Integration of calcium ammonium nitrate and ammonium sulfate for safe and stable nutrient complexes

Abstract

Fertilizers containing calcium ammonium nitrate and ammonium sulfate are disclosed. The invention also discloses a preparation method and a use method of the fertilizer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 425,056, filed on November 14, 2022, the entire contents of which are incorporated herein by reference. Background of the Invention I. Technical Field

[0003] The present disclosure generally relates to fertilizer compositions containing slow-release agents. In certain embodiments, the present disclosure relates to fertilizers containing calcium ammonium nitrate and ammonium sulfate. II. Background Technology

[0004] Soil nutrients, such as nitrogen, phosphorus, potassium, and sulfur, as well as trace elements like iron, zinc, copper, calcium, and magnesium, are essential for agricultural prosperity and plant growth. Over repeated cropping cycles, the availability of these nutrients in the soil can become depleted, resulting in stunted plant growth and reduced yields. To counteract this effect, fertilizers have been developed to help replace depleted vital nutrients. To meet the diverse needs of global crop production, both single-nutrient fertilizers and multi-nutrient fertilizers, such as blended fertilizers, have been developed.

[0005] Fertilizer application doesn't always provide plants with the full amount of nutrients in the fertilizer in a short period of time. Some fertilizers contain nutrients with compounds that are not easily absorbed and utilized by plants after application. In these cases, some people apply fertilizer before planting or over-fertilize close to planting to provide plants with sufficient nutrients early on. However, this comes at a cost in time, may require multiple soil treatments before or after planting, and / or may increase costs.

[0006] Plants, such as crop plants, require nutrients at least throughout the plant's growth and maturity period. However, many fertilizers disperse when applied to the soil, degrade, or are absorbed within a short period of time after application. To address this issue, fertilizers can be applied to the same plant multiple times or slow-release fertilizers can be used. Some methods of slowing the release of fertilizers include coating the fertilizer core with a polymer. However, many polymer coatings are expensive and / or can accumulate undesirably in the soil over time after repeated applications. Some methods of slowing the release of fertilizers include coating or mixing 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

[0007] Disclosed herein are solutions to at least some of the problems discussed above, including the production of fertilizer products that do not require urea, although urea can also be used in addition, and the production of fertilizer products that have slow-release properties for their nutrients. In some aspects, one or more components accumulate in the soil and serve as a reservoir of nutrients that are released over time. In one aspect, the solution is to provide a fertilizer that includes calcium (Ca), nitrogen (N) in the form of ammonium and nitrates, and sulfur (S) in the form of sulfates. In some aspects, the fertilizer contains calcium ammonium nitrate (for example, but not limited to, Ca(NH4)2(NO3)4) and ammonium sulfate. The calcium ammonium nitrate can serve as a binder for other ingredients in the fertilizer, such as ammonium sulfate. Calcium ammonium nitrate is also more stable and safer than ammonium nitrate.

[0008] In some embodiments, at least part of the fertilizer is synthesized by reacting a metal sulfate with nitric acid. Non-limiting exemplary reactions may include the following:

[0009] CaSO4+2HNO3→Ca(NO3)2+H2SO4

[0010] In some embodiments, at least part of the fertilizer is synthesized by reacting nitric acid with an ammonia source, such as ammonium hydroxide (NH4OH) and / or ammonia gas, to produce ammonium nitrate. Non-limiting exemplary reactions may include the following:

[0011] 2HNO3+2NH3→2NH4NO3

[0012] In some embodiments, at least part of the fertilizer is synthesized by reacting a metal nitrate, such as calcium nitrate, and ammonium nitrate to produce a metal ammonium nitrate salt, such as calcium ammonium nitrate. Non-limiting exemplary reactions may include the following:

[0013] Ca(NO3)2+2NH4NO3→Ca(NH4)2(NO3)4

[0014] In some embodiments, at least part of the fertilizer synthesis is performed by reacting sulfuric acid with an ammonia source to produce ammonium sulfate ((NH4)2SO4). Non-limiting exemplary reactions may include the following:

[0015] H2SO4+2NH3→(NH4)2SO4

[0016] The final product may contain a mixture of the above chemical compositions, including but not limited to any one of calcium ammonium nitrate and ammonium sulfate.

[0017] In some aspects, the reaction is carried out in one or more than one container. In some aspects, the reaction is carried out simultaneously or sequentially, or both.

[0018] Embodiments of the present disclosure are improvements to known fertilizers, including those involving the use of slow-release agents in fertilizers containing nitrogen (N), sulfur (S), and metals such as calcium (Ca). Current slow-release fertilizer products typically use physical intervention to slow the release of the fertilizer, such as by coating the fertilizer with a polymer-insoluble material to slow the release of the fertilizer. Current slow-release fertilizers may also employ enzyme inhibitors, such as urease inhibitors or nitrification inhibitors, to slow the utilization of the fertilizer. Although the fertilizers described herein may also contain physical intervention and / or inhibitors, the fertilizers described herein do not always require such measures to produce a slow-release nutrient fertilizer composition. In addition, the slow-release fertilizer, calcium ammonium nitrate, is more stable (e.g., less likely to explode) than ammonium nitrate and has more improved storage stability. In addition, the fertilizer compositions disclosed herein also provide sulfur that is not present in ammonium nitrate.

[0019] Embodiments herein describe mixtures of nutrients, and the preparation of such mixtures, that accumulate fertilizers in the soil as a reservoir of nutrients for release over time. Fertilizers may include immediate-release fertilizers, which may comprise or consist of soluble reactants or products of the reactions described herein, and any combination thereof, such as ammonium sulfate. Slow-release fertilizers may comprise or consist of one or more double salts, such as calcium ammonium nitrate.

