KNH4SO4, CaCO3 and CaCl2 fertilizer

Abstract

Fertilizer containing a mixture containing potassium ammonium phosphate, slow release calcium, and immediate release calcium, and methods of making and using the fertilizer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of European Patent Application No. 22182220.8 filed on June 30, 2022, the entire contents of which are incorporated herein by reference. Background Art

[0003] I. Technical field

[0004] The present disclosure generally relates to fertilizers containing calcium. In specific embodiments, the present disclosure relates to fertilizers containing calcium, potassium, carbon, and sulfur.

[0005] II. Background

[0006] Soil nutrients, such as nitrogen, phosphorus, potassium and sulfur, and trace elements such as iron, zinc, copper and magnesium, are useful for achieving agricultural prosperity and plant growth. After repeated cropping cycles, the amount of these nutrients in the soil may be depleted, resulting in inhibited plant growth and reduced yields. To offset this effect, fertilizers have been developed to help replenish depleted important nutrients. Single-nutrient fertilizers and multi-nutrient fertilizers, such as fertilizer blends, have been developed to meet the different needs of crop production around the world.

[0007] The application of fertilizers does not always provide plants with all the nutrients in the fertilizer in a short period of time. Some fertilizers contain nutrients that contain compounds that are not readily available to plants after application. In these cases, some people apply fertilizers long before the plants are planted, or some people over-fertilize close to the time when the plants are planted to provide plants with sufficient nutrients in the early stages. However, this comes at the expense of time and may require multiple soil treatments before or after planting and / or increased costs.

[0008] Plants, such as crops, need nutrients at least during their entire growth period and maturity, except for quick-release (immediate release) fertilizers. However, many fertilizers, after being dispersed and applied to the soil, can be degraded or absorbed in a short time after application. In order to solve this problem, fertilizers can be applied to the same plant multiple times or slow-release (slow release) fertilizers can be used. Some methods of slow-release fertilizers are included in the fertilizer core coating polymer. However, many polymer coatings are expensive and can accumulate undesirably in the soil over time after repeated application.

[0009] Fertilizing plants can increase the growth of plants and the yield of plants, and increase the photosynthesis of plants. Accordingly, the increase in plant photosynthesis will increase the consumption of carbon dioxide (CO2), which is the most important issue in many industries due to environmental awareness and industrial regulations. However, the production of some fertilizers, the transportation of fertilizers and other activities related to the fertilizer industry can produce CO2. Some industries have tried to capture CO2 and store CO2 or chemically change CO2 to meet environmental protection goals and regulatory requirements. As an example, CO2 has been captured and reacted to produce CO, urea or other products with industrial value or products that can be stored. However, these reactions usually require excessive energy consumption. As another example, some industries are working hard to store CO2 in deep underground layers.

[0010] There needs to be other ways to reduce CO2 as well as provide other cost-effective fertilizers and other methods of producing cost-effective fertilizers. Summary of the invention

[0011] Disclosed herein are solutions to at least some of the problems discussed above, including providing quick-release calcium and slow-release calcium in a fertilizer product that also consumes CO2 in the production of the fertilizer. In one aspect, the solution is to provide a fertilizer comprising potassium ammonium sulfate (KNH4SO4); and at least two different calcium (Ca) compounds. In some cases, at least part of the Ca may be present in the form of calcium carbonate and / or calcium chloride. The method for producing the fertilizer is capable of consuming CO2 as well as NH3 and CaSO4. In some cases, CO2, NH3 and CaSO4 may be derived from waste products, such as CO2 and / or NH3 from waste products of a manufacturing plant, and CaSO4 from phosphogypsum of phosphoric acid production, or CaSO4 from slag of metal smelting or metal refining. Phosphogypsum may be generated as a by-product in the phosphoric acid production process. Therefore, the raw materials may be readily available and the use of the raw materials may reduce waste. In some embodiments, the synthesis of at least part of the fertilizer occurs by reacting calcium sulfate (CaSO4) with carbon dioxide (CO2) and ammonia (NH3).

[0012] CaSO4.2H2O+CO2+2NH3→CaCO3+(NH4)2SO4+H2O

[0013] In some embodiments, potassium chloride (KCl) is also reacted with CaSO4, CO2, and NH3 to produce a fertilizer.

[0014] 2CaSO4+H2O+CO2+2NH3+2KCl→CaCO3+2KNH4SO4+CaCl2

[0015] Intermediate reactions to produce fertilizer may include:

[0016] 2KCl+CaSO4→CaCl2+K2SO4

[0017] K2SO4+NH3+H2O→KNH4SO4+KOH

[0018] 2KOH+CaSO4→K2SO4+Ca(OH)2

[0019] Ca(OH)2+CO2→CaCO3+H2O.

[0020] The final product may contain a mixture of the chemical substances of the above combination, which includes KNH4SO4 / CaCl2 / CaCO3 complex. In some cases, CaCl2 and CaCO3 are produced simultaneously, generating a mixture of CaCl2 / CaCO3. In some embodiments, when the mixture is used as a fertilizer, this mixture can be used for the quick release of calcium by CaCl2, and can also be used for the controlled slow release of calcium by CaCO3. In some embodiments, CaCO3 at least partially encapsulates KNH4SO4 and / or CaCl2, which can slow down the release of nutrients from these at least partially encapsulated compounds.

