WO2025141411A1

WO2025141411A1 - Sustainable slow-release complex calcium, nitrogen, potassium, and sulfur fertilizer

Info

Publication number: WO2025141411A1
Application number: PCT/IB2024/062904
Authority: WO
Inventors: Aghaddin Mamedov; Mohamed AL-RABHI
Original assignee: SABIC Agri Nutrients Co
Current assignee: SABIC Agri Nutrients Co
Priority date: 2023-12-27
Filing date: 2024-12-19
Publication date: 2025-07-03
Anticipated expiration: 2026-06-27

Abstract

Disclosed is a fertilizer containing a mixture containing calcium nitrate (Ca(NO₃)₂), urea sulfate (H₂SO₄·CO(NH₂)₂), and/or the potassium sulfate (K₂SO₄). Methods of making and using the fertilizer are also disclosed.

Description

DESCRIPTION SUSTAINABLE SLOW-RELEASE COMPLEX CALCIUM, NITROGEN, POTASSIUM, AND SULFUR FERTILIZER ENCAPSULATED WITH BENTONITE CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63/615,133, filed December 27, 2023, the contents of which is incorporated into the present application by reference. BACKGROUND OF THE INVENTION I. Field of the Disclosure [0001] This disclosure generally concerns fertilizer compositions containing a slow-release agent. In particular embodiments, the disclosure concerns fertilizers containing calcium nitrate, urea sulfate, and potassium sulfate. II. Background [0002] Soil nutrients, such as nitrogen, phosphorus, potassium, and sulfur, as well as trace elements such as iron, zinc, copper, calcium, 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. [0003] Application of a fertilizer does not always provide the full amount of the nutrients in the fertilizer to the plant within a short period of time. Some fertilizers contain nutrient containing compounds that are not readily available to the plant upon application. In these circumstances, some apply fertilizer well before the planting of plants, or some over fertilize closer to the planting of the plants to provide sufficient nutrients to the plant initially. However, this comes at the cost of time, may require multiple treatments to the soil before or after planting, and/or may increase expenses. Continuous use of fertilizers leads to loss of soil fertility and nutrient balance. To increase the crop yield and satisfy the growing need of increasing population, more fertilizers are being used. In addition, large application or usage of urea and urea’s rapid hydrolysis and nitrification in the soil is causing deterioration of soil

295740975.1 - 1 - health and environmental issues such as greenhouse emissions and ground water contamination. [0004] Plants, such as crop plants, need nutrients at least over the entire growth and maturation period for the plant. However, many fertilizers, when applied to a soil, disperse, are degraded, or are taken up within a short period of time after application. To address this issue, fertilizers can be applied multiple times to the same plants or slow release fertilizers can be used. Some approaches to slow release fertilizers include polymer coating a fertilizer core. However, many polymer coatings are expensive and/or will undesirably build up in the soil over time after repeated applications. Some approaches to slow the release of fertilizers include coating or mixing with insoluble metal oxides, such as MgO and CaO. However, these metal oxides do not provide much, if any, nutrients to the plant. SUMMARY OF THE INVENTION [0005] A solution to at least some of the problems discussed above is disclosed herein, including generating a fertilizer product by combining urea sulfate, calcium nitrate, such as calcium nitrate derived from waste gypsum, and potassium sulfate. In some aspects, the components of the fertilizer are combined so that the fertilizer has slow-release characteristics for nutrients therein. In some aspects, the component(s) build up in soil as a reservoir of nutrients for release over a time. In one aspect, the solution resides in providing a fertilizer comprising calcium (Ca), nitrogen (N), potassium (K), and sulfur (S), present as calcium nitrate (Ca(NO₃)₂), urea sulfate (H₂SO₄·CO(NH₂)₂), and potassium sulfate (K₂SO₄). In some aspects, the calcium nitrate (Ca(NO₃)₂) at least partially binds and/or at least partially surrounds the urea sulfate (H2SO4·CO(NH2)2) and/or the potassium sulfate (K2SO4). In some aspects, the calcium nitrate forms a continuous phase in the fertilizer composition. In some aspects, at least a portion of the urea sulfate (H₂SO₄·CO(NH₂)₂) and/or potassium sulfate (K₂SO₄) are absorbed on the surface of the calcium nitrate (Ca(NO3)2). Applicant has determined that the method reduces the process steps to generate the fertilizer product, which may minimizes the capital and/or operational expenditure. Moreover, there is an environmental benefits associated with this process due to the ability to utilize CaSO4 waste from phosphoric acid plant and/or use of SO4 ion from CaSO4. In some aspects, the binder containing compositions have additional advantages. For example, compositions that contain bentonite clay mechanically strengthen the composition, which can improve product quality during storage, transportation, and application. Further, these compositions that contain urea sulfate can be less hydroscopic than