[0020] In some aspects, the fertilizer comprises or consists of calcium ammonium nitrate and ammonium sulfate.

[0021] Fertilizers contemplated in certain embodiments herein comprise ingredients that can be used to directly replenish N and S deficiencies in the soil in the form of readily soluble ammonium sulfate, while also meeting long-term Ca and N requirements through the slow release of calcium ammonium nitrate.

[0022] Certain aspects relate to a fertilizer comprising a homogeneous mixture comprising a nitrogen source, a sulfur source, and a calcium source. In some aspects, the homogeneous mixture comprises a binder. The binder may comprise a slow-release agent, which may comprise calcium ammonium nitrate. In some aspects, the homogeneous mixture comprises a fast-release agent. The fast-release agent may comprise ammonium sulfate and optionally calcium sulfate, calcium nitrate, and ammonium nitrate.

[0023] Certain aspects relate to fertilizers comprising at least a portion of a rapid-release agent encapsulated by calcium ammonium nitrate. Certain aspects relate to fertilizers comprising at least a portion of a rapid-release agent contained on the surface of calcium ammonium nitrate. Certain aspects relate to fertilizers comprising at least a portion of a rapid-release agent contained within a dried gel of calcium ammonium nitrate.

[0024] In some aspects, the fertilizer does not include a binder other than calcium ammonium nitrate.The fertilizer can be a granular fertilizer.

[0025] In some aspects, the fertilizer contains at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight % of nitrogen (N): 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, and 25%; at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight % of sulfur (S): 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, and 17%; and / or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight % of calcium (Ca): 2%, 3%, 4%, 5%, 6%, 7%, and 8%. In some cases, the immediate-release agent and the sustained-release agent are included in a weight ratio of about 5:1 to about 1:5, for example, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, or 1:5.

[0026] In some aspects, the fertilizer is free of urea and / or polymers. In some aspects, the fertilizer further comprises urea and / or polymers. In some aspects, the fertilizer is free of ammonium nitrate. In some aspects, the fertilizer is free of phosphorus and / or potassium.

[0027] In some aspects, the calcium sulfate is gypsum. In some aspects, the gypsum is red gypsum or waste gypsum, and / or the gypsum is derived from red gypsum or waste gypsum, or the gypsum is contained in red gypsum or waste gypsum.

[0028] Some aspects relate to a method for preparing a fertilizer, which includes any fertilizer described herein. The method may include steps (a) and / or steps (b). In step (a), metal sulfate reacts with nitric acid and an ammonia source to generate a first reaction product comprising metal nitrate, ammonium nitrate and sulfuric acid. In some cases, step (a) includes contacting the metal sulfate with nitric acid to generate an initial reaction product comprising metal nitrate and sulfuric acid, and contacting the initial reaction product with an ammonia source to react with remaining nitric acid to generate the first reaction product. In some cases, step (a) does not react the initial reaction product with an ammonia source, but separates the reaction of nitric acid and an ammonia source from the reaction that produces the initial reaction product. The initial reaction product can then be combined with a product reacted separately by nitric acid and an ammonia source to form a first reaction product. In step (b), the first reaction product can be contacted with a metal nitrate and an ammonia source to generate a second reaction product comprising ammonium sulfate and metal ammonium nitrate. In some cases, step (b) comprises contacting a metal nitrate with ammonium nitrate, to generate an initial reaction product comprising calcium ammonium nitrate, and contacting the initial reaction product with an ammonia source to react with remaining sulfuric acid to generate a second reaction product. In some cases, step (b) does not react the initial reaction product with an ammonia source, but separates the reaction of sulfuric acid and ammonia source from the reaction that produces the initial reaction product. Then, the initial reaction product can be combined with the product reacted separately by sulfuric acid and ammonia source to form a second reaction product. In some aspects, the method for preparing fertilizer comprises drying the fertilizer mixture to form a solid fertilizer composition.Step (a) and step (b) and / or drying can be carried out at about 30°C to about 150°C, for example, at 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, , 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°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, and 150°C. In some aspects, step (a) and / or step (b) can be carried out at a temperature of 30°C to 75°C, or any range therein. In some aspects, the fertilizer composition comprises or consists of calcium ammonium nitrate, ammonium sulfate, calcium nitrate, sulfuric acid, ammonium hydroxide, ammonium nitrate, calcium sulfate, nitric acid, and / or ammonia. In some aspects, the ammonia source comprises an ammonium hydroxide solution, an ammonium solution, an ammonium carbonate solution, an ammonia gas solution, a succinimide solution, and / or a phthalimide solution.

[0029] The following aspects 1 to 20 of the present invention are also disclosed.

[0030] Aspect 1 is a fertilizer composition comprising calcium ammonium nitrate and ammonium sulfate ((NH4)2SO4).

[0031] Aspect 2 is the fertilizer composition according to aspect 1, wherein the composition comprises 17 to 22 weight % of nitrogen (N), 3 to 7 weight % of calcium (Ca), and 10 to 15 weight % of sulfur (S).

[0032] Aspect 3 is the fertilizer composition according to any one of aspects 1 and 2, wherein the composition further comprises calcium nitrate (Ca(NO 3 ) 2 ), sulfuric acid (H 2 SO 4 ) and / or ammonium nitrate (NH 4 NO 3 ).

[0033] Aspect 4 is the fertilizer composition according to any one of aspects 1 to 3, wherein the composition further comprises calcium sulfate (CaSO 4 ), nitric acid (HNO 3 ), ammonium hydroxide (NH 4 OH) and / or ammonia (NH 3 ).

