tests were performed at a contract research laboratory and determined by ion conductivity plasma mass spectrometry.

[0057] Corn tissue sampling

[0058] Crop tissue earleaf sampling was obtained from representative plants in each plot after corn reached the R3 stage in both the 2021 and 2022 growing seasons. Both sulfur and aluminum content were measured in each sample.

[0059] result

[0060] The results of the study indicate that the application of alumina increased corn yield in the year of application, with no adverse effect on yield in the following season. By reducing sulfur leaching in the soil, the application of alumina increased sulfur retention over multiple growing seasons. This increased sulfur retention results in greater sulfur uptake by the crop, even throughout the season after application. Although the application of alumina increased the total aluminum concentration of the soil after application, no significant effect on increasing ionic aluminum concentration in the soil was observed. Without being bound by theory, it is believed that the lack of significant effect on increasing aluminum ion concentration in the soil may be due to the inherent chemically stable structure of alumina and other metal oxides.

[0061] Referring to Figure 2, there are no statistically significant differences in the means associated with the same plots for corn yield at various alumina application rates and (A) poultry litter treatments, (B) granular MAP treatments, and (C) powdered MAP treatments measured in 2021. The numerical and statistical differences between plots with and without alumina treatments indicate that alumina has a positive impact on corn yield.

[0062] Referring to Figure 3, there were no statistically significant differences in the means associated with the different treatments for corn yield at various alumina application rates and for the (A) poultry litter treatment, (B) granular MAP treatment, and (C) powder MAP treatments measured in 2022 after treatment in 2021. The lack of statistical differences between treatments after one year suggests that high-level alumina applications had no seasonal effect on corn yield.

[0063] Referring to Figure 4, there are no statistically significant differences in the mean values ​​associated with the same plots for R3 corn ear leaf sulfur concentrations measured at various alumina application rates and in the (A) poultry litter treatment, (B) granular MAP treatment, and (C) powdered MAP treatments in 2021. The numerical values ​​and statistical differences between plots indicate that alumina application increased sulfur uptake by corn.

[0064] Referring to Figure 5, there were no statistically significant differences in the mean values ​​associated with the different treatments for R3 corn ear-level leaf sulfur concentrations measured in 2022 at different alumina application rates and for the (A) poultry litter treatment, (B) granular MAP treatment, and (C) powdered MAP treatments after treatment in 2021. There were no statistical differences between the different treatments after one year, indicating that alumina application had minimal seasonal effects on corn sulfur uptake.

[0065] Referring to Figure 6, there were no statistically significant differences in the mean values ​​associated with the different treatments for R3 corn ear leaf aluminum concentrations at various alumina application rates and (A) poultry litter treatment, (B) granular MAP treatment, and (C) powdered MAP treatment measured in 2021. The lack of statistical differences between the different treatments suggests that there was no change in aluminum absorption despite the high alumina application rates.

[0066] Referring to Figure 7, regarding the leaf aluminum concentrations at the ear position of R3 corn at different alumina application rates and (A) poultry litter treatment, (B) granular MAP treatment, and (C) powdered MAP treatment measured in 2022 after treatment in 2021, the means associated with the different treatments one year later were not statistically different. The lack of statistical differences between the groups suggests that there was no change in aluminum absorption despite the large amount of alumina applied in the previous growing season.

[0067] Referring to Figure 8, there are no statistically significant differences in the mean values ​​associated with the same plots for corn soil sulfur concentrations measured at various alumina application rates and at (A) 0-3 inch soil depths, (B) 3-6 inch soil depths, and (C) 6-12 inch soil depths in 2021. The statistical differences between those plots that received the alumina application treatments and those that did not receive any alumina application suggest that alumina reduced soil sulfur leaching throughout the growing season.

[0068] Referring to Figure 9, the means associated with the same letter were not statistically different with respect to corn soil sulfur concentrations measured in 2022 at various alumina application rates and at (A) 0-3 inch soil depth, (B) 3-6 inch soil depth, and (C) 6-12 inch soil depth following the 2021 treatment. The statistical differences between those plots that received the alumina application treatment and those that did not receive any alumina application indicate that alumina successfully reduced soil sulfur leaching throughout the 2021 growing season and promoted higher soil sulfur concentrations throughout the 2022 growing season.

