Fertilizers containing urea, ammonium sulfate, and calcium carbonate and methods for producing and using the same

Abstract

A composition containing urea, ammonium sulfate, and calcium carbonate and methods for making and using the same are disclosed. The composition may contain a core-shell structure, the core may include at least portion of solidified fertilizer melt and the shell may include at least a portion of ammonium sulfate and calcium carbonate.

Description

DESCRIPTION FERTILIZERS CONTAINING UREA, AMMONIUM SULFATE, AND CALCIUM CARBONATE AND METHODS FOR PRODUCING AND USING THE SAME CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to European Application No. 24200629.4. filed September 16, 2024, the contents of which is incorporated into the present application be reference in its entirety. BACKGROUND OF THE INVENTION A. Field of the Invention

[0002] The invention generally concerns a composition containing urea, ammonium sulfate, and calcium carbonate and methods of making and using the same. B. Background

[0003] Soil nutrients, such as nitrogen, phosphorus, potassium, and sulfur, as well as trace elements such as iron, zinc, copper, and magnesium, are useful for achieving thriving agriculture and growth of plants. Upon repeated planting cycles, the quantity of these nutrients in the soil may be depleted, resulting in inhibited plant growth and decreased production. To counter this effect, fertilizers have been developed to help replace the depleted vital nutrients. Single-nutrient fertilizers and multi-nutrient fertilizers, such as fertilizer blends, have been developed to meet the varied needs of crop production worldwide.

[0004] Mixing of fertilizer ingredients (e.g., urea, potassium compounds, calcium compounds, phosphorous compounds, etc.) can result in the production of fertilizers having a large number of ratios of primary nutrient contents. However, bulk blending is only a practical proposition as long as the fertilizer materials are stable when in contact with each other in the blended fertilizer. Urea (CH4N2O) is a compound that contains nitrogen and is widely used as a nitrogen source in fertilizers; however, urea undesirably reacts with compounds such as hydrates of calcium phosphate and sulfate and organic fertilizers. These reactions can produce water that liquefies solid granules or dry mixture products, which299518500.1 - 1 -causes clumping and loss of product and increases the rate at which these undesirable reactions take place. See Biskupski et al. (EP 2,774,907); see also Achard et al. (US 5,409,516). Further, the production of water increases the amount of water that has to be removed during production of urea containing fertilizers, making these blended fertilizers more difficult and expensive to make. See Schwob (FR 2,684,372). Further, in urea production process, oversize, undersize, and powder urea can be challenging and costly to cycle it back in the system. Also, rapid hydrolysis and nitrification of urea in the soil can cause loss of nitrogen from urea.

[0005] There is a continued need to provide low cost, stable, multi-nutrient fertilizer products.

[0006] Further, over the past decade, the world has become more conscious of the adverse effects on the environment posed by disposing industrial processing wastes such as waste gypsums like phosphogypsum (PG) or red gypsum (RG). Waste gypsums have been disposed by stacking on land or discharge to the sea. However, both methods of disposal have possible adverse environmental effects.

[0007] Reduction of CO2 emission is also presently among the top priorities of many industries. Chemical utilization of CO2through its reduction to CO and involvement of chemical reactions requires excessive consumption of energy. That is one of the reasons why, presently, many chemical companies have made significant efforts to reduce CO2 emission by storing CO2in underground deep storage.

[0008] There is a need for additional ways to reduce CO2as well as reduce waste gypsums. SUMMARY OF THE INVENTION

[0009] A discovery has been made that addresses at least some of the needs for combinations of plant nutrients in a single fertilizer or single fertilizer blend. The discovery is premised on using a urea, ammonium sulfate, and calcium carbonate in a composition, such as a fertilizer. The composition can have a core-shell structure and / or can contain amounts of nutrients that are helpful to plants, such as 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate based on the weight of the composition. For example, the composition can be formed by contacting an ammonium299518500.1 - 2 -sulfate and calcium carbonate with molten urea, the combination can be solidified, and / or the solidified combination can be contacted with additional ammonium sulfate and calcium carbonate to form the composition. The ammonium sulfate and calcium carbonate and / or the additional ammonium sulfate and calcium carbonate may be in the form of a gel. The gel in some instances, may not contain another solvent other than water. Use of such a gel can decrease costs and environmental impact of using an organic solvent. These compositions can contain particular amounts of the ingredients therein, such as 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate based on the weight of the composition. The composition can, in some instances, supply nitrogen in two or more of uric (NH2) and ammoniacal (NH3) forms. Further the composition can be beneficial to provide the desired nutrients in a slow release application. The compositions and methods provide a way to valorize low cost, low value materials and produce a composition for crop nutrition, with the added benefit of being slow release while providing Ca for enhanced crop nutrition.