[0021] Fertilizers herein may contain nitrogen and sulfur as well as calcium, which are essential for plant growth, overall health, and yield. Calcium plays a role in the production of plant tissues and therefore promotes plant growth. For example, calcium may be responsible for holding the cell walls of plants together. Calcium can also activate certain enzymes and is used to send signals that coordinate certain cellular activities. Calcium can be used to treat blossom end rot in tomatoes and tip burn in cabbage. Calcium can also be used to reduce the risk of bitter pit, fruit softening, postharvest damage, and slight cracking.

[0022] The fertilizers disclosed herein may also contain chlorine compounds, such as CaCl2. Chlorine compounds can improve plant growth, tissue water balance, plant water relations, photosynthetic performance, and water use efficiency. They can increase plant biomass and can also improve nitrogen (N) use efficiency. Miguel Rosales et al. (Front. Plant Sci., 26 May 2020) showed that Cl - Promote NO3 in plants - The chlorine content can be varied to meet the needs of crops. In some embodiments, chlorine-containing mixtures are used in high rainfall areas.

[0023] One aspect of the present invention relates to fertilizer. The fertilizer may include a homogeneous mixture comprising a KNH4SO4 double salt and at least two different calcium compounds. One of the two different calcium compounds may be calcium chloride (CaCl2). One of the two different calcium compounds may be calcium carbonate (CaCO3). In some aspects, the two different calcium compounds include CaCl2 and CaCO3. In some aspects, slow-release calcium, such as CaCO3, may at least partially encapsulate at least a portion of the KNH4SO4 double salt and / or CaCl2. In some cases, the encapsulation may be attributed to the method for producing fertilizer disclosed herein. In some aspects, sulfur is derived from recycled gypsum and / or waste gypsum, such as phosphogypsum. In some aspects, CO2 is derived from a waste stream and / or is concentrated by a waste stream.

[0024] In certain aspects, the fertilizer comprises 12 wt % to 16 wt % nitrogen, e.g., 12 wt % to 15 wt % nitrogen, which may be in the form of ammonium (NH4), 20 wt % to 23 wt % sulfur, which may be in the form of sulfate (SO4), and 10 wt % to 14 wt % potassium (K), wherein the wt % are based on the total weight of the fertilizer.

[0025] Certain aspects relate to a method for preparing a fertilizer, the fertilizer comprising any fertilizer described herein. The method may include steps (a), (b) and / or (c). In step (a), calcium sulfate, such as a calcium sulfate suspension, may be contacted with ammonia and carbon dioxide to generate a first product comprising calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4). In step (b), calcium sulfate, which may or may not be from the same calcium sulfate source in step (a), such as a calcium sulfate suspension, may be contacted with potassium chloride to generate a second product comprising calcium chloride (CaCl2) and potassium sulfate (K2SO4). In step (c), the product from step (a) and the product from step (b) may be mixed to generate fertilizer. The source of calcium sulfate from step (a) or step (b) may include gypsum, such as phosphogypsum. In some aspects, step (b) includes contacting at least a portion of the first product with potassium chloride. In some aspects, at least a portion of the calcium sulfate of step (b) is obtained from the unreacted calcium sulfate of step (a). In some aspects, all of the calcium sulfate of step (b) is obtained from the unreacted calcium sulfate of step (a). In some aspects, in step (b), at least a portion of the first product is reacted with potassium chloride to produce KNH4SO4 by, for example, the following reaction:

[0026] K2SO4+NH3+H2O→KNH4SO4+KOH.

[0027] In some aspects, step (c) produces a fertilizer comprising KNH4SO4, CaCl2, and CaCO3. Step (a) and / or step (b) can occur at about 40°C to 80°C, such as at any one of the following temperatures, between the following temperatures, above the following temperatures, or below the following temperatures, or any range thereof: 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℃ or 90℃.

[0028] The following Aspect 1 to Aspect 15 of the present invention are also disclosed.

[0029] Aspect 1 is a fertilizer comprising a mixture, the mixture comprising:

[0030] Potassium ammonium sulfate (KNH4SO4); and

[0031] At least two different calcium compounds.

[0032] Aspect 2 is the fertilizer according to aspect 1, wherein the at least two different calcium compounds comprise calcium chloride (CaCl 2 ).

[0033] Aspect 3 is the fertilizer according to any one of aspects 1 or 2, wherein the at least two different calcium compounds comprise calcium carbonate (CaCO 3 ).

[0034] Aspect 4 is the fertilizer according to any one of aspects 1 to 3, wherein CaCO 3 at least partially encapsulates at least a portion of KNH 4 SO 4 .

[0035] Aspect 5 is the fertilizer according to any one of aspects 1 to 4, wherein the at least two different calcium compounds comprise CaCl 2 and CaCO 3 .

[0036] Aspect 6 is the fertilizer according to aspect 5, wherein the weight ratio of CaCO 3 to CaCl 2 is 4:1 to 10:1.

[0037] Aspect 7 is a fertilizer according to any one of aspects 1 to 6, wherein the mixture comprises

[0038] 12 to 16 wt. % nitrogen in the form of ammonium;

[0039] 20 to 23 wt. % sulfur in the form of sulfate; and

[0040] 10 wt % to 14 wt % potassium; wherein the wt % are based on the total weight of the fertilizer.

