Composite mineral fertilizer from calcium phosphate, nitric acid and urea and method of preparation

Abstract

Fertilizers comprising a mixture containing calcium nitrate (Ca(NO3)2) and one or both of urea phosphate (H3PO4.CO(NH2)2) and urea diphosphate ((H3PO4)2.CO(NH2)2) are disclosed. Methods of making and using the fertilizers are also disclosed.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to European application No. 23201406.8, filed on 3 October 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to fertilizer compositions containing slow-release agents. In specific embodiments, this disclosure relates to fertilizers containing calcium nitrate and one or both of urea phosphate and urea diphosphate. Background Technology

[0004] Soil nutrients, such as nitrogen, phosphorus, potassium, and sulfur, as well as micronutrients such as iron, zinc, copper, calcium, and magnesium, are essential for thriving agriculture and plant growth. After repeated cropping cycles, the amounts of these nutrients in the soil can be depleted, leading to inhibited plant growth and reduced yields. To counteract this effect, fertilizers have been developed to help replenish depleted essential nutrients. Mononutrient fertilizers and multinutrient fertilizers, such as fertilizer blends, have been developed to meet the diverse needs of crop production worldwide.

[0005] Applying fertilizer does not always provide plants with the full amount of nutrients in a short period of time. Some fertilizers contain nutrients that are not readily available to plants at the time of application. In these cases, some people fertilize well before planting, or over-fertilize close to planting to provide the plants with sufficient nutrients from the outset. However, this comes at the cost of 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 their entire growth and maturation period. However, many fertilizers disperse, degrade, or are absorbed shortly after application when applied to the soil. To address this, fertilizers can be applied to the same plant multiple times, or slow-release fertilizers can be used. Some approaches to slow-release fertilizers involve polymer coating the fertilizer core. However, many polymer coatings are expensive and / or accumulate undesirably in the soil over time after repeated applications. Some approaches to slow fertilizer release include mixing or coating with insoluble metal oxides such as MgO and CaO. However, these metal oxides do not provide plants with much (if any) of the nutrients. Summary of the Invention

[0007] This document discloses solutions to at least some of the aforementioned problems, including the production of fertilizer products by combining urea, calcium phosphate (e.g., in phosphate rock form), and nitric acid (e.g., nitric acid derived from renewable energy sources); and the production of fertilizer products with slow-release properties for the nutrients therein. In some aspects, one or more components accumulate in the soil as a reservoir of nutrients for release over time. In one aspect, the solution is to provide a fertilizer comprising calcium (Ca), nitrogen (N) in the form of nitrates and urea compounds (e.g., one or both of urea phosphate and urea diphosphate), and phosphorus (P) in the form of phosphates. In some aspects, the fertilizer contains calcium nitrate and one or both of urea phosphate and urea diphosphate. Calcium nitrate can act as a binder for other components in the fertilizer (e.g., urea phosphate and / or urea diphosphate). In some aspects, the fertilizer is produced by the methods for producing fertilizer products disclosed herein. In some embodiments, the synthesis of at least a portion of the fertilizer occurs by reacting a metal phosphate with nitric acid. Non-limiting example reactions may include the following:

[0008] Ca3(PO4)2 + 6HNO3 → 3Ca(NO3)2 + 2H3PO4

[0009] In some embodiments, at least a portion of the fertilizer synthesis occurs by reacting phosphoric acid and urea to produce urea phosphate. Non-limiting examples of the reaction may include the following:

[0010] H3PO4 + NH2CONH2 → H3PO4·CO(NH2)2

[0011] In some embodiments, at least a portion of the fertilizer synthesis occurs by reacting phosphoric acid with a previously formed urea phosphate to produce urea diphosphate. Non-limiting examples of the reaction may include the following:

[0012] H3PO4 + H3PO4·CO(NH2)2 → (H3PO4)2·CO(NH2)2

[0013] In some embodiments, at least a portion of the fertilizer synthesis occurs by reacting two equivalents of phosphoric acid and one equivalent of urea to directly produce urea diphosphate (H3PO4)2·CO(NH2)2. Non-limiting examples of the reaction may include the following:

[0014] 2 H3PO4 + NH2CONH2 →(H3PO4)2·CO(NH2)2

[0015] The final product may contain a mixture of the above-mentioned constituent chemicals, including but not limited to any one of Ca(NO3)2, H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2.