295740975.1 - 2 - a urea containing composition. Additionally, the compositions herein with NO₃ and/or calcium ions may provide NO3 and/or calcium to crops and/or regulate the pH of soil. [0006] In some aspects, the fertilizer composition further comprises a binder. In some aspects, the binder comprise a clay. In some aspects, the clay comprises bentonite. In some aspects, the binder is homogenously distributed throughout the fertilizer composition. In some aspects, the binder is at least partially surrounded and/or bound by the calcium nitrate (Ca(NO₃)₂). In some aspects, the binder at least partially surrounds and/or binds the calcium nitrate (Ca(NO3)2), urea sulfate (H2SO4·CO(NH2)2), and/or potassium sulfate (K2SO4). In some instances, the binder and the combination of calcium nitrate (Ca(NO3)2), urea sulfate (H₂SO₄·CO(NH₂)₂), and potassium sulfate (K₂SO₄) are comprised at a weight ratio between approximately 0.1:10 to 5:10, such as 0.1:10, 0.2:10, 0.3:10, 0.4:10, 0.5:10, 0.6:10, 0.7:10, 0.8:10, 0.9:10, 1:10, 1.1:10, 1.2:10, 1.3:10, 1.4:10, 1.5:10, 2:10, 3:10, 4:10, or 5:10. [0007] In some aspects, the composition further comprises urea (NH₂CONH₂), calcium sulfate (CaSO4), sulfuric acid (H2SO4), potassium chloride (KCl), hydrochloric acid (HCl), and/or nitric acid (HNO3). In some aspects, at least a portion of the nitric acid is derived from a renewable energy source or a process that uses a renewable energy source. In some aspects, the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and/or biomass renewable energy. [0008] In some aspects, the fertilizer is produced by the method of generating a fertilizer product disclosed herein. In some embodiments, synthesis of at least part of the fertilizer occurs through reacting a calcium sulfate with nitric acid to produce a calcium nitrate (Ca(NO3)2). Non-limiting example reactions can include the following: CaSO4 + 2HNO3 → Ca(NO3)2 + H2SO4 [0009] In some embodiments, synthesis of at least part of the fertilizer occurs through reacting urea with sulfuric acid, to produce a urea sulfate (H₂SO₄·CO(NH₂)₂. Non-limiting example reactions can include the following: H2SO4 + NH2CONH2 → H2SO4·CO(NH2)2 [0010] In some embodiments, synthesis of at least part of the fertilizer occurs through reacting two equivalents of potassium chloride with one equivalent of sulfuric acid, to produce a potassium sulfate (K2SO4). Non-limiting example reactions can include the following: 2KCl + H2SO4 → K2SO4 + HCl

295740975.1 - 3 - [0011] The final product may contain a mixture of the above composition chemicals, including, but not limited to any one of Ca(NO3)2, H2SO4·CO(NH2)2, and K2SO4. In some aspects, the sulfuric acid produced in the production of calcium nitrate is at least partially used to produce the urea sulfate and/or the potassium sulfate. [0012] In some aspects, the reactions are performed in one or more than one container. In some aspects, the reactions are performed simultaneously or sequentially or a mixture of both. [0013] Embodiments of the disclosure are improvements to known fertilizer, including by involving the use of a slow-release agent in a fertilizer comprising nitrogen (N), sulfur (S), and metals such as calcium (Ca) and potassium (K). Current slow-release fertilizer products often use physical intervention to slow the release of the fertilizer, such as by coating the fertilizer with a polymer insoluble material to slow the fertilizer’s release. Current slow-release fertilizers may also employ enzymatic inhibitors, such as urease inhibitors or nitrification inhibitors, to slow the utilization of the fertilizer. Though the fertilizers described herein may also contain physical interventions and/or inhibitors, the fertilizers described herein do not always require such measures to produce a slow-release nutrient fertilizer composition. [0014] Embodiments herein describe mixtures of nutrients, and the preparation of such mixtures, which play a role for generating a buildup of fertilizer in soil as reservoir of nutrients for release over time. The fertilizer can include an immediate-release aspect of the fertilizer that can comprise or consist of soluble reactants or products of the reactions described herein and any combination thereof. [0015] In some aspects, the fertilizer comprises or consists of calcium nitrate, urea sulfate, and potassium sulfate, and optionally one or more binder. [0016] Fertilizers encompassed in certain embodiments herein comprise ingredients that can be used to cover immediate soil Ca, N, K and S deficiency in the form of an easily soluble calcium nitrate, urea sulfate, and potassium sulfate, while also covering long-term Ca, N, K and S needs through a slow release of urea sulfate, calcium nitrate, and/or potassium sulfate, such as by encapsulation of the urea sulfate and/or potassium sulfate by calcium nitrate. [0017] Certain aspects are directed to a fertilizer comprising a mixture comprising a nitrogen source, a potassium source, a sulfur source, and a calcium source. The mixture, in some aspects, comprises a binder. The binder can comprise a slow-release agent. The binder, in some aspects, comprises an immediate-release agent. The immediate-release agent can comprise calcium nitrate, calcium sulfate, nitric acid, sulfuric acid, urea sulfate, potassium sulfate and/or potassium chloride.

295740975.1 - 4 - [0018] Certain aspects are directed to a fertilizer comprising at least a portion of the immediate-release agents encapsulated by the binder. Certain aspects are directed to a fertilizer comprising at least a portion of the immediate-release agents contained on the surface of the calcium nitrate and/or the binder. Certain aspects are directed to a fertilizer comprising at least a portion of the immediate-release agents contained in a dried gel of calcium nitrate. [0019] In some aspects, calcium nitrate and/or binder forms a continuous phase in the matrix of the fertilizer. [0020] In some aspects, the fertilizer does not comprise a binding agent separate from the calcium nitrate, urea sulfate, and/or potassium sulfate. The fertilizer can be a granular fertilizer. [0021] In some aspects, at least a portion of the urea sulfate and/or potassium sulfate in fertilizer is encapsulated by the calcium nitrate. In some aspects, at least a portion of the calcium nitrate, urea sulfate, and/or potassium sulfate in the fertilizer is encapsulated by the binder. In some aspects, the mixture and/or fertilizer is a homogenous mixture and/or fertilizer. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises amorphous phases made of components of the fertilizer. [0022] In some aspects, the composition may contain 12 to 18 wt.% nitrogen (N), 10 to 15 wt.% sulfur (S), 8 to 10 wt.% potassium (K), and/or 14 to 17 wt.% calcium (Ca). In certain aspects, the fertilizer contains at least any one of, at most any one of, equal to any one of, or between any two of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt.% nitrogen (N), at least any one of, at most any one of, equal to any one of, or between any two of 9, 10, 11, 12, 13, 14, 15, 16, or 17 wt.% sulfur (S), at least any one of, at most any one of, equal to any one of, or between any two of 7, 8, 9, 10, 11, or 12 wt.% potassium (K), and/or 12, 13, 14, 15, 16, 17, or 18 wt.% calcium (Ca). [0023] In certain aspects, the fertilizer does not contain a polymer. In certain aspects, the fertilizer further comprises a polymer. In certain aspects, the fertilizer further comprises a phosphorus source. [0024] In certain aspects, the calcium sulfate is sourced from or is comprised in waste gypsum. In certain aspects, the waste gypsum is phosphogypsum or red gypsum. In certain aspects, calcium sulfate is not produced or used by the method and/or is not present in the fertilizer. [0025] Certain aspects are directed to a method of making a fertilizer, including any fertilizer described herein. The method can include steps (a), (b), and/or (c). In step (a) calcium sulfate is contacted with nitric acid to generate a first reaction product comprising calcium nitrate and sulfuric acid. In step (b) the first reaction product and/or sulfuric acid is contacted