[0041] Aspect 8 is a method for preparing a fertilizer, the method comprising

[0042] (a) contacting calcium sulfate with ammonia and carbon dioxide to produce a first product and optionally unreacted calcium sulfate, wherein the first product comprises calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4);

[0043] (b) contacting calcium sulfate with potassium chloride to produce a second product, the second product comprising calcium chloride (CaCl2) and potassium sulfate (K2SO4); and

[0044] (c) mixing the first product and the second product to produce a fertilizer.

[0045] Aspect 9 is a method according to aspect 8, wherein in step (a) and / or step (b), the source of calcium sulfate is gypsum.

[0046] Aspect 10 is a method according to any one of aspects 8 or 9, wherein step (b) comprises contacting at least a portion of the first product with potassium chloride.

[0047] Aspect 11 is a method according to aspect 10, wherein at least part of the calcium sulfate of step (b) is obtained from unreacted calcium sulfate of step (a).

[0048] Aspect 12 is a method according to any one of aspects 10 to 11, wherein all of the calcium sulfate of step (b) is obtained from unreacted calcium sulfate of step (a).

[0049] Aspect 13 is a method according to any one of aspects 10 to 12, wherein in step (b), at least a portion of the first product is contacted with potassium chloride to generate KNH4SO4 by reacting potassium sulfate with ammonia in water.

[0050] Aspect 14 is a method according to any one of aspects 8 to 13, wherein step (c) produces a fertilizer comprising KNH4SO4, CaCl2 and CaCO3.

[0051] Aspect 15 is a method according to aspects 8 to 14, wherein the contacting step (a) and / or the contacting step (b) occurs at about 50°C to 70°C.

[0052] Aspect 16 is the method according to any one of aspects 8 to 15, wherein the fertilizer comprises the fertilizer according to any one of aspects 1 to 5.

[0053] The term "fertilizer" is defined as a material that is applied to the soil or plant tissue to provide one or more plant nutrients essential or beneficial to plant growth and / or a stimulant or enhancer that increases or promotes plant growth.

[0054] The term "particle" may include solid materials. Particles may have a variety of different shapes, non-limiting examples of which include spheres, spheres, ovoids, rods, oblongs, or any shape.

[0055] The term "particle" may include solid material having a largest dimension less than 1 mm.

[0056] The term "particulate" or "powder" may include a plurality of particles.

[0057] The term "about" or "approximately" as used herein is defined as close to what is understood by those of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as within ±10% deviation, preferably within ±5%, more preferably within ±1%, and most preferably within ±0.5%.

[0058] The terms "wt %, "volume %" or "mole %" refer to the weight percent, volume percent or mole percent of a component based on the total weight, total volume or total moles of the material, respectively. In a non-limiting example, 10 grams of a component in 100 grams of a material is a 10 wt % component.

[0059] When used with the terms "including" or "comprising", the term without a quantifier can mean "a", but also has the meaning of "one or more", "at least one" and "one or more than one".

[0060] 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".

[0061] The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0062] Compositions and methods for their use may "comprise" or "contain," "consist essentially of," or "consist of" any ingredient or any step disclosed throughout the specification. Compositions and methods that "consist essentially of" any ingredient or any step disclosed 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.

[0063] 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. In addition, the compositions of the invention can be used to implement the methods of the invention.

[0064] Other objects, features and advantages of the present invention will become clear from the following detailed description. However, it should be understood that the detailed description and specific examples, although indicating specific embodiments of the present invention, are given by way of illustration only, because various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art based on this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The following drawings constitute part of this specification and are included to further demonstrate certain aspects of the present invention. The present invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments provided herein.

[0066] Figure 1 : A cross-sectional illustration of a fertilizer granule according to a non-limiting example of a fertilizer granule described herein.

[0067] Figure 2 : Schematic diagram of a system and method for producing fertilizer according to a non-limiting example of the systems and methods disclosed herein.

[0068] Figure 3 : Schematic diagram of a system and method for producing fertilizer according to another non-limiting example of the systems and methods disclosed herein. DETAILED DESCRIPTION

[0069] Some aspects of the present disclosure provide benefits that are superior to existing fertilizers, including quick-release properties and slow-release properties with calcium. Some aspects provided herein can make fertilizers release calcium quickly into the soil for plant use, and fertilizers can also be made to slowly release calcium into the soil over a period of time, such as throughout the growth cycle of plants. In some aspects, this dual release capability can be achieved without the intervention of compounds other than adhesives, inhibitors or other fertilizer nutrients. In some embodiments, fertilizers are composed of two calcium compounds and double salts, one of the two calcium compounds being quick-release and the other being slow-release, and the fertilizer can be a chemical composition and / or a uniform mixture. In some cases, the method for producing fertilizers can consume CO2 and NH3 and CaSO4. In some cases, CO2, NH3 and CaSO4 can be derived from waste products, such as CO2 and / or NH3 from waste products of a manufacturing plant and CaSO4 from phosphogypsum produced by phosphoric acid or CaSO4 from slag of metal smelting or metal refining. Phosphogypsum can be generated as a byproduct in the phosphoric acid production process. Therefore, the raw materials may be easily obtained and use of the raw materials may reduce waste.