[0016] In some respects, the reaction takes place in one or more containers. In other respects, the reaction occurs simultaneously, sequentially, or in a mixture of both.

[0017] Embodiments of this disclosure represent improvements to known fertilizers, including those involving the use of slow-release agents in fertilizers containing nitrogen (N), phosphorus (P), and metals such as calcium (Ca). Current slow-release fertilizer products typically employ physical interventions to slow fertilizer release, such as coating fertilizers with polymer-insoluble materials. Current slow-release fertilizers may also use enzyme inhibitors, such as urease inhibitors or nitrification inhibitors, to slow fertilizer utilization. While the fertilizers described herein may also contain physical interventions and / or inhibitors, such measures are not always necessary to produce slow-release nutrient fertilizer compositions.

[0018] The embodiments described herein depict mixtures of nutrients and the preparation of such mixtures, which serve to generate fertilizer accumulation in the soil as a reservoir of nutrients released over time. The fertilizer may include an immediate-release aspect, which may contain or consist of soluble reactants or products of the reactions described herein, or any combination thereof. The slow-release aspect of the fertilizer may contain or consist of one or more phosphates, such as urea phosphate and urea diphosphate.

[0019] In some respects, the fertilizer contains calcium nitrate as well as one or more of urea phosphate and urea diphosphate, or is composed of them.

[0020] The fertilizers covered in certain embodiments herein contain ingredients that can be used to cover immediate soil Ca, N, and P deficiencies in the form of readily soluble calcium nitrate, urea phosphate, and / or urea diphosphate, while also covering long-term Ca, N, and P requirements by slowly releasing urea phosphate and / or urea diphosphate, such as by encapsulating urea phosphate and / or urea diphosphate with calcium nitrate.

[0021] Some aspects involve fertilizers comprising mixtures containing nitrogen, phosphorus, and calcium sources. In some aspects, the mixture contains a binder. The binder may contain a slow-release agent. In some aspects, the mixture contains an immediate-release agent. The immediate-release agent may contain ammonium sulfate, calcium nitrate, calcium sulfate, nitric acid, phosphoric acid, urea phosphate, and / or urea diphosphate.

[0022] Some aspects relate to fertilizers containing at least a portion of an instant-release agent encapsulated by calcium nitrate. Some aspects relate to fertilizers containing at least a portion of an instant-release agent contained on the surface of calcium nitrate. Some aspects relate to fertilizers containing at least a portion of an instant-release agent contained in a dried gel of calcium nitrate.

[0023] In some respects, calcium nitrate forms a continuous phase in the fertilizer matrix.

[0024] In some respects, the fertilizer does not contain binders separate from calcium nitrate, urea phosphate, and / or urea diphosphate. The fertilizer may be a granular fertilizer.

[0025] In some aspects, at least a portion of urea diphosphate and / or urea phosphate in the fertilizer is encapsulated with calcium nitrate. In some aspects, the mixture and / or fertilizer is a homogeneous mixture and / or fertilizer. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises an amorphous phase made from the components of the fertilizer.

[0026] In some respects, the fertilizer contains at least one, at most one, equal to one, or between any two of the following nitrogen (N): 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 by weight; at least one, at most one, equal to one, or between any two of the following phosphorus (P) in an amount equivalent to P2O5: 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 by weight; and / or the following calcium (Ca): 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 by weight. In some cases, calcium nitrate is contained with urea phosphate and / or urea diphosphate in a weight ratio between approximately 5:1 and 1:5, such as 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4 or 1:5.

[0027] In some respects, fertilizers do not contain polymers. In other respects, fertilizers contain polymers. In other respects, fertilizers contain potassium sources.