[0034] Aspect 5 is the fertilizer composition according to aspect 4, wherein the composition comprises calcium sulfate contained in waste gypsum and / or recycled gypsum.

[0035] Aspect 6 is the fertilizer composition according to any one of aspects 1 to 5, wherein the composition does not contain a binder other than calcium ammonium nitrate.

[0036] Aspect 7 is the fertilizer composition according to any one of aspects 1 to 6, wherein at least a portion of the ammonium sulfate is adsorbed on the surface of the calcium ammonium nitrate.

[0037] Aspect 8 is the fertilizer composition according to any one of aspects 1 to 7, wherein the fertilizer composition further comprises a phosphorus source and / or a potassium source.

[0038] Aspect 9 is the fertilizer composition according to any one of aspects 1 to 8, wherein the fertilizer is homogeneous.

[0039] Aspect 10 is the fertilizer composition according to any one of aspects 1 to 9, wherein the composition comprises a gel.

[0040] Aspect 11 is the fertilizer composition according to any one of aspects 1 to 10, wherein the composition comprises a dried gel.

[0041] Aspect 12 is the fertilizer composition according to any one of aspects 1 to 11, wherein at least a portion of the ammonium sulfate is encapsulated by calcium ammonium nitrate.

[0042] Aspect 13 is the fertilizer composition according to any one of aspects 1 to 12, wherein the fertilizer composition is a granular fertilizer.

[0043] Aspect 14 is the fertilizer composition according to any one of aspects 1 to 13, wherein the composition does not comprise at least one of urea, ammonium nitrate, or a polymer.

[0044] Aspect 15 is a method for preparing the fertilizer composition according to any one of aspects 1 to 14, the method comprising the following steps:

[0045] (a) contacting calcium sulfate with nitric acid and an ammonia source to produce a first reaction product comprising:

[0046] calcium nitrate, sulfuric acid, and ammonium nitrate; and

[0047] (b) contacting the first reaction product with calcium nitrate and an ammonia source to produce a second reaction product comprising:

[0048] Calcium ammonium nitrate and ammonium sulfate.

[0049] Aspect 16 is the method according to aspect 15, wherein step (a) comprises:

[0050] Calcium sulfate is contacted with nitric acid to produce a product comprising:

[0051] calcium nitrate and sulfuric acid; and

[0052] The nitric acid is contacted with an ammonia source to produce a product comprising:

[0053] ammonium nitrate, and / or

[0054] Step (b) comprises:

[0055] Calcium nitrate is contacted with ammonium nitrate to produce a product comprising:

[0056] Calcium ammonium nitrate; and

[0057] The sulfuric acid is contacted with an ammonia source to produce a product comprising:

[0058] Ammonium sulfate.

[0059] Aspect 17 is the method according to any one of aspects 15 to 16, further comprising drying the second reaction product to form a solid fertilizer composition.

[0060] Aspect 18 is a method according to any one of aspects 15 to 17, wherein the calcium sulfate comprises red gypsum and / or waste gypsum from phosphoric acid production, and / or wherein the source of ammonia is ammonium hydroxide and / or ammonia.

[0061] Aspect 19 is a method according to any one of aspects 15 to 18, wherein step (a) and / or step (b) occurs at 30° C. to 150° C. and / or lasts for 30 minutes to 12 hours.

[0062] Aspect 20 is a method of fertilizing, comprising contacting a plant, soil, water, or a combination thereof with the fertilizer composition of any one of aspects 1 to 14.

[0063] The term "fertilizer" is defined as a substance applied to soil or plant tissue to provide one or more plant nutrients necessary or beneficial to plant growth, and / or a growth promoter or enhancer that promotes or enhances plant growth.

[0064] The term "granule" may include solid materials. Granules may have a variety of shapes, non-limiting examples of which include spheres, spheres, ovoids, rods, oblongs, or random shapes.

[0065] The term "particle" may include solid materials having a largest dimension less than 1 mm.

[0066] The term "particulate" or "powder" may include a plurality of particles.

[0067] The terms "about" or "approximately" as used herein are defined approximately as understood by one of ordinary skill in the art. In one non-limiting embodiment, these terms are defined to be within ±10%, preferably within ±5%, more preferably within ±1%, and most preferably within ±0.5%.

[0068] The terms "wt %," "vol %," or "mole %" refer to the weight percent, volume percent, or mole percent, respectively, of a component based on the total weight, total volume, or total moles of the material in which it is contained. In a non-limiting example, 10 grams of a component in 100 grams of material is 10 wt %.

[0069] When an element is preceded by an indefinite quantifier and used with the terms "include" or "comprising", it can mean "a", but can also be consistent with the meaning of "one or more", "at least one" and "one or more than one".

[0070] The phrase "and / or" means "and" or "or." For example, 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 of B and C, or a combination of A, B, and C. In other words, "and / or" serves as an inclusive "or."

[0071] The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0072] Compositions and methods of use thereof may "comprise," "consist essentially of," or "consist of" any ingredient or any step disclosed throughout the specification. Compositions and methods that "consist essentially of" any disclosed ingredient or any step limit the scope of the claims to the specific materials or steps that do not materially affect the basic and novel characteristics of the claimed invention.

[0073] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method or any composition of the invention, and vice versa. Additionally, the compositions of the invention can be used to implement the methods of the invention.

[0074] Other purposes, features and advantages of the present invention will become apparent from the following detailed description. However, it should be understood that the detailed description and specific examples, while indicating specific embodiments of the present invention, are given only in an illustrative manner, as various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art based on the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] The following drawings form part of this specification and are included to further illustrate certain aspects of the present invention. The present invention may be better understood by reference to one or more of these drawings in conjunction with the detailed description of specific embodiments provided herein.