[0070] I. Fertilizer

[0071] Certain embodiments herein relate to compound fertilizers comprising KNH4SO4, CaCO3 and CaCl2. Certain aspects relate to the synthesis of nutrient complexes using fertilizer ingredients from natural sources, such as CaSO4, KCl and CO2. In addition to these raw materials, ammonia is also used in some embodiments.

[0072] Fertilizer can be fertilizer granules, and the fertilizer can contain a homogeneous mixture, and the mixture contains calcium (Ca), potassium (K), nitrogen (N) in the form of ammonium, carbon (C) in the form of carbonate, and sulfur (S) in the form of sulfate. The ratio of the elements present in the fertilizer can be adjusted according to the specific application. At least part of Ca can exist in the form of calcium carbonate and / or calcium chloride. In some aspects, based on the gross weight of Ca in the homogeneous mixture, at least 90% by weight, or at least 95% by weight, or 90% by weight to 100% by weight, or at least any one of the following contents, at most any one of the following contents, equal to any one of the following contents, or between any two of the following contents, the Ca can exist in the form of calcium carbonate and / or calcium chloride: 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, 99.5% by weight, and 100% by weight. In some embodiments, the Ca in the homogeneous mixture may be present in the form of calcium carbonate in an amount of at least any one of the following amounts, at most any one of the following amounts, equal to any one of the following amounts, or between any two of the following amounts: 0.5 wt%, 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%, %, 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 %, and 99.5 wt %. In some embodiments, the Ca in the homogeneous mixture may be present in the form of calcium chloride in an amount of at least any one of the following amounts, at most any one of the following amounts, equal to any one of the following amounts, or between any two of the following amounts: 0.5 wt%, 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%, %, 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%, and 99.5 wt%. In some aspects, the homogeneous mixture may contain i) KNH4SO4 in an amount of at least any one of the following amounts, at most any one of the following amounts, equal to any one of the following amounts, or between any two of the following amounts, based on the total weight of the homogeneous mixture and / or the fertilizer granules: 0.5 wt%, 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%, 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%, and 99 wt%; ii) CaCO3, based on the total weight of the homogeneous mixture and / or the fertilizer granules, in an amount of at least any one of the following amounts, at most any one of the following amounts, equal to any one of the following amounts, or between any two of the following amounts: 0.5 wt%, 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 0 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%, %, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 7 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, and 99 wt%; and iii) CaCl2, based on the total weight of the homogeneous mixture and / or the fertilizer granules, in an amount of at least any one of the following amounts, at most any one of the following amounts, equal to any one of the following amounts, or between any two of the following amounts: 0.%, 5 wt %, 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 %, 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 %, and 99 wt %. In some cases, the weight ratio of CaCO 3 to CaCl 2 is at least any of the following ratios, at most any of the following ratios, equal to any of the following ratios, or between any two of the following ratios: 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and 10:1. .

[0073] In some aspects, the homogenous mixture comprises Ca, S, N and / or C, based on the total weight of the homogenous mixture and / or the fertilizer, wherein i) the Ca content of the homogenous mixture is at least any one of the following contents, at most any one of the following contents, equal to any one of the following contents, or between any two of the following contents: 0.5 wt%, 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% %, 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%, %, 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%, and 98.5 wt%, ii) the S content of the homogeneous mixture is at least any one of the following contents, at most any one of the following contents, equal to any one of the following contents, or between any two of the following contents: 0.5 wt%, 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% 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, 7 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%, and 98.5 wt%, iii) the N content of the homogeneous mixture is at least any one of the following contents, at most any one of the following contents, equal to any one of the following contents, or between any two of the following contents: 0.5 wt%, 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% 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, 7 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%, and 98.5 wt%, and iv) the C content of the homogeneous mixture is at least any one of the following contents, at most any one of the following contents, equal to any one of the following contents, or between any two of the following contents: 0.5 wt%, 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% 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 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%, and 98.5 wt%. .

[0074] Ca, S, N and / or C can exist in the form of water-soluble compounds or water-insoluble compounds or can be derived from water-soluble compounds or water-insoluble compounds. In some cases, Ca, S, N and / or C can exist in the form of salts. In some aspects, Ca, S, N and / or C can exist in the form of water-soluble salts. In some cases, water-soluble Ca salts can be CaCl2. Ca salts, S salts, N salts and / or C salts can be non-hydrate forms and / or one or more than one hydrate forms.

[0075] Fertilizer can be produced by the following steps: (a) contacting calcium sulfate with ammonia and carbon dioxide to produce a first product and optionally unreacted calcium sulfate, the first product comprising calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4); (b) contacting calcium sulfate with potassium chloride to produce a second product, the second product comprising calcium chloride (CaCl2) and potassium sulfate (K2SO4); and (c) mixing the first product and the second product to produce fertilizer.