295740975.1 - 5 - with urea to generate a second reaction product comprising urea sulphate. In step (c) potassium chloride is contacted with sulfuric acid and/or the first reaction product to form a third reaction product comprising potassium sulfate. In some instances, at least a portion of the sulfuric acid of step (c) and/or (b) is generated in step (a). In some instances, at least two of steps (a), (b), and (c) are performed as a one pot synthesis. In some instances, the method further comprising contacting the first reaction product, the second reaction product, and/or the third reaction product with a binder. In some instances, the method further comprising contacting the first reaction product, the second reaction product, and/or the third reaction product with bentonite. In some instances, the fertilizer further comprises unreacted calcium sulfate, nitric acid, urea, potassium chloride, hydrochloric acid, and/or sulfuric acid. In some instances, the fertilizer does not contain any one or more of calcium sulfate, nitric acid, urea, potassium chloride, hydrochloric acid, and/or sulfuric acid. [0026] In certain aspects, the method of making the fertilizer comprises drying the fertilizer mixture to form a solid fertilizer composition. Steps (a), (b), (c), and/or drying may occur at approximately 20° C to 150° C, such as 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, and 150° C. In some aspects, steps (a), (b), and/or (c) may occur at 20 to 75° C or any temperature or range therein. [0027] Also disclosed are the following aspects 1 to 20 of the present invention. [0028] Aspect 1 is a fertilizer composition comprising a calcium nitrate (Ca(NO₃)₂), urea sulfate (H2SO4·CO(NH2)2), and potassium sulfate (K2SO4), wherein the calcium nitrate (Ca(NO3)2) at least partially binds and/or at least partially surrounds the urea sulfate (H₂SO₄·CO(NH₂)₂) and/or the potassium sulfate (K₂SO₄). [0029] Aspect 2 is the fertilizer composition of aspect 1, wherein the calcium nitrate forms a continuous phase. [0030] Aspect 3 is the fertilizer composition of any one of aspects 1 and 2, wherein the composition comprises 12 to 18 wt.% nitrogen (N), 10 to 15 wt.% sulfur (S), 8 to 10 wt.% potassium (K), and 14 to 17 wt.% calcium (Ca). [0031] Aspect 4 is the fertilizer composition of any one of aspects 1 to 3, wherein the composition further comprises a binder.

295740975.1 - 6 - [0032] Aspect 5 is the fertilizer composition of aspect 4, wherein the binder comprises a clay. [0033] Aspect 6 is the fertilizer composition of aspect 5, wherein the clay comprises bentonite. [0034] Aspect 7 is the fertilizer composition of any one of aspects 4 to 6, wherein the binder is homogenously distributed throughout the fertilizer composition. [0035] Aspect 8 is fertilizer composition of any one of aspects 1 to 7, wherein the composition further comprises urea (NH2CONH2), calcium sulfate (CaSO4), sulfuric acid (H2SO4), potassium chloride (KCl), hydrochloric acid (HCl), and/or nitric acid (HNO3). [0036] Aspect 9 is the fertilizer composition of aspect 8, wherein the calcium sulfate is in the form of a waste gypsum. [0037] Aspect 10 is the fertilizer composition of aspect 9, wherein the waste gypsum is phosphogypsum or red gypsum. [0038] Aspect 11 is the fertilizer composition of any one of aspects 8 to 10, wherein at least a portion of the nitric acid is derived from a renewable energy source and/or a process that uses a renewable energy source. [0039] Aspect 12 is the fertilizer composition of aspect 11, wherein the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and/or biomass renewable energy. [0040] Aspect 13 is the composition of any one of aspects 4 to 12, wherein the binder is at least partially surrounded by and/or at least partially bound by the calcium nitrate (Ca(NO₃)₂). [0041] Aspect 14 is the fertilizer composition of any one of aspects 1 to 13, wherein at least a portion of the urea sulfate (H2SO4·CO(NH2)2) and/or potassium sulfate (K2SO4) are absorbed on the surface of the calcium nitrate (Ca(NO3)2). [0042] Aspect 15 is the fertilizer composition of any one of aspects 1 to 14, wherein the fertilizer composition further comprises a phosphorus source. [0043] Aspect 16 is the fertilizer composition of any one of aspects 1 to 15, wherein the fertilizer composition is a granular fertilizer. [0044] Aspect 17 is a method of producing the fertilizer composition of any one of aspects 1 to 16, the method comprising the steps of: (a) contacting calcium sulfate with nitric acid to generate a first reaction product comprising calcium nitrate and sulfuric acid; (b) contacting the first reaction product with urea to generate a second reaction product comprising urea sulphate;