[0028] In some respects, calcium phosphate is derived from or contained in calcium phosphate rocks. In some respects, calcium sulfate is not produced by this method and / or is not present in the fertilizer. In some respects, calcium sulfate is present in amounts less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01% by weight of the fertilizer.

[0029] Some aspects relate to methods for preparing fertilizers, including any fertilizers described herein. The method may include steps (a) and / or (b). In step (a), calcium phosphate is contacted with nitric acid to produce a first reaction product comprising calcium nitrate and phosphoric acid. In step (b), the first reaction product is contacted with urea to produce a second reaction product comprising urea phosphate and / or urea diphosphate. In some cases, the second reaction product is combined with the calcium nitrate produced in step (a) to produce a fertilizer mixture. In some cases, the fertilizer mixture additionally comprises unreacted calcium phosphate, nitric acid, urea, and / or phosphoric acid. In some cases, the fertilizer mixture does not contain any one or more of calcium phosphate, nitric acid, urea, and / or phosphoric acid.

[0030] In some respects, methods for preparing fertilizers include drying fertilizer mixtures to form solid fertilizer compositions. Steps (a) and (b) and / or drying can be carried out at approximately 20°C to 150°C, such as 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88. 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149 and 150℃. In some aspects, steps (a) and / or (b) may occur at temperatures or ranges from 20 to 75°C or any temperature or range thereof. In some aspects, the fertilizer composition comprises or consists of the following: calcium nitrate, urea phosphate, urea diphosphate, phosphoric acid, calcium phosphate, nitric acid, and / or urea.

[0031] The following aspects 1 to 20 of the present invention are also disclosed.

[0032] Aspect 1 is a fertilizer composition comprising a calcium nitrate (Ca(NO3)2) matrix that at least partially surrounds one or both of urea phosphate (H3PO4·CO(NH2)2) and / or urea diphosphate ((H3PO4)2·CO(NH2)2).

[0033] Aspect 2 is a fertilizer composition of aspect 1, wherein calcium nitrate forms a continuous phase in the matrix.

[0034] Aspect 3 is a fertilizer composition of any one of Aspects 1 and 2, wherein the composition comprises 10 to 20% by weight of nitrogen (N), phosphorus (P) in an amount equivalent to 30 to 35% by weight of P2O5, and 8 to 12% by weight of calcium (Ca).

[0035] Aspect 4 is a fertilizer composition of any one of Aspects 1 to 3, wherein the composition further comprises phosphoric acid (H3PO4) and / or urea (NH2CONH2).

[0036] Aspect 5 is a fertilizer composition of any one of Aspects 1 to 4, wherein the composition further comprises calcium phosphate (Ca3(PO4)2) and / or nitric acid (HNO3).

[0037] Aspect 6 is a fertilizer composition of aspect 5, wherein the composition comprises phosphate rock, said phosphate rock comprising at least a portion of calcium phosphate.

[0038] Aspect 7 is a fertilizer composition of any one of aspects 4 to 6, wherein the phosphoric acid is derived from a natural source.

[0039] Aspect 8 is a fertilizer composition of any one of aspects 5 to 7, wherein at least a portion of the nitric acid is derived from renewable energy sources.

[0040] Aspect 9 is the fertilizer composition of aspect 8, wherein renewable energy includes solar, wind, hydro, tidal, geothermal and / or biomass renewable energy.

[0041] Aspect 10 is a fertilizer composition of any one of aspects 1 to 9, wherein the composition does not contain a binder separate from calcium nitrate.

[0042] Aspect 11 is a fertilizer composition of any one of aspects 1 to 10, wherein at least a portion of urea phosphate and / or urea diphosphate is absorbed on the surface of calcium nitrate.

[0043] Aspect 12 is a fertilizer composition of any one of aspects 1 to 11, wherein the fertilizer composition further comprises a potassium source.

[0044] Aspect 13 is a fertilizer composition of any one of aspects 1 to 12, wherein the fertilizer is a homogeneous and / or an amorphous phase containing fertilizer components.