[0076] Contacting step (a) and / or contacting step (b) may occur at any temperature suitable for causing the reaction, including at or between 40°C and 90°C, such as any one of, between, above, or below 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℃, 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℃ or 90℃.The contacting step (a) and / or the contacting step (b) may occur for any time sufficient to achieve 0.5%, 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%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111 1%, 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% or 100% of any of the starting materials are reacted for a period of time including the following: 0.5, 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 98, 99, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100, 100 Ammonia and / or carbon dioxide can be pressurized to any pressure suitable for the contacting step, for example, the pressure of the contacting step is within 5 bar to 30 bar, for example, any of the following pressures, between the following pressures, or above the following pressures, or below the following pressures: 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 11 bar, 12 bar, 13 bar, 14 bar, 15 bar, 16 bar, 17 bar, 18 bar, 19 bar, 20 bar, 21 bar, 22 bar, 23 bar, 24 bar, 25 bar, 26 bar, 27 bar, 28 bar, 29 bar, 30 bar.

[0077] Contact step (a) and contact step (b) can occur at the same time or at different times. Contact step (b) can occur when mixing step (c) is occurring. The raw materials for any step can be added at any time during any contact step, including when the contact step is occurring. The raw materials for any contact step can be added in any order. In some aspects, before ammonia contacts calcium sulfate, during contact, or after contact, carbon dioxide is contacted with calcium sulfate. In some aspects, before ammonia contacts calcium sulfate or during contact, carbon dioxide is mixed with ammonia. In some aspects, when two products are mixed in step (c), contact step (a) and / or contact step (b) are still occurring.

[0078] At least a portion of the unreacted calcium sulfate from step (a) can be used as the calcium sulfate in step (b). In some aspects, at least a portion of the unreacted calcium sulfate in step (a) is separated from calcium carbonate and ammonium sulfate before the unreacted calcium sulfate is contacted with potassium chloride. In some aspects, the unreacted calcium sulfate in step (a) is not separated from calcium carbonate and ammonium sulfate before the calcium sulfate is contacted with potassium chloride.

[0079] The moisture content of the dried fertilizer can be less than 1 wt %, such as 0.1 wt % to 0.9 wt %, or any of the following, or between the following, or any range thereof: 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt % or 1 wt %, based on the weight of the fertilizer. As a non-limiting example, the moisture content can be measured by drying the sample at 50° C. for 25 minutes and measuring the mass loss of the fertilizer after drying.

[0080] In some particular aspects, the homogenous mixture can contain phosphogypsum and / or can be obtained from phosphogypsum.

[0081] Granular 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 that is circular, elliptical, ovate, triangle, square, rectangle, pentagon or hexagon, but can also be made into the cylindrical core that cross section is other shapes.In some respects, the widest dimension of granular fertilizer can be 0.5mm to 6mm, or be 0.5mm to 5mm, preferably 1mm to 4mm, or be any one size of following size at least, any one size of following size at most, equal any one size of following size or between any two sizes of following size: 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm and 6mm. In some particular aspects, the fertilizer particles 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 sizes, at most any one of the following sizes, equal to any one of the following sizes, or between any two of the following sizes: 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.

[0082] 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 being added to the water can be decomposed into particles 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.

[0083] A homogeneous mixture can have a substantially uniform composition. In some cases, the composition of a 1 mm×1 mm×1 mm cube at any location of the mixture can be similar to the composition of a 1 mm×1 mm×1 mm cube at any other location of the mixture (within ±20%, or ±10%, or ±5%, or ±3%, ±2%, or ±1%, or ±0.5%).

[0084] Reference Figure 1 , a fertilizer granule 100 according to one embodiment of the present invention is shown. The fertilizer granule 100 may contain a homogenous mixture 101. The homogenous mixture 101 may have a composition as described above. In some cases, the homogenous mixture 101 may have an optional coating 102 on the outer surface of the homogenous mixture 101.

[0085] In some cases, the fertilizer comprises a CaCO3 matrix that at least partially surrounds and / or encapsulates at least a portion of the CaCl2 and / or KNH4SO4. In some aspects, the fertilizer comprises CaCO3 particles, CaCl2 particles, and / or KNH4SO4 particles.

[0086] In some respects, other fertilizer materials may or may not be included in the fertilizer. If other fertilizer materials are included, other fertilizers may be selected based on the special needs of certain types of soil, climate or other growth conditions, to maximize the effectiveness of fertilizers in promoting plant growth and crop yield. Other additives may also be included in the fertilizer. The non-limiting example of the additive that fertilizers of the present invention may or may not include includes nitrogen nutrients, phosphorus nutrients, potassium nutrients, other trace element nutrients, other minor nutrients, adhesives, inhibitors, pH buffers, desiccant etc. In some cases, other fertilizer materials and / or other additives are included in the optional coating of the fertilizer.

[0087] Trace element nutrients can be copper, iron, chlorine, manganese, molybdenum or nickel or any combination thereof. Nitrogen nutrients can be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea formaldehyde, ammonium chloride and potassium nitrate. In some aspects, additional secondary nutrients can include lime and / or superphosphate.

[0088] In some cases, the inhibitor includes 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), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole sold under the trade name NBTPT, 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT) or 2-sulfathiazole (ST) and any combination thereof. In one aspect, the nitrification inhibitor may include DMPP, DCD, TU, nitrapyrin, 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, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST or a combination thereof.

[0089] In some cases, the adhesive includes phosphate, polyphosphate, biodegradable polymer, or wax or a combination thereof. Suitable waxes include, but are not limited to, vegetable wax, high melting point wax, ethylene bis stearamide wax, paraffin, polyethylene wax, and olefin wax. 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 polymer materials, such as polylactic acid, poly (3-hydroxypropionic acid), polyvinyl alcohol, poly e-caprolactone, poly L-lactide, polybutylene succinate, and biodegradable starch-based polymers. The adhesive may include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silicon dioxide, or a combination thereof. 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.