[0076] Figure 1 : Schematic diagram of a system and method for preparing fertilizer according to a non-limiting example of the systems and methods disclosed herein.

[0077] Figure 2 : Schematic diagram of a system and method for preparing fertilizer according to another non-limiting example of the systems and methods disclosed herein. DETAILED DESCRIPTION

[0078] Certain aspects of the present disclosure provide benefits over existing fertilizers, including nutrients contained in the fertilizer having slow-release properties. Certain aspects provided herein allow fertilizers to slowly release nutrients into the soil over a period of time, such as throughout the growth cycle of a plant. In some aspects, this capability can be achieved without the use of binders, inhibitors, or other interventions that add compounds other than fertilizer nutrients. In some embodiments, the fertilizer includes a double salt, such as a metallic ammonium nitrate, such as calcium ammonium nitrate, and a water-soluble nutrient, such as ammonium sulfate ((NH4)2SO4), which can be a composition and / or a homogeneous mixture. The metallic ammonium nitrate compound can serve as a binder for other components in the fertilizer. Moreover, calcium ammonium nitrate is safer and more stable than ammonium nitrate.

[0079] I. Fertilizer

[0080] Certain embodiments herein relate to compound fertilizers comprising: a double salt, such as a metal ammonium nitrate, which may include calcium ammonium nitrate. Certain aspects relate to synthesizing nutrient complexes using fertilizer ingredients from natural sources, such as calcium ammonium nitrate, ammonium sulfate, calcium nitrate, sulfuric acid, ammonium hydroxide, ammonium nitrate, calcium sulfate, nitric acid, and / or ammonia. In some aspects, the compound fertilizer is a mixture, wherein the mixture is a homogeneous mixture.

[0081] The fertilizer may be a fertilizer granule that may comprise a mixture containing calcium (Ca), nitrogen (N) in the form of ammonium and / or nitrates, and sulfur (S) in the form of sulfates. The ratio of the elements present in the fertilizer may be adjusted according to the specific application.

[0082] At least a portion of the Ca can be present in the form of calcium ammonium nitrate. In some aspects, based on the total weight of Ca in the mixture, the Ca in the mixture can be present in the form of calcium ammonium nitrate in an amount of at least 90% by weight, or at least 95% by weight, or between 90% by weight and 100% by weight, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, and 100% by weight. In some embodiments, at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following Ca in the mixture may be present in the form of calcium ammonium nitrate: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 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%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 9 wt%, 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%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 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%, %, 75 wt %, 76 wt %, 77 wt %, 78 wt %, 79 wt %, 80 wt %, 81 wt %, 82 wt %, 83 wt %, 84 wt %, 85 wt %, 86 wt %, 87 wt %, 88 wt %, 89 wt %, 90 wt %, 91 wt %, 92 wt %, 93 wt %, 94 wt %, 95 wt %, 96 wt %, 97 wt %, 98 wt %, 99 wt %, 99.5 wt % and 100 wt %.

[0083] In some aspects, the compound fertilizer may contain: i) calcium ammonium nitrate, based on the total weight of the mixture and / or fertilizer granules, the amount of calcium ammonium nitrate is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1 weight %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight %, 10 weight %, 11 weight %, 12 weight %, 13 weight %, 14 weight %, 15 weight %, 16 weight %, %, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight %, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight %, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.% by weight, 5% by weight, and 100% by weight; and ii) ammonium sulfate, based on the total weight of the mixture and / or the fertilizer granules, in an amount of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, %, 17 wt %, 18 wt %, 19 wt %, 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 %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt %, 44 %, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 2%, 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% by weight.

[0084] In some aspects, the homogeneous mixture comprises Ca, N, and / or S, wherein i) the Ca content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 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%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 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%, 75 wt%, 76 wt %, 16 wt %, 17 wt %, 18 wt %, 19 wt %, 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 %, 35 wt %, 36 wt %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, 41 wt %, 42 wt %, 43 wt % %, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 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%, 2 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.5 wt % and 100 wt %, ii) the N content of the homogeneous mixture may be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, 16 wt %, 17 wt %, 18 wt % %, 19 wt%, 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%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 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%, 3 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight, 9 wt%, 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%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 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%, %, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 99.5wt% and 100wt%.

[0085] Ca, N and / or S can exist in the form of a water-soluble compound or a water-insoluble compound and / or be derived from a water-soluble compound or a water-insoluble compound. In some cases, Ca, N and / or S can exist in the form of a salt. In some aspects, Ca, N and / or S can exist in the form of a water-soluble salt. In some cases, the water-soluble S salt and N salt can be ammonium sulfate. The Ca salt, N salt and / or S salt can be in the form of a non-hydrate and / or one or more than one hydrate.

[0086] In some aspects, the calcium sulfate is gypsum. In some aspects, the gypsum is red gypsum or waste gypsum, and / or the gypsum is derived from red gypsum or waste gypsum, or the gypsum is contained in red gypsum or waste gypsum.

[0087] The dried fertilizer may have a moisture content of less than 1% by weight, based on the weight of the fertilizer granules, such as from 0.1% to 0.9% by weight, or any one or two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% by weight, or any range thereof. As a non-limiting example, the moisture content can be measured by drying a sample at 50° C. for 25 minutes and measuring the mass loss of the fertilizer after drying.