295740975.1 - 7 - (c) contacting potassium chloride with sulfuric acid to form a third reaction product comprising potassium sulfate, wherein at least a portion of the sulfuric acid of step (b) and/or step (c) is generated in step (a). [0045] Aspect 18 is the method of aspect 17, wherein at least two of steps (a), (b), and (c) are performed as a one pot synthesis. [0046] Aspect 19 is the method of any one of aspects 17 and 18, further comprising contacting the first reaction product, the second reaction product, and/or the third reaction product with bentonite. [0047] Aspect 20 is the method of any one of aspects 17 to 19, further comprising a drying step to form a solid fertilizer composition. [0048] 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. [0049] 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 a random shape. [0050] The term “particle” can include a solid material less than a millimeter in its largest dimension. [0051] The terms “particulate” or “powder” can include a plurality of particles. [0052] The terms “about” or “approximately” as used herein 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%. [0053] The terms “wt. %,” “vol.%,” or “mol.%” refers to a weight, volume, 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 of the material is 10 wt. % of component. [0054] The use of the word “a” or “an” when used in conjunction with the term “comprising” may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” [0055] The phrase “and/or” means “and” or “or”. To illustrate, A, B, and/or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination

295740975.1 - 8 - of B and C, or a combination of A, B, and C. In other words, “and/or” operates as an inclusive or. [0056] 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. [0057] The compositions and methods for their use can “comprise,” “consist essentially of,” or “consist of” any of the ingredients or steps disclosed throughout the specification. Compositions and methods “consisting essentially of” any of the ingredients or steps disclosed limits the scope of the claim to the specified materials or steps which do not materially affect the basic and novel characteristic of the claimed invention. [0058] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention. [0059] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS [0060] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein. [0061] FIG.1: a schematic of a system and method for producing a fertilizer according to a non-limiting example of a system and method disclosed herein. [0062] FIG.2: a schematic of a system and method for producing a fertilizer according to another non-limiting example of a system and method disclosed herein. DETAILED DESCRIPTION OF THE INVENTION [0063] Certain aspects of the present disclosure provide benefits over existing fertilizers, including by having slow-release characteristics for nutrients comprising the fertilizer. Certain

295740975.1 - 9 - aspects provided herein allow for the fertilizer to slowly release nutrients into the soil over a period of time, such as throughout a growing cycle for a plant. This capability can be achieved, in some aspects, without the use of binders other than calcium nitrate, without the use of inhibitors, or without the use of other interventions that add compounds beyond the fertilizer’s nutrients. In some embodiments, the fertilizer comprises a urea sulfate (H2SO4·CO(NH2)2), calcium nitrate (Ca(NO3)2), and/or potassium sulfate (K2SO4) which may be one composition and/or one homogenous mixture. The calcium nitrate may act as a binder for the other components in the fertilizer. In some embodiments, the fertilizer my include a different or an additional binder. In some instances, the binder may include bentonite. Applicant has determined that the method reduces the process steps to generate the fertilizer product, which may minimizes the capital and/or operational expenditure. Moreover, there is an environmental benefits associated with this process due to the ability to utilize CaSO4 waste from phosphoric acid plant and/or use of SO4 ion from CaSO4. In some aspects, the binder containing compositions have additional advantages. For example, compositions that contain bentonite clay mechanically strengthen the composition, which can improve product quality during storage, transportation, and application. Further, these compositions that contain urea sulfate can be less hydroscopic than a urea containing composition. Additionally, the compositions herein with NO3 and/or calcium ions may provide NO3 and/or calcium to crops and/or regulate the pH of soil. I. Fertilizer [0064] Certain embodiments herein concern a complex fertilizer comprising: a urea compound, such as a urea sulfate (H2SO4·CO(NH2)2); a potassium compound such as potassium sulfate (K2SO4); and a calcium compound, such as Ca(NO3)2. Certain aspects involve synthesis of the nutrient complex using natural sources of ingredients of the fertilizer, such as CaSO4, HNO3, Ca(NO3)2, H2SO4, KCl, and NH2CONH2. In some aspects, the complex fertilizer is a mixture that is a homogeneous mixture. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises amorphous phases made of components of the fertilizer. In certain aspects, the complex fertilizer further comprises a binder. [0065] The fertilizer, which may be a fertilizer granule, can contain a mixture containing calcium (Ca), potassium (K), sulfur (S) present as a sulfate, nitrogen (N) present as a nitrate and/or urea compound. The ratio of elements present in the fertilizer may be tailored to specific applications.

295740975.1 - 10 - [0066] At least a portion of Ca can be present as calcium nitrate. In some aspects, at least 90 wt. %, or at least 95 wt. %, or 90 wt. % to 100 wt. %, or at least any one of, at most any one of, equal to any one of, or between any two of 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % of the Ca in the mixture can be present as calcium nitrate, based on the total weight of Ca in the mixture. In some embodiments, at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % of the Ca in the mixture can be present as calcium nitrate. [0067] In some aspects, the complex fertilizer can contain i) urea sulfate (H2SO4·CO(NH2)2) in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % based on the total weight of the mixture and/or the fertilizer granule; ii) potassium sulfate (K2SO4) in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. % based on the total weight of the mixture and/or the fertilizer granule; and iii) calcium nitrate (Ca(NO3)2) in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % based on the total weight of the mixture and/or the fertilizer granule. [0068] In some aspects, the fertilizer further contains a binder. In some aspects, the binder comprise a clay. In some aspects, the clay comprises bentonite. In some aspects, the binder is homogenously distributed throughout the fertilizer composition. In some aspects, the binder is