[0090] In some cases, the pH buffer comprises MgO, KH2PO4, NaHCO3, chalk, aluminum, 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 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, 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.

[0091] Fertilizer as described herein can be included in the composition for application to soil. In some respects, in addition to fertilizer, composition can also include other fertilizer compounds, trace element nutrients, major nutrients, urea, other nitrogen nutrients, pesticides, herbicides or fungicides or its combination. Fertilizer as described herein can also be included in the mixed composition comprising other fertilizers. Other fertilizers can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride salt (MOP), monopotassium phosphate (MKP), triple superphosphate (TSP), phosphate rock powder, single superphosphate (SSP), ammonium sulfate, etc.

[0092] The fertilizer formed into particles can have desired physical properties, such as desired levels of abrasion resistance, particle strength, granulation, hygroscopicity, particle shape, and particle size distribution. In some aspects, the compressive strength of the fertilizer particles can be higher than 1.5 kgf, such as higher than 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of the following compressive strengths, equal to any one of the following compressive strengths, or between any two of the following compressive strengths: 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 densities, at most any one of the following densities, equal to any one of the following densities, or between any two of the following densities: 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, 100 mg or more, for example 10 mg to 40 mg, at least any one of the following masses, at most any one of the following masses, equal to any one of the following masses, or between any two of the following masses of fertilizer granules can be dissolved in 1 ml of water at pH 7 with stirring at a speed 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, such as 0.02 weight percent to 0.12 weight percent, or up to any one of the following weight percents, equal to any one of the following weight percents, or between any two of the following weight percents: 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. The following attrition loss test can be used to measure attrition loss.

[0093] Wear loss test: weigh single particles with a size of 2mm to 4mm and a total volume of 100cm 3 A plurality of sieved fertilizer granules (W1) were placed in a test drum together with 50 stainless steel balls with a total weight of 100 grams. The test drum was sealed 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. The total weight of the granules on the 2 mm sieve was then reweighed (W2). The results were calculated in weight loss % using the following formula:

[0094]

[0095] II. Method for preparing fertilizer

[0096] Reference Figure 2 , a schematic diagram of a system and method for preparing fertilizer according to one embodiment of the present invention is depicted. System 200 may include a granulator 202 and a dryer 204. A feed mixture 206 may be granulated in granulator 202 in the presence of water to form a wet granular mixture 208. Water may be provided with feed mixture 206, and / or water may be added separately to granulator 202. The wet granular mixture 208 may be dried in dryer 204 to obtain a dry granular mixture 210 containing fertilizer.

[0097] Reference Figure 3, a schematic diagram of a system and method for preparing fertilizer according to another embodiment of the present invention is described in the figure. System 300 may include a mixer / reactor 312, but the mixer and reactor may be two components, three components, four components, or more than four components, such as two reactors and a mixer or one reactor and a mixer. System 300 may include a granulator 302, a spheroidizer 314, one or more than one size screen 316, and a dryer 304 or any combination thereof. Feed mixture components 318 may be added to the mixer / reactor 312 individually and / or in any possible combination. In the mixer / reactor 312, the feed components may react and / or mix to form a feed mixture 306. The feed mixture 306 may be granulated in the granulator 302 in the presence or absence of additional water to form a wet granular mixture 320. The particles in the wet granular mixture 320 may be spheroidized in the spheroidizer 314 to form a wet granular mixture 322 containing substantially spherical particles. The wet granular mixture 322 can be passed through one or more size screens 316 to separate particles having a size less than a desired size or greater than a desired size from the wet granular mixture 322 to obtain a wet granular mixture 324 containing particles of the desired size. At least a portion of the particles 326 separated from the granular mixture 324 containing particles of the desired size can be recycled to the granulator 302. The wet granular mixture 324 containing particles of the desired size can be dried in the dryer 304 to obtain a dry granular mixture 310 containing fertilizer particles. In some aspects, the mixer / reactor 312 can include a ribbon mixer.

[0098] The feed mixture composition 318 may include i) a Ca source, such as phosphogypsum, ii) a N source, such as NH3, iii) a C source, such as CO2, and iv) a K source, such as KCl. In some cases, the mixture composition provides more than one Ca species, N species, C species, K species, S species, and / or Cl species. In certain aspects, one or more components may be added as an aqueous solution. In some cases, one or more components may be added as a gas. In some cases, NH3 and / or CO2 are provided at a pressure above 1 bar, for example, at any one of the following pressures, or between the following pressures, or any range of the following pressures: 1.2 bar, 1.3 bar, 1.4 bar, 1.5 bar, 2 bar, 2.5 bar, 3 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 as powders.

[0099] Feed mixture 206, feed mixture 306 may contain Ca, N, C, K, S and / or Cl. In some aspects, feed mixture 206, feed mixture 306 may contain unreacted i) phosphogypsum, ii) ammonia, iii) carbon dioxide, and iv) potassium chloride, or a combination thereof. In some aspects, feed mixture 318 may contain i) phosphogypsum, ii) ammonia, iii) carbon dioxide, and iv) potassium chloride, or any combination thereof.