[0088] Fertilizer can be any suitable shape.Non-restrictive shape comprises sphere, cube, cylinder, spherical, ovate and oblong.In some respects, granular fertilizer can be cylindrical, and it has the cross section of circle, ellipse, ovate, triangle, square, rectangle, pentagon or hexagon, but also can be made into the cylindrical core that has cross section and is other shapes.In some respects, the widest size of granular fertilizer can be 0.5mm to 6mm, or 0.5mm to 5mm, preferred 1mm to 4mm, or for at least following any one, following any one at the most, equal following any one or between following any two: 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm and 6mm. In some specific aspects, the fertilizer granules can be substantially spherical with an average diameter of 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 the following, at most any one of the following, equal to any one of the following, or between any two of the following: 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.

[0089] The fertilizer can be water dispersible and / or soil dispersible. In some aspects, the fertilizer particles having a size of 2 mm to 4 mm before addition to the water can be disintegrated into microparticles having a size of 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 particles to water having a pH of 7 at ambient temperature with stirring at a rate of 90 rpm to 110 rpm.

[0090] The mixture can have a substantially uniform composition. In some cases, the composition of a 1 mm x 1 mm x 1 mm cube at any location in the mixture can be similar (within ±20%, or ±10%, or ±5%, or ±3%, ±2%, or ±1%, or ±0.5%) to the composition of a 1 mm x 1 mm x 1 mm cube at any other location in the mixture.

[0091] In some aspects, the fertilizer granules may comprise a homogeneous mixture. The homogeneous mixture may have a composition as described above. In some cases, the homogeneous mixture may have an optional coating on the outer surface of the homogeneous mixture. In some cases, calcium ammonium nitrate may serve as a binder in the fertilizer. In some cases, calcium ammonium nitrate is the only binder in the fertilizer. In some cases, calcium ammonium nitrate forms an amorphous phase, a continuous phase, and / or encapsulates other components in the fertilizer. In some cases, the fertilizer comprises a matrix of calcium ammonium nitrate that at least partially surrounds and / or encapsulates at least a portion of the ammonium sulfate. In some cases, the fertilizer comprises particles of calcium ammonium nitrate and / or microparticles of ammonium sulfate.

[0092] In some respects, the fertilizer may include or not include other fertilizer materials. If other fertilizer materials are included, other fertilizers can be selected based on the special needs of certain types of soil, climate or other growth conditions to maximize the effectiveness of fertilizer in enhancing plant growth and crop yield. The fertilizer may also include or not include extra additives. Non-limiting examples of the additives that can be included or excluded from the fertilizer of the present invention include extra nitrogen nutrients, extra phosphorus nutrients, extra potassium nutrients, extra trace element nutrients and / or extra secondary nutrients. Trace element nutrients can be copper, iron, chloride, manganese, molybdenum or nickel or their arbitrary combination. Nitrogen nutrients can be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde resin, ammonium chloride and potassium nitrate. In some respects, extra secondary nutrients can include lime and / or superphosphate. In some cases, extra fertilizer materials and / or extra additives are included in the optional coating of the fertilizer.

[0093] In some cases, the inhibitor comprises a nitrification inhibitor and / or a urease 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), In one aspect, the nitrification inhibitor may include DMPP, DCD, TU, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or a combination thereof. In some embodiments, the fertilizer composition may include NBTPT, DMPP, TU, DCD, PPDA, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST, or a combination thereof.

[0094] In some cases, the adhesive includes phosphate, polyphosphate, biodegradable polymer or wax or its combination. Suitable wax includes but is not limited to vegetable wax, high melting point wax, ethylene bis stearamide wax, paraffin, polyethylene wax and olefin wax. Suitable phosphate includes but is not limited to diammonium phosphate (diammonium phosphate) and monoammonium phosphate (monoammonium phosphate). Suitable polyphosphate includes but is not limited to ammonium polyphosphate. Suitable biodegradable polymer includes but is not limited to polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid and other biodegradable polymer materials, such as polylactic acid, poly (3-hydroxypropionic acid), polyvinyl alcohol, poly ε-caprolactone, poly L-lactide, polybutylene succinate, and biodegradable starch-based polymer. Adhesive can include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silicon dioxide or its combination. Suitable flour includes but is not limited to rice flour, wheat flour and bleached wheat flour. Suitable starch includes but is not limited to dextrin modified starch.

[0095] In some cases, the pH buffer comprises MgO, KH2PO4, NaHCO3, chalk powder, aluminum hydroxide, magnesium hydroxide, aluminum hydroxide / magnesium hydroxide coprecipitate, aluminum hydroxide / sodium bicarbonate coprecipitate, 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, 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 pyrophosphate, tripotassium phosphate, trisodium phosphate, and tromethamine, and combinations thereof.

[0096] Fertilizers as described herein can be included in compositions for application to soil. In some aspects, in addition to fertilizers as described herein, compositions can also include other fertilizer compounds, trace element nutrients, primary nutrients, urea, other nitrogen nutrients, pesticides, herbicides or fungicides or combinations thereof. Fertilizers as described herein can also be included in blended compositions comprising other fertilizers. Other fertilizers can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), monopotassium phosphate (MKP), triple superphosphate (TSP), phosphate rock, superphosphate (SSP), ammonium sulfate, etc.