295740975.1 - 11 - at least partially surrounded by and/or at least partially bound by the calcium nitrate (Ca(NO3)2). In some instances, the binder and the fertilizer are comprised at a weight ratio between approximately 0.1:10 to 5:10, such as 0.1:10, 0.2:10, 0.3:10, 0.4:10, 0.5:10, 0.6:10, 0.7:10, 0.8:10, 0.9:10, 1:10, 1.1:10, 1.2:10, 1.3:10, 1.4:10, 1.5:10, 2:10, 3:10, 4:10, or 5:10. [0069] In some instances, a binder includes a phosphate, a polyphosphate, a biodegradable polymer, or a wax, or a combination thereof. Suitable waxes include, but are not limited to, vegetable waxes, high melt waxes, ethylene bis(stearamide) wax, paraffin waxes, polyethylene based waxes, and olefin waxes. Suitable phosphates include, but are not limited to, diammonium phosphate, and monoammonium phosphate. Suitable polyphosphates include, but are not limited to, ammonium polyphosphate. Suitable biodegradable polymers include, but are not limited to, polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid and other biodegradable polymeric material such as polylactic acid, poly(3- hydroxypropionic acid), polyvinyl alcohol, poly e-caprolactone, poly L-lactide, poly butylene succinate, and biodegradable starch based polymers. The binder can include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silica, or combinations thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin modified starches. [0070] In some aspects, the mixture comprises Ca, N, K, and/or S wherein i) the Ca content of the mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, ii) the N content of the mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, iii) the K content of the mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, iv)the S

295740975.1 - 12 - content of the mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. based on the total weight of the mixture and/or fertilizer. [0071] The Ca, N, K, and/or S can be present as and/or sourced as a water soluble compound or a water insoluble compound. In some instances, the Ca, N, K, and/or S can be present as a salt. In some aspects, the Ca, N, K, and/or S can be present as a water soluble salt. In some instances, the water soluble Ca and N salt can be Ca(NO₃)₂. In some instances, the water soluble N and S can be (H₂SO₄·CO(NH₂)₂). In some instances, the water soluble K and S can be (K2SO4). The Ca, N, K, and/or S salt can be in a non-hydrate and/or one or more hydrate form. [0072] In certain aspects, the calcium sulfate is sourced from or is comprised in waste gypsum. In certain aspects, the waste gypsum is phosphogypsum or red gypsum. [0073] Moisture content of the dried fertilizer can be less than 1 wt. %, such as 0.1 wt. % to 0.9 wt. %, or any one of or between any two of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt. %, or any range thereof, based on the weight of the fertilizer granule. As a non-limiting example, the moisture content can be measured by drying the sample at 50° C for 25 min and measuring the amount of mass lost by the fertilizer after being dried. [0074] The fertilizer can be of any suitable shape. Non-limiting shapes include spherical, cuboidal, cylindrical, puck shape, oval, and oblong shapes. In some aspects, the fertilizer granule can be of cylindrical shape with a circular, elliptical, ovular, triangular, square, rectangular, pentagonal, or hexagonal cross section, although cylindrical shaped core having a cross-section of other shapes can also be made. In some aspects, the fertilizer granule at its widest dimension can be 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm. In some particular aspects, the fertilizer granule can have a substantially spherical shape with an average diameter 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm. [0075] The fertilizer can be water and/or soil dispersible. In some aspects, a fertilizer granule having a size of 2 mm to 4 mm prior to adding to water, can disintegrate into particles

295740975.1 - 13 - having sizes less than 1 mm, less than 0.9 mm, less than 0.8 mm, less than 0.7 mm, less than 0.6 mm, less than 0.5 mm, less than 0.4 mm, or less than 0.3 mm, within 1 minute of adding the granule to water at a pH 7, under stirring at a rate 90 rpm to 110 rpm, at an ambient temperature. In some instances, a fertilizer granule having a size of 2 mm to 4 mm prior to adding to water, does not disintegrate into only particles having sizes less than 1 mm, less than 0.9 mm, less than 0.8 mm, less than 0.7 mm, less than 0.6 mm, less than 0.5 mm, less than 0.4 mm, or less than 0.3 mm, before 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or greater than 10 hours of adding the granule to water at a pH 7, under stirring at a rate 90 rpm to 110 rpm, at an ambient temperature. [0076] The mixture can have a compositional make-up that is substantially homogeneous. In some instances, a compositional make-up for a 1 mm × 1 mm × 1 mm cube at any position of the mixture can be similar (within ± 20 %, or ± 10 %, or ± 5 %, or ± 3 %, ± 2 %, or ± 1 %, or ± 0.5 %) to that of a 1 mm × 1 mm × 1 mm cube at any other position of the mixture. [0077] In some aspects, the fertilizer granule can contain an homogeneous mixture. The homogeneous mixture can have compositions as described above. In some instances, the homogenous mixture can have an optional coating on the outer surface of the homogenous mixture. In some instances, the Ca(NO3)2 can act as a binder in the fertilizer. In some instances the Ca(NO₃)₂ is the only binder in the fertilizer. In some instances, the Ca(NO₃)₂ forms an amorphous phase, a continuous phase, and/or encapsulates other ingredients in the fertilizer. In some instances, the fertilizer comprises a matrix of Ca(NO3)2 that at least partially binds and/or encapsulates and/or surrounds at least a portion of the urea sulfate and/or potassium sulfate. In some instances, the fertilizer comprises particles of the Ca(NO₃)_2, potassium sulfate, and/or of urea sulfate. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises amorphous phases made of components of the fertilizer. [0078] In some aspects, additional fertilizer substances can be included or excluded in the fertilizer. If included, additional fertilizers can be chosen based on the particular needs of certain types of soil, climate, or other growing conditions to maximize the efficacy of the fertilizer in enhancing plant growth and crop yield. Additional additives may also be included or excluded in the fertilizer. Non-limiting examples of additives that can be included or excluded from the fertilizer of the present invention include additional nitrogen nutrients, additional phosphorus nutrients, additional potassium nutrients, additional micronutrients, and/or additional secondary nutrients. The micronutrient can be copper, iron, chloride,