[0010] In one aspect, a method of making the composition, such as in the form of a fertilizer granule, is described. In some aspects, the method may include the steps of, (a) contacting an ammonium sulfate and calcium carbonate with molten urea to produce a product, (b) allowing the product to solidify to form a solidified product, and (c) contacting the solidified product with additional ammonium sulfate and additional calcium carbonate to form the composition.

[0011] In some aspects, the composition formed may contain a core-shell structure. In some aspects, the composition may include 60 wt.% to 75 wt.% urea, or at least any one of, at most any one of, equal to any one of, or between any two of 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, or 75 wt.% urea, or any range thereof, based on the weight of the composition. In some aspects, the composition may include 20 wt.% to 30 wt.% ammonium sulfate, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.% ammonium sulfate, or any range thereof, based on the weight of the composition. In some aspects, the composition may include 5 wt.% to 10 wt.% calcium carbonate, or at least any one of, at most any one of, equal to any one of, or between any two299518500.1 - 3 -of 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% calcium carbonate, or any range thereof, based on the weight of the composition.

[0012] In some aspects, the composition may contain a core-shell structure. In some aspects, the core may contain a solidified fertilizer melt, ammonium sulfate, and calcium carbonate and the shell may contain ammonium sulfate and calcium carbonate. In some instances ammonium sulfate and calcium carbonate are homogeneously distributed throughout the solidified fertilizer melt. In some instances, the solidified fertilizer melt may be a solidified urea melt. In some aspects, step (a) may include contacting molten urea with ammonium sulfate and calcium carbonate. In some instances, the ammonium sulfate and calcium carbonate can be in the form of a gel. In some aspects, step (c) may include granulating the solidified product with the additional ammonium sulfate and the additional calcium carbonate to form the composition, such as a fertilizer granule. In some instances, the additional ammonium sulfate and calcium carbonate can be in the form of a gel. In some instances, the additional ammonium sulfate and calcium carbonate do not contain a solvent other than optionally water when contacting the solidified product. In some aspects, step (c) may further include drying.

[0013] In some aspects, the composition may include 20 wt.% to 46 wt.% nitrogen, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, or 35 wt.% 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, or 46 wt.% nitrogen based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 0.5 wt.% to 11 wt.% sulfur, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, or 11 wt.% sulfur based on the total weight of the composition, or any range thereof. In some aspects, the composition may include more than 0 wt.% calcium to 10 wt.% calcium, or at least any one of, at most any one of, equal to any one of, or between any two of 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, or 2.5 wt.% calcium based on the total weight of the composition, or any range thereof. In some instances, the weight ratios of nitrogen to sulfur to calcium of the compositions may include299518500.1 - 4 -N:S:Ca product composition weight ratios of 45.5:0.5:0; 35.3:10:0.8; and 23.1:7.5:2.4, such as 20 to 46:0.5 to 11:0 to 10 or any range or number therein.

[0014] In some instances, at least a portion of the molten urea may include recycled urea. In some instances, at least a portion of the ammonium sulfate may be from an ammonia production plant. In some instances, at least a portion of the ammonium sulfate may be a byproduct from a caprolactam production plant. In some instances at least a portion of the calcium carbonate can be mined chalk, limestone, and / or marble.

[0015] In some instances, the method may further include reacting calcium sulfate, CO2, and a source of ammonia to produce at least a portion of the ammonium sulfate and / or at least a portion of the calcium carbonate. In some instances, the source of ammonia may include ammonia gas and / or ammonium hydroxide. In some instances, the ammonium sulfate can be produced by utilization of waste gypsum and / or CO2 from a decarbonization source. In some instances, the waste gypsum is red gypsum, phosphogypsum, and / or flue gas gypsum. In some instances, the method reduces the environmental impact and / or reduces waste, such as carbon emissions and gypsums from an industrial source.