[0097] The granulated fertilizer can have desired physical properties, such as a desired degree of abrasion resistance, granule strength, granulation, hygroscopicity, granule shape, and particle size distribution. In some aspects, the compressive strength of the fertilizer granules can be greater than 1.5 kgf, such as greater than 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 2 kgf, 2.5 kgf, 3 kgf, 3.5 kgf, 4 kgf, 4.5 kgf, 5 kgf, 5.5 kgf, and 6 kgf. The bulk density of the fertilizer granules can be between 1 g / cm3 and 1.2 g / cm3, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1 g / cm3, 1.02 g / cm3, 1.04 g / cm3, 1.06 g / cm3, 1.08 g / cm3, 1.1 g / cm3, 1.12 g / cm3, 1.14 g / cm3, 1.16 g / cm3, 1.18 g / cm3, and 1.2 g / cm3. In some aspects, 10 mg or more, for example, 10 mg to 40 mg, or at least any one of, at most any one of, equal to, or between any two of the following fertilizer granules can be dissolved in 1 mL of water at a pH of 7 with stirring at a rate of 90 rpm to 110 rpm and at ambient temperature within 5 minutes of adding 100 mg of the fertilizer granules to the water. In some aspects, the fertilizer granules can lose less than 0.13 weight percent in an attrition loss test, e.g., 0.02 weight percent to 0.12 weight percent, or lose at most, equal to, or between any two of: 0.02 weight percent, 0.03 weight percent, 0.04 weight percent, 0.05 weight percent, 0.06 weight percent, 0.07 weight percent, 0.08 weight percent, 0.09 weight percent, 0.1 weight percent, 0.11 weight percent, and 0.12 weight percent. Attrition loss can be measured using the following attrition loss test.

[0098] Abrasion loss test: Weigh a number of sieved particles with a single particle size of 2 mm to 4 mm and a total volume of 100 cm 3Fertilizer granules (W1) of 100 g were placed in a test drum along with 50 stainless steel balls weighing a total of 100 g. The drum was closed and rotated at 30 rpm for 10 minutes. The balls were then separated from the sample and the material was sieved on a 2 mm sieve using a vibrating sieve shaker. The total weight of the granules on the 2 mm sieve was then reweighed (W2). The results were calculated as weight loss in % using the following formula:

[0099]

[0100] II. Method for preparing fertilizer

[0101] Reference Figure 1 , depicts a schematic diagram of a system and method for preparing fertilizer according to one embodiment of the present invention. System 100 may include a granulator 102 and a dryer 104. A feed mixture 106 may be granulated in granulator 102, with or without water, to form a wet granulated mixture 108. If water is present, it may be provided with feed mixture 106, and / or it may be added separately to granulator 102. Wet granulated mixture 108 may be dried in dryer 104 to obtain a dry granulated mixture 110 containing fertilizer.

[0102] Reference Figure 2, depicts a schematic diagram of a system and method for preparing fertilizer according to another embodiment of the present invention. System 200 may include a mixer / reactor 212, although the mixer and reactor may be two, three, four, or more components, such as two reactors and a mixer or one reactor and a mixer. System 200 may include a granulator 202, a pelletizer 214, one or more particle size screens 216, and a dryer 204, or any combination thereof. Feed mixture components 218 may be added to mixer / reactor 212 individually and / or in any possible combination. In mixer / reactor 212, the feed components may react and / or mix to form feed mixture 206. Feed mixture 206 may be granulated in granulator 202, with or without additional water, to form wet granulated mixture 220. The particles in wet granulated mixture 220 may be spheroidized in pelletizer 214 to form wet granulated mixture 222 containing substantially spherical particles. The wet granulated mixture 222 can be passed through one or more size screens 216 to separate particles smaller than or larger than the desired size from the wet granulated mixture 222 to obtain a wet granulated mixture 224 containing particles of the desired size. At least a portion of the particles 226 separated from the granular mixture 224 containing particles of the desired size can be recycled to the granulator 202. The wet granulated mixture 224 containing particles of the desired size can be dried in the dryer 204 to obtain a dry granulated mixture 210 containing fertilizer particles. In some aspects, the mixer / reactor 212 can include a ribbon mixer.

[0103] The feed mixture composition 218 may include i) a Ca source, such as calcium sulfate, ii) a N source, such as nitric acid, NH4 + , NH4OH and / or NH3, iii) a source of S, such as calcium sulfate. In some cases, the mixture components provide more than one of Ca, N and / or S. In some cases, the mixture components provide additional nutrients and / or trace elements, such as P, K, Mg, Fe and / or Si. In certain aspects, one or more components may be added as an aqueous solution. In some cases, the mixture components are provided in powder form. In some cases, one or more components may be added as a gas. In some cases, NH3 is provided at a pressure higher than 1 bar, for example, or at a pressure between or in any range of 1.2 bar, 1.3 bar, 1.4 bar, 1.5 bar, 2 bar, 2.5 bar, 3.5 bar, 4 bar, 4.5 bar, 5 bar, 5.5 bar, 6 bar, 6.5 bar, 7 bar, 7.5 bar, 8 bar, 9 bar, 10 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar and 40 bar. In some cases, some of the mixture ingredients are provided in powder form.

[0104] The feed mixture 106 , 206 may contain Ca, N, and / or S. In some aspects, the feed mixture 106 , 206 may contain calcium ammonium nitrate, ammonium sulfate, calcium nitrate, sulfuric acid, ammonium hydroxide, ammonium nitrate, calcium sulfate, nitric acid, and / or ammonia.

[0105] Water can be added to the feed mixture in the mixer / reactor 212 and / or pelletizer 102, pelletizer 202. In certain aspects, water can be added to the feed mixture (e.g., together with one or more feed mixture components and / or separately) in a total amount of 5 grams to 20 grams, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following, per 100 grams of feed mixture: 5 grams, 6 grams, 7 grams, 8 grams, 9 grams, 10 grams, 11 grams, 12 grams, 13 grams, 14 grams, 15 grams, 16 grams, 17 grams, 18 grams, 19 grams, and 20 grams.