295740975.1 - 14 - manganese, molybdenum, or nickel, or any combinations thereof. The nitrogen nutrient can be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride, and potassium nitrate. In some aspects, the additional secondary nutrients may include lime and/or superphosphate. In some instances, the additional fertilizer substances and/or the additional additives are contained in the optional coating of the fertilizer. [0079] In some instances, the inhibitors include nitrification inhibitors and/or urease inhibitors. 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, a 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 some instances, the urease inhibitor may include, but are not limited to, triamide, such as N-(n-butyl) thiophosphoric triamide (NBTPT) and N-(n-propyl) thiophosphoric triamide. In some embodiments, a fertilizer composition can comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, AM, MBT, ST, or a combination thereof. [0080] In some instances, the pH buffers include MgO, KH₂PO₄, NaHCO₃, chalk powder, aluminum, magnesium hydroxide, aluminum hydroxide/magnesium hydroxide co-precipitate, aluminum hydroxide/sodium bicarbonate co-precipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, dibasic sodium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, disodium hydrogen phosphate, magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate, potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, sodium gluconate, sodium hydrogen phosphate, sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, tetrasodium

295740975.1 - 15 - pyrophosphate, tripotassium phosphate, trisodium phosphate, and trometamol, and combinations thereof. [0081] The fertilizer described herein can be comprised in a composition useful for application to soil. In some aspects, in addition to the fertilizer described herein, the composition may include other fertilizer compounds, micronutrients, primary nutrients, urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof. The fertilizer described herein can also be included in a blended composition comprising other fertilizers. The other fertilizer can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), monopotassium phosphate (MKP), triple super phosphate (TSP), rock phosphate, single super phosphate (SSP), ammonium sulfate, and the like. [0082] A fertilizer formed into a granule can have desirable physical properties such as desired levels of abrasion resistance, granule strength, pelletizability, hygroscopicity, granule shape, and size distribution. In some aspects, The fertilizer granule can have a crush strength above 1.5 kgf, such as above 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of, equal to any one of, or between any two of 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, and 6 kgf. Bulk density of the fertilizer granules can be 1 g/cc to 1.2 g/cc, or at least any one of, at most any one of, equal to any one of, or between any two of 1, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18, and 1.2 g/cc. In some aspects, 10 mg or more, such as 10 mg to 40 mg, or at least any one of, at most any one of, equal to any one of, or between any two of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 mg of the fertilizer granule can dissolve in 1 ml of water at a pH 7, under stirring at a rate 90 to 110 rpm, and at an ambient temperature, within 5 minutes of adding 100 mg of the fertilizer granules to the water or only after 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 15 hours, or 24 hours of adding 100 mg of the fertilizer granules to the water. In some aspects, the fertilizer granule is capable of losing less than 0.13 wt. %, such as 0.02 % to 0.12 wt. %, or at most any one of, equal to any one of, or between any two of 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, and 0.12 wt. % in an attrition loss test. Attrition loss can be measured using the following attrition loss test. [0083] Attrition loss test: A plurality of sieved fertilizer granules with individual size 2 to 4 mm, and total volume 100 cm³ is weighed (W1) and is placed into the test drum along with the 50 stainless steel balls having a total weight of 100 gm. The drum is closed and rotated for 10 min at 30 rpm. Then, the steel balls are separated from the sample and the material is

295740975.1 - 16 - screened over 2 mm sieve using a sieve shaker. The total weight of the granules over 2 mm are then re-weighed (W2). Results are calculated in terms of % weight loss using the formula: _{Weight loss due to attrition (wt. %) =} ^^^^^^ ^^ ^^^^^^ ^^^^^^^^ ^^ ^ ^^ ^^^^^ ((^^^^ ^^^^^^ ^^^^^^ ^^ ^^^ ^^^^^^ (^^^ _{× 100} II. Method of Making a Fertilizer [0084] Referring to FIG. 1, a schematic of a system and method for making a fertilizer according to one example of the present invention is described. The system 100 can include a granulator 102 and a dryer 104. A feed mixture 106 can be granulated in the granulator 102 in the presence or absence of water to form a wet granulated mixture 108. The water, if present, can be provided with the feed mixture 106, and/or can be added separately to the granulator 102. The wet granulated mixture 108 can be dried in the dryer 104 to obtain dry granulated mixture 110 containing the fertilizer. [0085] Referring to FIG. 2, a schematic of a system and method for making a fertilizer according to another example of the present invention is described. The system 200 can include a mixer/reactor 212, though the mixer and the reactor can be two, three, four, or more components, such as two reactors and a mixer or a reactor and a mixer. The system 200 can include a granulator 202, a spheronizer 214, one or more size screens 216, and a dryer 204, or any combination thereof. The feed mixture ingredients 218, separately and/or at any possible combination can be added to the mixer/reactor 212. In the mixer/reactor 212, the feed ingredients can be reacted and/or mixed to form the feed mixture 206. Feed mixture 206 can be granulated in the granulator 202 in presence or absence of additional water to form a wet granulated mixture 220. Granules of the wet granulated mixture 220 can be spheronized in the spheronizer 214 to form a wet granulated mixture 222 containing substantially spherical granules. The wet granulated mixture 222 can be passed through one or more size screens 216 to separate granules having a size smaller or bigger than a desired size from the wet granulated mixture 222 and obtain a wet granulated mixture 224 containing granules of desired size. At least a portion of the granules separated 226 from the granulation mixture 224 containing granules of desired size can be recycled to the granulator 202. The wet granulated mixture 224 containing granules of desired size can be dried in the dryer 204 to obtain dry granulated mixture 210 containing the fertilizer granule. In some aspects, the mixer/reactor 212 can contain a ribbon mixer. [0086] The feed mixture ingredients 218 can include i) a Ca source, e.g., calcium sulfate and/or calcium nitrate, ii) a N source, e.g., nitric acid, urea, urea sulfate, and/or calcium nitrate, iii) a K source, e.g., potassium chloride and/or potassium sulfate, iv) a S source, e.g., urea