[0016] In some instances, step (a) may be performed at a temperature of 120 °C to 150 °C, or at least any one of, at most any one of, equal to any one of, or between any two of temperatures such as 120 °C, 121 °C, 122 °C, 123 °C , 124 °C, 125 °C, 126 °C, 127 °C, 128 °C, 129 °C, 130 °C, 131 °C, 132 °C, 133 °C, 134 °C, 135 °C, 136 °C, 137 °C, 138 °C, 139 °C, 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C, or 150 °C, or any range thereof. In some instances, step (a) may be performed at a pressure of 1 bar to 10 bar, or at least any one of, at most any one of, equal to any one of, or between any two of pressures such as 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, or 10 bar, or any range thereof.

[0017] In some instances, the composition can be dried to form a solid composition, such as a solid fertilizer composition. The composition can be a granule, powder, pellet, etc.

[0018] In another aspect of the invention, a composition is described herein. In some aspects, the composition may include urea, ammonium sulfate, and calcium carbonate. In some aspects, the composition may contain a core-shell structure. In some aspects, the composition may include 60 wt.% to 75 wt.% urea, or at least any one of, at most any one of, equal to any one of, or between any two of 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65299518500.1 - 5 -wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, or 75 wt.% urea based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 20 wt.% to 30 wt.% ammonium sulfate, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.% ammonium sulfate based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 5 wt.% to 10 wt.% calcium carbonate, or at least any one of, at most any one of, equal to any one of, or between any two of 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% calcium carbonate based on the total weight of the composition, or any range thereof.

[0019] In some aspects, the composition may include 20 wt.% to 46 wt.% nitrogen, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, or 35 wt.% 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, or 46 wt.% nitrogen based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 0.5 wt.% to 11 wt.% sulfur, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, or 11 wt.% sulfur based on the total weight of the composition, or any range thereof. In some aspects, the composition may include just over 0 wt.% calcium to 10 wt.% calcium, or at least any one of, at most any one of, equal to any one of, or between any two of 0.1 wt. %, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, or 2.5 wt.% calcium based on the total weight of the composition, or any range thereof. In some instances, the weight ratios of nitrogen to sulfur to calcium of the compositions may include N:S:Ca product composition weight ratios of 45.5:0.5:0; 35.3:10:0.8; and 23.1:7.5:2.4, such as 20 to 46:0.5 to 11:0 to 10 or any range or number therein

[0020] In some aspects, the composition may contain a core-shell structure. In some aspects, the core may contain a solidified fertilizer melt, ammonium sulfate, and calcium carbonate, and the shell may contain ammonium sulfate and calcium carbonate. In some instances the ammonium sulfate and calcium carbonate are homogeneously distributed299518500.1 - 6 -throughout the solidified fertilizer melt. In some instances, the solidified fertilizer melt can be a solidified urea melt.

[0021] Also disclosed are the following Aspects 1 to 15 of the present invention.

[0022] Aspect 1 is a method of making a fertilizer granule, the method comprising the steps of: (a) contacting an ammonium sulfate and calcium carbonate with molten urea to produce a product; (b) allowing the product to solidify to form a solidified product; and (c) contacting the solidified product with additional ammonium sulfate and additional calcium carbonate to form the fertilizer granule, wherein: the fertilizer granule formed comprises a core-shell structure; and / or the fertilizer granule comprises 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate.

[0023] Aspect 2 is the method of aspect 1, wherein the fertilizer granule formed comprises a core-shell structure, the core comprising the solidified product and the shell comprising ammonium sulfate and calcium carbonate.

[0024] Aspect 3 is the method of any one of aspects 1 to 2, wherein step (a) comprises contacting the molten urea with a gel comprising ammonium sulfate and calcium carbonate.

[0025] Aspect 4 is the method of any one of aspects 1 to 3, wherein the contacting in step (c) comprises granulating the solidified product with the additional ammonium sulfate and the additional calcium carbonate to form the fertilizer granule and / or step (c) further comprises drying.

[0026] Aspect 5 is the method of any one of aspects 1 to 4, wherein the fertilizer granule comprises 20 wt.% to 46 wt.% nitrogen, 0.5 wt.% to 10 wt.% sulfur, and 0.5 wt.% to 2.5 wt.% calcium.