[0100] Water may be added to the feed mixture in the mixer / reactor 312 and / or the pelletizer 202, pelletizer 302. In certain aspects, water may be added (e.g., together with one or more of the feed mixture components and / or separately) in a total amount of 5 to 20 grams, or at least any of the following masses, at most any of the following masses, equal to any of the following masses, or between any two of the following masses per 100 grams of the 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.

[0101] In some aspects, granulator 202 and granulator 302 can be drum granulator, stirring granulator, disc granulator, solid mixer, grinding drum, extruder, high shear mixer granulator, roller granulator, high shear granulator (mycromix) or round bottom flask. In granulator 202 and granulator 302, feed mixture 206 and feed mixture 306 can be granulated by agglomeration, spray granulation, pressing, slurry granulation and / or high shear mixer granulation. In some special aspects, feed mixture 206 and feed mixture 306 can be granulated by pressing in granulator 202 and granulator 302. In some aspects, granulator 202 and granulator 302 can include at least two rollers, and pressing granulation can include using at least two rollers to compress the feed mixture. In some aspects, during pressing, two rollers can move in countercurrent direction. In some respects, the feed mixture can be compressed into the granule of molding, such as cylindrical granule, by at least two rollers. In some respects, the surface of a roller can have the hole of expectation, so that the feed mixture is pressed into the hole, and the surface of another roller can push the feed mixture into the hole. Granulation, for example, the pressure in the compression granulation process can be 1 bar to 40 bar, or any one pressure of at least following pressure, any one pressure of at most following pressure, equal any one pressure of following pressure or between any two pressures of following pressure: 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 granulated in granulator 202, granulator 302 at ambient temperature to 50°C, or at any temperature of at least the following temperatures, at most the following temperatures, equal to any temperature, or between any two of the following temperatures: -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.

[0102] In some aspects, the reaction of the feed mixture components, mixing, and granulation of the feed mixture can be performed in different containers, for example, the mixer / reactor 312 and the granulator 302 can be different containers. In some aspects, the reaction of the feed mixture components, mixing, and granulation of the feed mixture can be performed in the same container, for example, the mixer / reactor 312 and the granulator 302 can be the same container (not shown).

[0103] 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 a pressure of 4 bar, at 5 bar, at 6 bar, at 7 bar, at 8 bar, at 9 bar, at 10 bar, at 11 bar, at 12 bar, at 13 bar, at 14 bar, at 15 bar, at 16 bar, at 17 bar, at 18 bar, at 19 bar, at 20 bar, at 21 bar, at 22 bar, at 23 bar, at 24 bar, at 25 bar, at 26 bar, at 27 bar, at 28 bar, at 29 bar, at 30 bar, at 31 bar, at 32 bar, at 33 bar, at 34 bar, at 35 bar, at 36 bar, at 37 bar, at 38 bar, at 39 bar, and at 40 bar. The extruder can extrude the fertilizer at a temperature of at least, at most, at, or between any two of the following temperatures: -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, for example, by a die, before drying.

[0104] In some aspects, the final fertilizer product, such as a desired size of granules, can be 0.5 mm to 5 mm, or 1 mm to 4 mm, and granules less than 0.5 mm or 1 mm in size and / or greater than 4 mm or 5 mm in size can be separated from the wet granular mixture 322 in one or more size screens 316. In some aspects, the wet granular mixture can be spheronized in a spheronizer. In some cases, the wet granular mixture is contacted with the spheronizer for at least any of the following times, at most any of the following times, equal to any of the following times, or between any two of the following times: 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 rotating disk or a rotatable disk capable of rotating at least any one of the following speeds, at most any one of the following speeds, at any one of the following speeds, or between any two of the following speeds: 200 rpm, 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm. In some aspects, the wet granule mixture can be dried in the dryer 208, the dryer 308 at a temperature of 40°C to 85°C, or at least any one of the following temperatures, at most any one of the following temperatures, at any one of the following temperatures, or between any two of the following temperatures: 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, and 85°C. In some aspects, the dryer 208, the dryer 308 can be a fluidized bed dryer, a rotary drum dryer, or an airflow dryer. In some aspects, the wet granular mixture can be dried in the dryer 208, the dryer 308 at a rotation of at least any of the following speeds, at most any of the following speeds, equal to any of the following speeds, or between any two of the following speeds: 5 rpm, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm, 35 rpm, 40 rpm, 45 rpm, and 50 rpm, with a hot air flow having at least any of the following flow rates, at most any of the following flow rates, equal to any of the following flow rates, or between any two of the following flow rates: 100 m 3 / h、150m 3 / h、200m 3 / h、250m 3 / h、300m 3 / h、350m 3 / h、400m 3 / h、450m 3 / h and 500m3 / h.

[0105] III. Methods of using fertilizers

[0106] Fertilizers of the present disclosure, including fertilizer granules, compositions containing fertilizers, and fertilizer mixtures containing fertilizers of the present disclosure, can be used to increase the content of one or more plant nutrients in soil and promote plant growth methods. These methods may include applying an effective amount of a composition and / or mixture containing the fertilizer of the present invention to the soil. The method may include increasing the growth and yield of crops, trees, ornamental plants, etc., such as the growth and yield of palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. The method may include applying the fertilizer mixture of the present invention to at least one of soil, organisms, liquid carriers, liquid solvents, etc. One or more compositions and / or one or more fertilizer mixtures containing fertilizers can be applied to plants and / or soil as topdressing fertilizers, base fertilizers, and / or by any suitable application method.