295740975.1 - 17 - sulfate, sulfuric acid, calcium sulfate, and/or potassium sulfate and/or v) a binder. In some instances, a mixture ingredient provides more than one of Ca, N, K, and/or S. In some instances, a mixture ingredient provides additional nutrients and/or micronutrients, such as P, Mg, Fe, and/or Si. In certain aspects, one or more ingredients can be added as a water solution. In some instances, the mixture ingredients are provided as a powder. In some instances, one or more ingredients can be added as a liquid. In some instances, one or more ingredients can be added as a gas. In some instances, a portion of the mixture of ingredients is provided as a powder. [0087] The feed mixture 106, 206 can contain Ca, N, S, K, and/or a binder. In some aspects, the feed mixture 106, 206 can contain calcium nitrate (Ca(NO3)2), urea sulfate (H₂SO₄·CO(NH₂)₂), potassium sulfate (K₂SO₄), urea (NH₂CONH₂), calcium sulfate (CaSO₄), sulfuric acid (H₂SO₄), potassium chloride (KCl), hydrochloric acid (HCl), nitric acid (HNO₃), and/or a binder. [0088] Water can be added to the feed mixture in the mixer/reactor 212 and/or in the granulator 102, 202. In certain aspects, 5 gm to 20 gm, or at least any one of, at most any one of, equal to any one of, or between any two 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 gm of water in total (e.g., added with one or more feed mixture ingredients and/or separately) can be added to the feed mixture, per 100 gm of feed mixture. [0089] In some aspects, the granulator 102, 202 can be a drum granulator, pugmill granulator, pan granulator, solid mixer, abrasion drum, extruder, high-shear mixer granulator, roller granulator, mycromix, or a round bottom flask. In the granulator 102, 202 the feed mixture 106, 206 can be granulated by agglomeration, spray granulation, compaction, slurry granulation and/or high-shear mixer granulation. In some particular aspect, the feed mixture 106, 206 can be granulated in the granulator 102, 202 by compaction. In some aspects, the granulator 102, 202 can contain at least two rollers and compaction granulation can include compressing the feed mixture using the at least two rollers. In some aspects, the two rollers can be moved in counter current direction during compaction. In some aspects, the feed mixture can be compressed into shaped pellets, such as cylindrical pellets, by the at least two rollers. In some aspects, a surface of one roller can have desired holes to compress the feed mixture into the holes, and the surface of the other roller can push the feed mixture into the holes. Pressure during granulation, e.g. compaction granulation can be 1 bar to 40 bar, or at least any one of, at most any one of, equal to any one of, or between any two 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, and 40 bar. In certain aspects, the feed mixture can be granulated in the granulator 102, 202 at ambient temperature to 50° C, or at least any one of, at most any one of, equal to any one of, or between any two of -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50° C.

295740975.1 - 18 - [0090] In some aspects, reacting of the feed mixture ingredients, mixing, and granulating the feed mixture can be performed in different containers, e.g., the mixer/reactor 212 and the granulator 202 can be different containers. In some aspects, reacting of the feed mixture ingredients, mixing, and granulating the feed mixture can be performed in the same container, e.g., the mixer/reactor 212 and the granulator 202 can be the same container (not shown). In some aspects, the mixer/reactor 212 and the granulator 202 can be more than two containers. In some instances, calcium nitrate (Ca(NO₃)₂), urea sulfate (H₂SO₄·CO(NH₂)₂), and potassium sulfate (K2SO4) are formed in one container. In some instances, calcium nitrate (Ca(NO3)2) and K2SO4 are formed in one container. In some instances, calcium nitrate (Ca(NO3)2) and urea sulfate (H₂SO₄·CO(NH₂)₂) are formed in one container. In some instances, urea sulfate (H₂SO₄·CO(NH₂)₂) is formed in one container, potassium sulfate (K₂SO₄) is formed in one container, and/or Ca(NO3)2 and H2SO4 are formed in one container. In some instances, the H2SO4 and Ca(NO3)2 are formed in one container and the urea sulfate (H2SO4·CO(NH2)2) and potassium sulfate (K₂SO₄) are formed in one container. [0091] In some aspects, the (H2SO4·CO(NH2)2),, (K2SO4), and Ca(NO3)2 are formed at a temperature of at least, at most, equal to, or between any two of 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, or 150° C, such as between 20 and 80° C or between 100 and 150° C or between 75 and 150° C or between 55 to 75° C or between 20 and 150° C. [0092] In some instances, the fertilizer can be extruded before drying. The extruder can extrude the fertilizer at pressures at least, at most, equal to, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 bar. The extruder can extrude the fertilizer at temperatures at least, at most, equal to, or between any two of -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50° C. The extrudate can be sliced or divided before drying, such as by a die. [0093] In certain aspects, the desired size of a final fertilizer product, such as a granule, can be 0.5 to 5 mm, or 1 to 4 mm, and having a size lower than 0.5 mm or 1 mm, and/or having a size bigger than 4 mm or 5 mm can be separated from the wet granulated mixture 222 in the one or more size screens 216. In certain aspects, the wet granulated mixture can be rounded