[0027] Aspect 6 is the method of any one of aspects 1 to 5, wherein at least a portion of the molten urea comprises recycled urea.299518500.1 - 7 -

[0028] Aspect 7 is the method of any one of aspects 1 to 6, wherein at least a portion of the ammonium sulfate is from an ammonia production plant and / or at least a portion of the ammonium sulfate is a byproduct from a caprolactam production plant.

[0029] Aspect 8 is the method of any one of aspects 1 to 7, wherein at least a portion of the calcium carbonate is mined chalk, limestone, and / or marble.

[0030] Aspect 9 is the method of any one of aspects 1 to 8, wherein the method further comprises reacting calcium sulfate, CO2, and a source of ammonia to produce at least a portion of the ammonium sulfate and / or at least a portion of the calcium carbonate.

[0031] Aspect 10 is the method of aspect 9, wherein the source of ammonia comprises ammonia gas and / or ammonium hydroxide.

[0032] Aspect 11 is the method of any one of aspects 9 or 10, wherein the ammonium sulfate is produced by utilization of waste gypsum and / or CO2 from a decarbonization source.

[0033] Aspect 12 is the method of aspect 11, wherein the waste gypsum is red gypsum, phosphogypsum, and / or flue gas gypsum.

[0034] Aspect 13 is the method of any one of aspects 1 to 12, wherein step (a) is performed at a temperature of 120 °C to 150 °C and / or a pressure of 1 bar to 10 bar.

[0035] Aspect 14 is a fertilizer composition comprising urea, ammonium sulfate, and calcium carbonate, wherein: the fertilizer comprises a core-shell structure; and / or the fertilizer comprises 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate.

[0036] Aspect 15 is the fertilizer composition of aspect 14, comprising: 20 wt.% to 46 wt.% nitrogen, 0.5 wt.% to 10 wt.% sulfur, and 0.5 wt.% to 2.5 wt.% calcium; and / or a core-shell structure, the core comprising a solidified fertilizer melt and the shell comprising ammonium sulfate and calcium carbonate.299518500.1 - 8 -

[0037] The following includes definitions of various terms and phrases used throughout this specification.

[0038] The term “fertilizer” is defined as a material applied to soils or to plant tissues to supply one or more plant nutrients essential or beneficial to the growth of plants and / or stimulants or enhancers to increase or enhance plant growth. Non-limiting examples of fertilizers include materials having one or more of urea, ammonium nitrate, calcium ammonium nitrate, one or more superphosphates, binary NP fertilizers, binary NK fertilizers, binary PK fertilizers, NPK fertilizers, molybdenum, zinc, copper, boron, cobalt, and / or iron. In some aspects, fertilizers include agents that enhance plant growth and / or enhance the ability for a plant to receive the benefit of a fertilizer, such as, but not limited to biostimulants, urease inhibitors, and nitrification inhibitors.

[0039] The term “micronutrient” is defined as a chemical element or substance required in trace amounts for the normal growth and development of a plant. Non-limiting examples of micronutrients include B, Cu, Fe, Mn, Mo, Zn, Se, and Si or compounds thereof.

[0040] The term “secondary nutrient” is defined as a chemical element or substance required in moderate amounts for plant growth and are less likely to limit crop growth in comparison to N, P, and K. Non-limiting examples of secondary nutrients include Ca, Mg, and S or combinations thereof.

[0041] The term “organic agent” is defined as a substance that is produced by or part of an organism. Non-limiting examples of organic agents suitable for a fertilizer include neem oil, seaweed extract, bio-stimulants, char, ashes from incineration of animal waste or animal tissues, and diatomaceous earth.

[0042] The term “granule” can include a solid material. A granule can have a variety of different shapes, non-limiting examples of which include a spherical, a puck, an oval, a rod, an oblong, or an amorphous shape.

[0043] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.299518500.1 - 9 -

[0044] The terms “wt.%,” “vol.%,” or “mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams total of the material is 10 wt.% of component.

[0045] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0046] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and / or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0047] The term “free moisture content,” as the term used in this specification and / or claims means the water or moisture not associated with calcium sulfate dihydrate or hemihydrate. This term means any other free water or moisture.

[0048] The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0049] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0050] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”), or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0051] The composition of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase “consisting essentially of,” in one non-limiting aspect, a basic and novel characteristic of the composition of the present299518500.1 - 10 -invention is the presence of a stable composition and / or the presence of a composition product of combining urea, (NH4)2SO4, and CaCO3. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0053] THE FIGURE is a schematic of a method and / or a system that can be used to produce a composition in which urea, ammonium sulfate, and calcium carbonate can be used as starting materials.