[0069] Referring to Figure 10, there are no statistically significant differences in the mean values ​​associated with the same plots with respect to corn soil aluminum concentrations at various alumina application rates and at (A) 0-3 inch soil depths, (B) 3-6 inch soil depths, and (C) 6-12 inch soil depths measured in 2021. The difference in values ​​between those plots that received the alumina application treatment and those that did not receive any alumina application indicates that the addition of alumina to the soil increased the concentration of aluminum in the soil.

[0070] Referring to Figure 11, the means associated with the same plots were not statistically different with respect to the different alumina application rates and corn soil aluminum concentrations at (A) 0-3 inch soil depth, (B) 3-6 inch soil depth, and (C) 6-12 inch soil depth measured in 2022 after treatment in 2021. Although not significant, the difference in values ​​between plots that received the alumina application treatment and plots that did not receive any alumina application suggests that the addition of alumina to the soil increased the concentration of aluminum in the soil, even one year after application.

[0071] Referring to Figure 12, the means associated with the same letter were not statistically different with respect to corn soil Mehlich-3-Al concentrations at various Alumina application rates and (A) 0-3 inch soil depth, (B) 3-6 inch soil depth, and (C) 6-12 inch soil depth measured in 2021. The lack of statistical differences between plots that received Alumina application treatments and plots that did not receive any Alumina application treatments indicates that despite the increase in total soil Al concentrations, no significant increase in ionic Al concentrations was observed.

[0072] Referring to Figure 13, the means associated with the same plots were not statistically different for different alumina application rates and corn soil Mehlich-3-Al concentrations at (A) 0-3 inch soil depth, (B) 3-6 inch soil depth, and (C) 6-12 inch soil depth measured in 2022 after treatment in 2021. There were no statistical differences between the plots that received the alumina application treatments and the plots that did not receive any alumina application treatments, indicating that despite the increase in total soil Al concentrations, no significant increase in Al ion concentrations was observed in the next growing season after the application.

[0073] Study 2: Metal oxides combined with ammonium sulfate into a single particle

[0074] Alumina powder (-100 US mesh) was co-granulated with ammonium sulfate (21-0-0-24SNPKS) powder in a 1:1 alumina:ammonium sulfate weight ratio using ammonium lignin sulfonate binder to produce a 9-0-0-10S NPKS product. Sulfur release profiles were obtained by placing a specified weight of pellets (0.3 g sulfur) into 50 mL of deionized water and monitoring the sulfate concentration in the water storage tank at specified time points. Aliquots of the liquid were removed and replaced from the liquid container at regular time points. The sulfate concentration in the aliquots was determined spectrophotometrically to determine sulfate release following the protocol outlined in EPA-165-C Rev. 2A Sulfate Determination Method. The method involves measuring the concentration turbidimetrically using barium chloride and a suspending agent.

[0075] refer to Fig.14 The release of sulfur from ammonium sulfate ("AMS") pellets and co-granulated alumina and ammonium sulfate ("alumina-S") pellets over time showed that the incorporation of alumina controlled the release of sulfur and prolonged the release time.

[0076] Although the foregoing description illustrates and describes exemplary embodiments, it will be appreciated by those skilled in the art that various changes may be made and equivalents may be substituted for its elements without departing from the scope of the present invention. In addition, many modifications may be made to adapt specific situations or materials to the teachings of the present invention without departing from the basic scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed as the best mode for carrying out the present invention, and the present invention will include all embodiments falling within the scope of the appended claims.

Claims

1. A soil conditioning dispersible granule comprising: at least one metal oxide domain; and at least one nutrient domain, in: The at least one metal oxide domain and the at least one nutrient domain are present in the soil conditioning dispersible particle as distinct domains aggregated together; and The soil conditioning dispersible granules contain no phosphorus.

2. The soil conditioning dispersible granules of claim 1, wherein the soil conditioning dispersible granules are bonded dispersible granules.

3. The soil conditioning dispersible granule of claim 2, wherein the bonded dispersible granule has a particle-to-particle variability of metal oxide:nutrient weight ratio of ±40% and a bonded dispersible granule crush strength of at least 3 lbf.

4. The soil conditioning dispersible particle of claim 1, wherein the at least one metal oxide domain comprises an activated metal oxide domain.