[0107] Non-limiting examples of plants that can benefit from the fertilizer of the present invention include lianas, trees, shrubs, culms, ferns, etc. Plants can include orchard crops, lianas, ornamental plants, food crops, timber, and harvested plants. Plants can include gymnosperms, angiosperms, and / or ferns.

[0108] The effectiveness of a fertilizer composition comprising the present invention can be determined by measuring the calcium and optionally other nutrient content in the soil at various times after the fertilizer composition is applied to the soil. 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 compared directly to other fertilizer compositions by making a side-by-side comparison in the same soil under the same conditions.

[0109] Example

[0110] The present invention will be described in more detail by 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 easily recognize various noncritical parameters that can be changed or altered to produce substantially the same results.

[0111] Example 1

[0112] Production of calcium fertilizers

[0113] Step 1: 100 g of CaSO4 suspension is charged into a Parr reactor and heated to a temperature of 60°C. Ammonia and CO2 gases with a flow rate of 125 cm3 / min each can be mixed in a 1:1 molar ratio and flowed through the CaSO4 suspension at a pressure of 5 bar to cause a reaction. The reaction can be continued for 5 hours at a temperature of 60°C. After the reaction is completed, 134 g of product is expected to be produced. The product produced will contain a mixture of (NH4)2SO4 and CaCO3 and some unreacted CaSO4.

[0114] Step 2: The product from step 1 containing a mixture of (NH4)2SO4 and CaCO3 is mixed with 15 g KCl and charged into a Parr reactor. The mixture can be heated at 60°C for 5 hours. The process of this step can be described by a stoichiometric reaction:

[0115] 2KCl+CaSO4→K2SO4+CaCl2.

[0116] The products of step 1 and step 2 can be mixed to produce a final product comprising a combination of NH4KSO4 and CaCl2 and CaCO3, wherein the nitrogen content is expected to be 12% to 16%, for example 12% to 15%, the sulfur content is 20% to 23%, and the potassium content is 10% to 14% (12%% to 17% as K2O), based on the weight of the composition.

[0117] ***

[0118] In light of the present disclosure, all methods disclosed and claimed herein can be prepared and implemented without undue experimentation. Although the compositions and methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that changes may 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 certain reagents that are both chemically and physiologically related may be substituted for 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 in the appended claims.

Claims

1. A fertilizer comprising a mixture comprising: Potassium ammonium sulfate (KNH4SO4); and At least two different calcium compounds.

2. The fertilizer of claim 1, wherein the at least two different calcium compounds comprise calcium chloride (CaCl2).

3. The fertilizer according to any one of claims 1 or 2, wherein the at least two different calcium compounds comprise calcium carbonate (CaCO3).

4. The fertilizer according to any one of claims 1 to 3, wherein CaCO3 at least partially encapsulates at least part of the KNH4SO4.

5. The fertilizer according to any one of claims 1 to 4, wherein the at least two different calcium compounds comprise CaCl2 and CaCO3, wherein preferably the weight ratio of CaCO3 to CaCl2 is from 4:1 to 10:

1.

6. The fertilizer according to any one of claims 1 to 5, wherein the mixture comprises 12 to 16 wt. % nitrogen in the form of ammonium; 20 to 23 wt. % sulfur in the form of sulfate; and 10 to 14 wt % potassium; The weight % are based on the total weight of the fertilizer.

7. A method for preparing a fertilizer, the method comprising (a) contacting calcium sulfate with ammonia and carbon dioxide to produce a first product and optionally unreacted calcium sulfate, wherein the first product comprises calcium carbonate (CaCO3) and ammonium sulfate ((NH4)2SO4); (b) contacting calcium sulfate with potassium chloride to produce a second product, the second product comprising calcium chloride (CaCl2) and potassium sulfate (K2SO4); and (c) mixing the first product and the second product to produce a fertilizer.

8. The method according to claim 7, wherein in step (a) and / or step (b), the source of calcium sulfate is gypsum.

9. A process according to any one of claims 7 or 8, wherein step (b) comprises contacting at least a portion of the first product with potassium chloride.

10. The process according to any one of claims 7 to 9, wherein at least part of the calcium sulfate of step (b) is obtained from unreacted calcium sulfate of step (a).

11. The process according to any one of claims 7 to 10, wherein all of the calcium sulfate of step (b) is obtained from unreacted calcium sulfate of step (a).

12. The process according to any one of claims 9 to 11, wherein in step (b), at least part of the first product is contacted with potassium chloride to produce KNH4SO4 by reacting potassium sulfate with ammonia and water.

13. The method of any one of claims 7 to 12, wherein step (c) produces a fertilizer comprising KNH4SO4, CaCl2 and CaCO3.

14. The method of any one of claims 7 to 13, wherein contacting step (a) and / or contacting step (b) occurs at about 50°C to 70°C and / or lasts for 3 hours to 12 hours.

15. The method of any one of claims 7 to 14, wherein the fertilizer comprises the fertilizer of any one of claims 1 to 6.

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