[0054] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale. DETAILED DESCRIPTION OF THE INVENTION

[0055] A discovery has been made that provides for a stable composition containing urea. The composition can be designed to provide the ideal amount of nutrients for plants, regions, and / or soils. Notably, the compositions are storage stable. For example the composition can reduce or avoid instances of the formation of water produced during storage by unwanted chemical reactions within the compositions and / or fertilizer blends of the present invention.

[0056] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections. A. Method of Making the Composition

[0057] A method of making a composition may use a system / method shown in THE FIGURE. The method and / or the system can be a continuous process capable of handling gels, liquids, slurries, powders, solids, or a process capable of blending solid fertilizers. The system can include a mixing zone (mixing) (102), a melting zone (104), a combination zone (106), and / or a granulator (108). The mixing zone (102) can include a mixing unit. The mixing unit can be a continuous stirred-tank reactor. In the mixing zone (102), ammonium sulfate (101) and calcium carbonate (103), and optionally water (not shown) can be combined299518500.1 - 11 -in a mixing unit (e.g., a continuous stirred-tank reactor) to form a ammonium sulfate-calcium carbonate gel (105). Urea powder and / or urea solid can be used as the urea (107), and can be introduced to the melting zone (104) to generate a molten urea (109). Additionally or alternatively, at least some portion of ammonium sulfate-calcium carbonate gel (105) can be injected to the combination zone (106) where the generated molten urea (109) present at a temperature of 120-150oC are combined to form a product. In some instances, the product is solidified to form a solidified product (111). In some instances, the method may uses heat from the molten urea to drive off any water associated with the ammonium sulfate-calcium carbonate gel (105), thus reducing energy consumption during preparation of the product. In some instances, the gel is pre-mixed with urea in the form of powder. In some instances, the solidified product (111) is contacted with additional ammonium sulfate and additional calcium carbonate (105) to form a fertilizer granule (113). Optionally, the granulator (108) may be used for granulating the solidified product (111) with the additional ammonium sulfate and the additional calcium carbonate to form a fertilizer granule with a core-shell structure (113). In some instances, the other remaining portion of ammonium sulfate-calcium carbonate gel (105) can be added during granulation, and serves as a coating agent to the granulated material. In some instances, coating during the granulation process may be carried out at about 90°C, and without use of any solvent to add the ammonium sulfate and calcium carbonate, except for water. The granulation process in the granulator (108) can be at 80 °C to 100 °C, preferably 80 °C to 95 °C, or at least, equal to, or between any two of 80 °C, 85 °C, 90 °C, 95 °C, and 100 °C, or any range thereof. In some instances, the granulation step further includes drying.

[0058] In some instances, the combination zone step (106) may be performed at a temperature of 120 °C to 150 °C, or at least any one of, at most any one of, equal to any one of, or between any two of temperatures such as 120 °C, 121 °C, 122 °C, 123 °C , 124 °C, 125 °C, 126 °C, 127 °C, 128 °C, 129 °C, 130 °C, 131 °C, 132 °C, 133 °C, 134 °C, 135 °C, 136 °C, 137 °C, 138 °C, 139 °C, 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C, or 150 °C, or any range thereof. In some instances, the combination zone step may be performed at a pressure of 1 bar to 10 bar, or at least any one of, at most any one of, equal to any one of, or between any two of pressures such as 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, or 10 bar, or any range thereof.299518500.1 - 12 -

[0059] In some instances, at least a portion of the molten urea may include recycled urea. In some instances, at least a portion of the ammonium sulfate may be from an ammonia production plant. In some instances, at least a portion of the ammonium sulfate may be a byproduct from a caprolactam production plant. In some instances at least a portion of the calcium carbonate can be mined chalk, limestone, and / or marble.

[0060] In some instances, the method may further include reacting calcium sulfate, CO2, and a source of ammonia to produce at least a portion of the ammonium sulfate and / or at least a portion of the calcium carbonate. In some instances, the source of ammonia may include ammonia gas and / or ammonium hydroxide. In some instances, the ammonium sulfate can be produced by utilization of waste gypsum and / or CO2from a decarbonization source. In some instances, the waste gypsum is red gypsum, phosphogypsum, and / or flue gas gypsum. In some instances, the method reduces the environmental impact and / or reduces waste, such as carbon emissions and gypsums from an industrial source.