[0106] In some aspects, granulator 102 and granulator 202 can be drum granulator, paddle granulator, disc granulator, solid mixer, wear-resistant drum, extruder, high shear mixing granulator, roller granulator, Mycromix or round bottom flask. In granulator 102 and granulator 202, feed mixture 106 and feed mixture 206 can be granulated by agglomeration, spray granulation, compaction, slurry granulation and / or high shear mixing granulation. In some specific aspects, feed mixture 106 and feed mixture 206 can be granulated by compaction in granulator 102 and granulator 202. In some aspects, granulator 102 and granulator 202 can contain at least two rollers, and compaction granulation can include using at least two rollers to compress the feed mixture. In some aspects, in the compaction process, two rollers can move in countercurrent direction. In some aspects, the feed mixture can be compressed into a shaped pellet, such as a cylindrical pellet, by at least two rollers. In some aspects, the surface of a roller can have the hole of expectation, so that the feed mixture is compressed into the hole, and the surface of another roller can push the feed mixture into the hole. The pressure in the granulation process, for example, the pressure in the compacting granulation process, can be 1 bar to 40 bar, or be at least any one of the following, at most any one of the following, equal to any one of the following or between any two of the following: 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 10 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar and 40 bar. In certain aspects, the feed mixture can be pelletized in pelletizer 102, pelletizer 202 at a temperature between ambient temperature and 50°C, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: -20°C, -15°C, -10°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, and 50°C.

[0107] In some aspects, the reaction, mixing, and granulation of the feed mixture components can be carried out in different containers, for example, the mixer / reactor 212 and the granulator 202 can be different containers. In some aspects, the reaction, mixing, and granulation of the feed mixture components can be carried out in the same container, for example, 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. As a non-limiting example, in some cases, calcium ammonium nitrate and ammonium sulfate are formed in two different containers. In some cases, calcium ammonium nitrate and ammonium sulfate are formed in one container. In some cases, ammonium nitrate and sulfuric acid are formed in two different containers. In some cases, ammonium nitrate and sulfuric acid are formed in one container. In some cases, calcium nitrate and ammonium sulfate are formed in two different containers, calcium ammonium nitrate and calcium nitrate are formed in two different containers, and calcium ammonium nitrate and ammonium sulfate are formed in one container. In some cases, calcium ammonium nitrate, calcium nitrate, ammonium nitrate, and ammonium sulfate are formed in one container. In some cases, calcium ammonium nitrate, calcium nitrate, ammonium nitrate, and ammonium sulfate are each formed in separate containers.

[0108] In some aspects, the calcium ammonium nitrate, ammonium sulfate, calcium nitrate, sulfuric acid, and ammonium nitrate are formed at a temperature of at least, at most, equal to, or between any two of: 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 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℃, for example at a temperature of 30℃ to 80℃ or at 100℃ to 150℃ or at 75℃ to 150℃ or at 55℃ to 75℃ or at 30℃ to 150℃.

[0109] In some cases, the fertilizer can be extruded before drying. The extruder can extrude the fertilizer at a pressure of at least 1 bar, at most 1 bar, at least ... The extruder can extrude the fertilizer at a temperature of at least, at most, equal to, or between any two of -20° C., -15° C., -10° C., 0° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., and 50° C. The extrudate can be sliced ​​or divided before drying, for example, by a die.

[0110] In some aspects, the desired size of the final fertilizer product, such as granules, can be 0.5 mm to 5 mm, or 1 mm to 4 mm, and can have a size less than 0.5 mm or 1 mm and / or a size greater than 4 mm or 5 mm that can be separated from the wet granulated mixture 222 using one or more particle size screens 216. In some aspects, the wet granulated mixture can be spheronized and / or spheronized in a spheronizer. In some cases, the wet granulated mixture is contacted with the spheronizer for at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 5 seconds, 10 seconds, 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 50 seconds, or 60 seconds. In some cases, the pelletizer has a turntable or rotatable disk that can rotate at a speed of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 200 rpm, 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm. In certain aspects, the wet granulated mixture can be dried in dryer 104, dryer 204 at a temperature of 40° C. to 150° C., or at a temperature of at least any one of, at most any one of, equal to, or between any two of the following: 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C. In certain aspects, dryer 104, dryer 204 can be a fluidized bed dryer, a rotary drum dryer, or an airflow dryer. In some aspects, the wet granulated mixture can be dried in dryer 104, dryer 204 with a hot air flow having a flow rate of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 100 cubic meters / hour, 150 cubic meters / hour, 200 cubic meters / hour, 250 cubic meters / hour, 300 cubic meters / hour, 350 cubic meters / hour, 400 cubic meters / hour, 450 cubic meters / hour, and 500 cubic meters / hour, and / or a rotation speed of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 5 rpm, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm, 35 rpm, 40 rpm, 45 rpm, and 50 rpm.

[0111] III. Methods of using fertilizers

[0112] Fertilizers of the present disclosure, including fertilizer granules, compositions containing fertilizers, and blended fertilizers containing fertilizers of the present disclosure, can be used in methods for increasing the amount of one or more plant nutrients in soil and enhancing plant growth. These methods can include applying an effective amount of a composition and / or blend containing the fertilizers of the present disclosure to the soil. The methods can include increasing the growth and yield of crops, trees, ornamental plants, and the like, such as palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. The methods can include applying the fertilizer blends of the present disclosure to at least one of soil, an organism, a liquid carrier, a liquid solvent, and the like. The one or more compositions containing fertilizers and / or the one or more fertilizer blends can be applied to plants and / or soil as a topdressing, a base fertilizer, and / or by any suitable application method.

[0113] Non-limiting examples of plants that can benefit from the fertilizer of the present invention include vines, trees, shrubs, straw plants, ferns, etc. Plants can include orchard crops, vines, ornamental plants, food crops, trees, and harvested plants. Plants can include gymnosperms, angiosperms, and / or ferns.