295740975.1 - 19 - and/or spheronized in a spheronizer. In some instances, the wet granulated mixture is contacted with a spheronizer for at least any one of, at most any one of, equal to any one of, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 50, or 60 seconds. The spheronizer in some instances has a rotating or rotatable disk capable of rotating at least any one of, at most any one of, equal to any one of, or between any two of 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000 rpm. In certain aspects, the wet granulated mixture can be dried in the dryer 104, 204 at a temperature 40° 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 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150° C. In some aspects, the dryer 104, 204 can be a fluid bed dryer, drum dryer, or flash dryer. In some aspects, the wet granulated mixture can be dried in the dryer 104, 204 with an hot air flow having a flow rate of at least any one of, at most any one of, equal to any one of, or between any two of 100, 150, 200, 250, 300, 350, 400, 450, and 500 m³/hr and/or a rotation of at least any one of, at most any one of, equal to any one of, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 rpm. III. Methods of Using the Fertilizer [0094] The fertilizer, including fertilizer granules, compositions containing the fertilizer, and fertilizer blends containing the fertilizer of the present disclosure can be used in methods of increasing the amount of one or more plant nutrients in soil and of enhancing plant growth. Such methods can include applying to the soil an effective amount of a composition and/or blend containing the fertilizer of the present invention. The method may include increasing the growth and yield of crops, trees, ornamentals, etc., such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and/or soybeans. The method can include applying the fertilizer blend of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc. The composition(s) and/or fertilizer blends(s) containing the fertilizer can be applied to plants and/or soil as a top dressing fertilizer, basal fertilizer, and/or through any suitable method of application. [0095] Non-limiting examples of plants that can benefit from the fertilizer 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. [0096] The effectiveness of compositions comprising the fertilizer of the present invention can be ascertained by measuring the amount of phosphorus and optionally other nutrients in the soil at various times after applying the fertilizer composition to the soil. It is understood

295740975.1 - 20 - that different soils have different characteristics, which can affect the stability of the nutrients in the soil. The effectiveness of a fertilizer 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. EXAMPLES [0097] 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 Preparation of a fertilizer [0098] 40 g of calcium sulfate was gradually added to 63 g of 70 % nitric acid in an hour and stirred at 190 rpm at 65^o C to dissolve the calcium sulfate in the nitric acid to form a mixture of calcium nitrate and sulfuric acid. To the mixture 35 g potassium chloride was added, which reacted with the in-situ produced sulfuric acid. To the resulting solution 27 g of urea was added gradually to form a first gel. The formed gel mixture was stirred for 30 min. Then to the gel, 6 g of bentonite clay was added and homogenously mixed. Then the mixture was dried at 92^o C for 24 hours, and granulated to the particles with a size of 3-4 mm. The following reactions took place: CaSO₄ + 2HNO₃ = Ca(NO₃)₂ + H₂SO₄ NH2CONH2 + H2SO4 = NH2CONH4SO4 2KCl + H2SO4 = K2SO4 + HCl The final product contained Ca(NO₃)₂/ NH₂CONH₄SO₄/K₂SO₄/bentonite clay. * * * [0099] All of the methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and

295740975.1 - 21 - modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

295740975.1 - 22 -

Claims

WHAT IS CLAIMED IS: 1. A fertilizer composition comprising a calcium nitrate (Ca(NO3)2), urea sulfate (H2SO4·CO(NH2)2), and potassium sulfate (K2SO4), wherein the calcium nitrate (Ca(NO3)2) at least partially binds the urea sulfate (H₂SO₄·CO(NH₂)₂) and/or the potassium sulfate (K₂SO₄).

2. The fertilizer composition of claim 1, wherein the calcium nitrate forms a continuous phase.

3. The fertilizer composition of any one of claims 1 and 2, wherein the composition comprises 12 to 18 wt.% nitrogen (N), 10 to 15 wt.% sulfur (S), 8 to 10 wt.% potassium (K), and 14 to 17 wt.% calcium (Ca).

4. The fertilizer composition of any one of claims 1 to 3, wherein the composition further comprises a binder other than calcium nitrate.

5. The fertilizer composition of claim 4, wherein the binder comprises a clay.

6. The fertilizer composition of claim 5, wherein the clay comprises bentonite.

7. The fertilizer composition of any one of claims 4 to 6, wherein the binder is homogenously distributed throughout the fertilizer composition.

8. The fertilizer composition of any one of claims 1 to 7, wherein the composition further comprises urea (NH₂CONH₂), calcium sulfate (CaSO₄), sulfuric acid (H₂SO₄), potassium chloride (KCl), hydrochloric acid (HCl), and/or nitric acid (HNO3).

9. The fertilizer composition of claim 8, wherein the calcium sulfate is in the form of a waste gypsum.

10. The fertilizer composition of claim 9, wherein the waste gypsum is phosphogypsum or red gypsum.

11. The fertilizer composition of any one of claims 8 to 10, wherein at least a portion of the nitric acid is derived from a renewable energy source and/or from a process that uses a renewable energy source.

12. The fertilizer composition of claim 11, wherein the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and/or biomass renewable energy.

295740975.1 - 23 -

13. The fertilizer composition of any one of claims 4 to 12, wherein the binder is at least partially surrounded by the calcium nitrate (Ca(NO3)2).

14. The fertilizer composition of any one of claims 1 to 13, wherein at least a portion of the urea sulfate (H₂SO₄·CO(NH₂)₂) and/or potassium sulfate (K₂SO₄) are absorbed on the surface of the calcium nitrate (Ca(NO3)2).

15. The fertilizer composition of any one of claims 1 to 14, wherein the fertilizer composition further comprises a phosphorus source.

16. The fertilizer composition of any one of claims 1 to 15, wherein the fertilizer composition is a granular fertilizer.

17. A method of producing the fertilizer composition of any one of claims 1 to 16, the method comprising the steps of: (a) contacting calcium sulfate with nitric acid to generate a first reaction product comprising calcium nitrate and sulfuric acid; (b) contacting the first reaction product with urea to generate a second reaction product comprising urea sulphate; (c) contacting potassium chloride with sulfuric acid to form a third reaction product comprising potassium sulfate, wherein at least a portion of the sulfuric acid of step (b) and/or step (c) is generated in step (a).

18. The method of claim 17, wherein at least two of steps (a), (b), and (c) are performed as a one pot synthesis.

19. The method of any one of claims 17 and 18, further comprising contacting the first reaction product, the second reaction product, and/or the third reaction product with bentonite.

20. The method of any one of claims 17 to 19, further comprising a drying step to form a solid fertilizer composition.

295740975.1 - 24 -