[0061] In some instances, urea, ammonium sulfate, and calcium carbonate can come from any source. In some instances, composition allows utilization of under-valued ammonium sulfate, calcium carbonate, and urea to produce mechanically stable, slow release, and / or high value fertilizers. In some instances, any additional active or inactive ingredients can be added to the method at any step. B. Compositions

[0062] In another aspect of the invention, a composition is described. In some aspects, the composition may include urea, ammonium sulfate, and calcium carbonate. In some aspects, the composition may contain a core-shell structure. In some aspects, the composition may include 60 wt.% to 75 wt.% urea, such as at least any one of, at most any one of, equal to any one of, or between any two of 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, or 75 wt.% urea based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 20 wt.% to 30 wt.% ammonium sulfate, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.% ammonium sulfate based on the total weight of the composition, or any range thereof. In some aspects, the composition may include 5 wt.% to 10 wt.% calcium carbonate, or at least299518500.1 - 13 -any one of, at most any one of, equal to any one of, or between any two of 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% calcium carbonate based on the total weight of the composition, or any range thereof.

[0063] In some aspects, the composition may include 20 wt.% to 46 wt.% nitrogen, or at least any one of, at most any one of, equal to any one of, or between any two of 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, or 35 wt.% 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, or 46 wt.% nitrogen, based on the weight of the composition, or any range thereof. In some aspects, the composition may include 0.5 wt.% to 11 wt.% sulfur, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, or 11 wt.% sulfur, based on the weight of the composition, or any range thereof. In some aspects, the composition may include just over 0 wt.% to 10 wt.% calcium, or at least any one of, at most any one of, equal to any one of, or between any two of 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, or 2.5 wt.% calcium, based on the weight of the composition, or any range thereof. In some instances, the weight ratios of nitrogen to sulfur to calcium of the compositions may include N:S:Ca product composition weight ratios of 45.5:0.5:0; 35.3:10:0.8; and 23.1:7.5:2.4, such as 20 to 46:0.5 to 11:0 to 10 or any range or number therein

[0064] In some aspects, the composition may contain a core-shell structure. In some aspects, the core may contain a solidified fertilizer melt and the shell may contain ammonium sulfate and calcium carbonate. In some instances, the core may include urea, ammonium sulfate, and / or calcium carbonate, or any combination thereof or all thereof. By way of non- limiting examples, at least a portion of the outer shell can be formed by ammonium sulfate and calcium carbonate. The granules can self-form or self-assemble during the production process of the composition.

[0065] The composition can be used alone or in combination with other fertilizer actives and micronutrients. The other fertilizer actives and micronutrients can be added with urea, ammonium sulfate, and / or calcium carbonate at the beginning of a granulation process, or a mixing or blending process, or at any later stage.299518500.1 - 14 -

[0066] Non-limiting examples of additional additives can be micronutrients, primary nutrients, and secondary nutrients. A micronutrient is a botanically acceptable form of an inorganic or organometallic compound such as boron, copper, iron, chloride, manganese, molybdenum, nickel, or zinc. A primary nutrient is a material that can deliver nitrogen, phosphorous, and / or potassium to a plant. Nitrogen-containing primary nutrients may include ammonium nitrate, diammonium phosphate, monoammonium phosphate, urea- formaldehyde, or combinations thereof. A secondary nutrient is a substance that can deliver calcium, magnesium, and / or sulfur to a plant. Secondary nutrients may include lime, superphosphate, or a combination thereof.

[0067] In one aspect, the composition can comprise one or more inhibitors. The inhibitor can be a urease inhibitor or a nitrification inhibitor, or a combination thereof. In one aspect, the composition can comprise a urease inhibitor and a nitrification inhibitor. In one aspect, the inhibitor can be a urease inhibitor. Suitable urease inhibitors include, but are not limited to, N-(n-butyl) thiophosphoric triamide (NBTPT) and phenylphosphorodiamidate (PPDA). In one aspect, the composition can comprise NBTPT or PPDA, or a combination thereof. In another aspect, the inhibitor can be a nitrification inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), 5-ethoxy-3- trichloromethyl-1,2,4-thiadiazol, which is sold under the tradename Terrazole®, by OHP Inc., USA, 2-amino 4-chloro 6-methyl pyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfanilamidothiazole (ST), and any combination thereof. In one aspect, nitrification inhibitor can comprise DMPP, DCD, TU, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4- thiadiazol, AM, MBT or ST, or a combination thereof. In one aspect, the composition can comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4- thiadiazol , AM, MBT, or ST or a combination thereof.