5. The soil conditioning dispersible particle of claim 1, wherein the at least one metal oxide domain comprises at least one metal oxide selected from the group consisting of alumina, alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, bauxite, alumina trihydrate, alumina monohydrate, boehmite, pseudoboehmite, gibbsite, diaspore, iron oxides, hematite, magmasite, magnetite, goethite, iron hydroxide, calcium oxide, calcium hydroxide, copper oxide, magnesium oxide, manganese oxide, manganese dioxide, nickel oxide, silicon dioxide, zinc oxide, and combinations thereof.

6. The soil conditioning dispersible particle of claim 5, wherein the at least one metal oxide domain comprises a metal oxide selected from the group consisting of alumina, alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, bauxite, alumina trihydrate, alumina monohydrate, boehmite, pseudoboehmite, gibbsite, diaspore, and combinations thereof.

7. The soil conditioning dispersible particle of claim 6, wherein the at least one metal oxide domain further comprises at least one additional metal oxide selected from the group consisting of iron oxides, hematite, maghemite, magnetite, goethite, iron hydroxides, and combinations thereof.

8. The soil conditioning dispersible granule of claim 7, wherein the at least one metal oxide domain further comprises at least one additional metal oxide selected from the group consisting of calcium oxide, calcium hydroxide, copper oxide, magnesium oxide, manganese oxide, manganese dioxide, nickel oxide, silicon dioxide, zinc oxide, and combinations thereof.

9. The soil conditioning dispersible granule of claim 6, wherein the at least one metal oxide domain further comprises at least one additional metal oxide selected from the group consisting of calcium oxide, calcium hydroxide, copper oxide, magnesium oxide, manganese oxide, manganese dioxide, nickel oxide, silicon dioxide, zinc oxide, and combinations thereof.

10. The soil conditioning dispersible granule of claim 1, wherein the nutrient domain comprises nutrients selected from the group consisting of the following bioavailable substances: molybdenum, selenium, zinc, copper, cobalt, iron, nickel, manganese, vanadium, calcium, potassium, sulfur, chlorine, silicon, magnesium, sodium, nitrogen, boron, and combinations thereof.

11. The soil conditioning dispersible granule of claim 10, wherein the nutrient domain comprises a bioavailable form of molybdenum.

12. The soil conditioning dispersible granule of claim 10, wherein the nutrient domain comprises a bioavailable form of sulfur.

13. The soil conditioning dispersible particle of claim 1, wherein the at least one metal oxide domain and the at least one nutrient domain are uniformly distributed within the particle in the soil conditioning dispersible particle.

14. The soil conditioning dispersible granule of claim 1, wherein the at least one metal oxide domain and the at least one nutrient domain are uniformly distributed among the particles in the soil conditioning dispersible granule.

15. The soil conditioning dispersible granule of claim 1, wherein at least 80% of the at least one metal oxide domain is surrounded by the at least one nutrient domain.

16. The soil conditioning dispersible granule of claim 1 having a weight ratio of metal oxide:nutrient in the range of 10:1 to 1:

10.

17. The soil conditioning dispersible granule of claim 1, further comprising at least one additional domain as a different domain, wherein the at least one additional domain is selected from the group consisting of at least one pesticide domain, at least one biological additive domain, and combinations thereof.

18. A soil conditioning dispersible granule comprising: at least one metal oxide domain comprising at least one metal oxide selected from the group consisting of alumina, alpha-alumina, beta-alumina, gamma-alumina, delta-alumina, bauxite, alumina trihydrate, alumina monohydrate, boehmite, pseudoboehmite, gibbsite, diaspore, and combinations thereof; and at least one nutrient domain comprising nutrients selected from the group consisting of bioavailable substances: molybdenum, selenium, zinc, copper, cobalt, iron, nickel, manganese, vanadium, calcium, potassium, sulfur, chlorine, silicon, magnesium, sodium, nitrogen, boron, and combinations thereof, in: The at least one metal oxide domain and the at least one nutrient domain are present in the soil conditioning dispersible particle as distinct domains aggregated together; and The soil conditioning dispersible granules contain no phosphorus.

19. The soil conditioning dispersible particle of claim 18, wherein the at least one metal oxide domain further comprises at least one additional metal oxide selected from the group consisting of iron oxides, hematite, maghemite, magnetite, goethite, iron hydroxides, and combinations thereof.

20. The soil conditioning dispersible particle of claim 18, wherein the at least one metal oxide domain is an activated metal oxide domain.

Images