[0114] After applying the fertilizer composition to the soil, the effectiveness of the composition comprising the fertilizer of the present invention can be determined by measuring the amount of phosphorus and optionally other nutrients in the soil at various times. It will be appreciated that different soils have different properties that can affect the stability of nutrients in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by side-by-side comparison in the same soil under the same conditions.

[0115] Example

[0116] The present invention will be described in more detail by way of specific examples. The following examples are provided only for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize various noncritical parameters that can be varied or changed to produce substantially the same results.

[0117] Example 1

[0118] Fertilizer preparation

[0119] 50 g of calcium sulfate can be mixed with 92 g of nitric acid at a temperature of 40° C. and stirred for 2 hours. This reaction can convert the calcium sulfate into calcium nitrate while producing sulfuric acid. The amount of nitric acid used in the reaction vessel can be more than the amount required for the stoichiometric reaction. 22.3 g of ammonia can react with the in-situ generated sulfuric acid and excess nitric acid to form ammonium sulfate and ammonium nitrate, respectively. The in-situ formed ammonium nitrate can form a double salt with the in-situ formed calcium nitrate to form calcium ammonium sulfate, such as, but not limited to, Ca(NH4)2(NO3)4. The produced material comprises calcium ammonium sulfate and ammonium sulfate. The produced material can be gradually dried at 60° C. until a dry material is formed. Final drying of the material can be carried out in an oven at 80° C. for 12 hours.

[0120] The produced fertilizer may contain 19.5 wt% N, 4.5 wt% Ca and 12.9 wt% S.

[0121] ***

[0122] All methods disclosed and claimed herein can be prepared and implemented according to the present disclosure without undue experimentation. Although the compositions and methods of the present invention have been described in accordance with preferred embodiments, it will be apparent to those skilled in the art that variations can be implemented in the methods and in the steps or sequence of steps of the methods described herein without departing from the concept, spirit, and scope of the present invention. More specifically, it will be apparent that specific reagents related to both chemical and physiological aspects can replace the reagents described herein while achieving the same or similar results. All such similar substitutions and changes apparent to those skilled in the art are considered to be within the spirit, scope, and concept of the present invention as defined by the appended claims.

Claims

1. A fertilizer composition comprising calcium ammonium nitrate and ammonium sulfate ((NH4)2SO4).

2. The fertilizer composition according to claim 1, wherein the composition comprises 17 to 22 wt% nitrogen (N), 3 to 7 wt% calcium (Ca), and 10 to 15 wt% sulfur (S).

3. The fertilizer composition according to any one of claims 1 and 2, wherein the composition further comprises calcium nitrate (Ca(NO3)2), sulfuric acid (H2SO4) and / or ammonium nitrate (NH4NO3).

4. The fertilizer composition according to any one of claims 1 to 3, wherein the composition further comprises calcium sulfate (CaSO4), nitric acid (HNO3), ammonium hydroxide (NH4OH) and / or ammonia (NH3).

5. The fertilizer composition of claim 4, wherein the composition comprises calcium sulfate contained in waste gypsum and / or recycled gypsum.

6. The fertilizer composition according to any one of claims 1 to 5, wherein the composition does not contain a binder other than calcium ammonium nitrate.

7. The fertilizer composition according to any one of claims 1 to 6, wherein at least part of the ammonium sulfate is adsorbed on the surface of the calcium ammonium nitrate.

8. The fertilizer composition according to any one of claims 1 to 7, wherein the fertilizer composition further comprises a phosphorus source and / or a potassium source.

9. The fertilizer composition according to any one of claims 1 to 8, wherein the fertilizer is homogeneous.

10. A fertilizer composition according to any one of claims 1 to 9, wherein the composition comprises a gel.

11. The fertilizer composition according to any one of claims 1 to 10, wherein the composition comprises a dried gel.

12. The fertilizer composition of any one of claims 1 to 11, wherein at least a portion of the ammonium sulfate is encapsulated by calcium ammonium nitrate.

13. The fertilizer composition according to any one of claims 1 to 12, wherein the fertilizer composition is a granular fertilizer.

14. The fertilizer composition of any one of claims 1 to 13, wherein the composition does not comprise at least one of urea, ammonium nitrate, or a polymer.

15. A method for preparing the fertilizer composition according to any one of claims 1 to 14, comprising the following steps: (a) contacting calcium sulfate with nitric acid and an ammonia source to produce a first reaction product comprising: calcium nitrate, sulfuric acid, and ammonium nitrate; and (b) contacting the first reaction product with calcium nitrate and an ammonia source to produce a second reaction product comprising: Calcium ammonium nitrate and ammonium sulfate.

16. The method of claim 15, wherein step (a) comprises: Calcium sulfate is contacted with nitric acid to produce a product comprising: calcium nitrate and sulfuric acid; and The nitric acid is contacted with an ammonia source to produce a product comprising: ammonium nitrate, and / or Step (b) comprises: Calcium nitrate is contacted with ammonium nitrate to produce a product comprising: calcium ammonium nitrate; and The sulfuric acid is contacted with an ammonia source to produce a product comprising: Ammonium sulfate.

17. The method of any one of claims 15 to 16, further comprising drying the second reaction product to form a solid fertilizer composition.

18. A method according to any one of claims 15 to 17, wherein the calcium sulfate comprises red gypsum and / or waste gypsum from phosphoric acid production, and / or wherein the ammonia source is ammonium hydroxide and / or ammonia.

19. The method according to any one of claims 15 to 18, wherein step (a) and / or step (b) occurs at 30°C to 150°C and / or lasts for 30 minutes to 12 hours.

20. A method of fertilizing, the method comprising contacting plants, soil, water, or a combination thereof with the fertilizer composition of any one of claims 1 to 14.

Images