[0068] The composition produced can also contain low amounts of moisture. The free moisture content of the composition can be less than 1 wt.%, preferably less than 0.8 wt.%, less than 0.5 wt.%, or 0.25 wt.% to 0.7 wt.% water. In some instances, the free moisture content is 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, or 0 wt.%.

[0069] The composition can be comprised of one or more particles. A first portion of the particles can be the solidified urea melt containing ammonium sulfate and calcium carbonate distributed therein, and a second portion of the particles can be ammonium sulfate and299518500.1 - 15 -calcium carbonate that form a layer that covers at least a portion of the first portion of the particles. In certain non-limiting aspects, the first portion of the particles can have an average particle size of 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, or 4400 micrometers or any size there between or range thereof, and the second portion of the particles can have an average particle size of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 micrometers or any size there between or range thereof. The layer can be made up of particles of urea, particles of calcium carbonate, particles of ammonium sulfate, or any combination, or all thereof. In some embodiments, the smaller and larger particles can be elongated particles or can be substantially spherical particles or other shapes, or combinations of such shapes. Non-limiting examples of shapes include a spherical, a puck, an oval, a rod, an oblong, or a random shape.

[0070] The composition can be a granule and can have a crush strength of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 kg / granule, or more, or any amount there between or range thereof, preferably 2 kg / granule to 5 kg / granule.

[0071] An additional non-limiting benefit of the composition of the present invention is that it can be a good acidifier, which can contribute to efficient nutrient distribution to the soil and / or plants. Even further, the composition can increase nutrient uptake by the plants due, at least in part, to the acidic feature. In some particular aspects, the composition can have a pH of 3, 3.5, 4, 4.5, 5, 5.5, or 6, preferably 4 to 5 when mixed with water. In some instances, no acid is added to form the composition. Also, the composition of the present invention can have an average size of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 mm, preferably about 2 mm to 4 mm. It is also believed that the contents and / or structure of the composition of the present invention can aid in reducing nitrogen volatilization. C. Method of Using the Composition

[0072] The composition of the present invention can be used in methods of increasing the amount of nitrogen, sulfur, and / or calcium in soil and of enhancing plant growth. Such methods can include applying to the soil an effective amount of a fertilizer comprising the composition of the present invention. The method may include increasing the growth and299518500.1 - 16 -yield of crops, trees, ornamentals, etc. such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and soybeans. The method can include applying composition of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc.

[0073] Non-limiting examples of plants that can benefit from the composition of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and / or Pteridophytes. The Gymnosperms may include plants from the Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae, and Ginkgoaceae families. The Angiosperms may include plants from the Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Capparidaceae, Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae, Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Grossulariaceae, Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae, Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Muntingiaceae, Myoporaceae, Myricaceae, Myrsinaceae, Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oxalidaceae, Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporaceae, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Styracaceae, Surianaceae, Symplocaceae, Tamaricaceae, Theaceae, Theophrastaceae, Thymelaeaceae, Tiliaceae, Ulmaceae, Verbenaceae, and / or Vitaceae family.

[0074] The effectiveness of fertilizers comprising the composition of the present invention can be ascertained by measuring the amount of nutrients provided by the composition, such as nitrogen, sulfur, and / or calcium, in the soil at various times after applying the fertilizer composition to the soil. It is understood that different soils have different characteristics, which can affect the stability of the nitrogen in the soil. The effectiveness of a composition can also be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.299518500.1 - 17 -EXAMPLES

[0075] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results. Example 1 (Lab Scale Process to Prepare A Composition)

[0076] A lab scale process for making a composition containing urea, ammonium sulfate, and calcium carbonate was performed.

[0077] 40 g ammonium sulfate was dissolved in 100 ml of water to form a solution. The solution was stirred at 40oC for 30 min and 0.8 g calcium carbonate powder was then added to the solution to form a solution mixture. The solution was mixed for an hour, and the temperature of solution mixture was increased to 55oC until it formed a thick ammonium sulfate-calcium carbonate gel. The gel was slowly added to 53.4 g granular urea and mixed to create a homogeneous coat. The coated urea granules were dried at 60oC for 2 hours to form urea coated with ammonium sulfate and calcium carbonate. Example 2

[0078] The process was the same as in Example 1, but the amount of urea, ammonium sulfate and calcium carbonate used as a feed was different. In this example, 40 g ammonium sulfate and 0.8 g calcium carbonate plus 100 ml water were used to obtain the gel. The gel was used to coat 66 g urea. The coated urea granules were dried at 60oC for 2 hours to form urea coated with ammonium sulfate and calcium carbonate. Example 3 (Product Composition) Stable compositions may use recovered ammonium sulfate, calcium carbonate, and urea to produce N-S-Ca slow release fertilizers. The fertilizers may contain core-shell structures with three prophetic examples of fertilizers with the following N:S:Ca product composition weight ratios including 45.5:0.5:0; 35.3:10:0.8; and 23.1:7.5:2.4.299518500.1 - 18 -

Claims

CLAIMS 1. A method of making a fertilizer granule, the method comprising the steps of: (a) contacting an ammonium sulfate and calcium carbonate with molten urea to produce a product; (b) allowing the product to solidify to form a solidified product; and (c) contacting the solidified product with additional ammonium sulfate and additional calcium carbonate to form the fertilizer granule, wherein: the fertilizer granule formed comprises a core-shell structure; and / or the fertilizer granule comprises 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate.

2. The method of claim 1, wherein the fertilizer granule formed comprises a core-shell structure, the core comprising the solidified product and the shell comprising ammonium sulfate and calcium carbonate.

3. The method of any one of claims 1 to 2, wherein step (a) comprises contacting the molten urea with a gel comprising ammonium sulfate and calcium carbonate.

4. The method of any one of claims 1 to 3, wherein the contacting in step (c) comprises granulating the solidified product with the additional ammonium sulfate and the additional calcium carbonate to form the fertilizer granule and / or step (c) further comprises drying.

5. The method of any one of claims 1 to 4, wherein the fertilizer granule comprises 20 wt.% to 46 wt.% nitrogen, 0.5 wt.% to 10 wt.% sulfur, and 0.5 wt.% to 2.5 wt.% calcium.

6. The method of any one of claims 1 to 5, wherein at least a portion of the molten urea comprises recycled urea.

7. The method of any one of claims 1 to 6, wherein at least a portion of the ammonium sulfate is from an ammonia production plant and / or at least a portion of the ammonium sulfate is a byproduct from a caprolactam production plant.

8. The method of any one of claims 1 to 7, wherein at least a portion of the calcium carbonate is mined chalk, limestone, and / or marble.299518500.1 - 19 -9. The method of any one of claims 1 to 8, wherein the method further comprises reacting calcium sulfate, CO2, and a source of ammonia to produce at least a portion of the ammonium sulfate and / or at least a portion of the calcium carbonate.

10. The method of claim 9, wherein the source of ammonia comprises ammonia gas and / or ammonium hydroxide.

11. The method of any one of claims 9 or 10, wherein the ammonium sulfate is produced by utilization of waste gypsum and / or CO2from a decarbonization source.

12. The method of claim 11, wherein the waste gypsum is red gypsum, phosphogypsum, and / or flue gas gypsum.

13. The method of any one of claims 1 to 12, wherein step (a) is performed at a temperature of 120 °C to 150 °C and / or a pressure of 1 bar to 10 bar.

14. A fertilizer composition comprising urea, ammonium sulfate, and calcium carbonate, wherein: the fertilizer comprises a core-shell structure; and / or the fertilizer comprises 60 wt.% to 75 wt.% urea, 20 wt.% to 30 wt.% ammonium sulfate, and 5 wt.% to 10 wt.% calcium carbonate.

15. The fertilizer composition of claim 14, comprising: 20 wt.% to 46 wt.% nitrogen, 0.5 wt.% to 10 wt.% sulfur, and 0.5 wt.% to 2.5 wt.% calcium; and / or a core-shell structure, the core comprising a solidified fertilizer melt and the shell comprising ammonium sulfate and calcium carbonate.299518500.1 - 20 -

Images