[0045] Aspect 14 is a fertilizer composition of any one of aspects 1 to 13, wherein at least a portion of urea diphosphate and / or urea phosphate is encapsulated with calcium nitrate.

[0046] Aspect 15 is a fertilizer composition of any one of aspects 1 to 14, wherein the fertilizer composition is a granular fertilizer.

[0047] Aspect 16 is a method for producing a fertilizer composition of any one of aspects 1 to 15, said method comprising the following steps:

[0048] (a) Contacting calcium phosphate with nitric acid to generate a first reaction product comprising calcium nitrate and phosphoric acid; and

[0049] (b) Contact the first reaction product with urea to generate a second reaction product comprising urea phosphate and / or urea diphosphate, wherein the second reaction product further comprises calcium nitrate generated in step (a).

[0050] Aspect 17 is the method of aspect 16, wherein steps a and b are performed by one-pot synthesis.

[0051] Aspect 18 is a method of either aspect 16 or 17, wherein no calcium phosphate remains in the first reaction product prior to contact with urea in step b.

[0052] Aspect 19 is a method of any one of Aspects 16 to 18, wherein step a is carried out for at least 45 minutes before the first reaction product of step b is contacted with urea.

[0053] Aspect 20 is a method of any one of aspects 16 to 19, which further includes drying the second reaction product to form a solid fertilizer composition.

[0054] The term "fertilizer" is defined as material applied to soil or plant tissue to provide one or more plant nutrients and / or stimulants or enhancers necessary or beneficial to plant growth in order to increase or enhance plant growth.

[0055] The term "particle" can include solid materials. Particles can have a variety of different shapes, and non-limiting examples include spherical, puck-shaped, elliptical, rod-shaped, rectangular, or random shapes.

[0056] The term "particle" can include solid materials whose maximum size is less than one millimeter.

[0057] The terms "granular material" or "powder" can include multiple particles.

[0058] As used herein, the terms “about” or “approximately” are defined as close to what is understood by one of ordinary skill in the art. In one non-limiting embodiment, the term is defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0059] The terms "weight%", "volume%", or "molar%" refer to the weight, volume, or molar percentage of a component based on the total weight, total volume, or total number of moles of the material comprising the component. In a non-limiting example, 10 grams of component in 100 grams of material is 10% by weight of the component.

[0060] When used in conjunction with the term "comprising," the words "a" or "a kind" can mean "one / kind," but are also consistent with the meanings of "one / kind or more / kinds," "at least one / kind," and "one / kind or more than one / kind."

[0061] The phrase “and / or” means “and” or “or”. For illustration, A, B and / or C includes: A alone, B alone, C alone, combinations of A and B, combinations of A and C, combinations of B and C, or combinations of A, B and C. In other words, “and / or” is used in an inclusive OR manner.

[0062] The words “comprising” (and any form of inclusion, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”), or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional unlisted elements or steps of procedure.

[0063] The composition and its method of use may “comprising” any component or step disclosed throughout the specification, “consistently composed of any component or step disclosed throughout the specification”, or “composed of any component or step disclosed throughout the specification”. Compositions and methods “consistently composed of any disclosed component or step” limit the scope of the claims to the specified materials or steps that do not substantially affect the essential and novel features of the claimed invention.

[0064] It is anticipated that any embodiment discussed in this specification can be implemented with respect to any method or composition of the present invention, and vice versa. Furthermore, the compositions of the present invention can be used to implement the methods of the present invention.

[0065] Other objects, features, and advantages of the invention will become apparent from the following detailed description. However, it should be understood that while the detailed description and specific embodiments indicate particular implementations of the invention, they are given by way of illustration only, as various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from the detailed description. Attached Figure Description

[0066] The following figures form part of this specification and are included to further illustrate certain aspects of the invention. A better understanding of the invention can be achieved by referring to one or more of these figures in conjunction with the detailed description of the specific embodiments presented herein.

[0067] Figure 1: A schematic diagram of a system and method for producing fertilizer based on a non-limiting example of the systems and methods disclosed herein.

[0068] Figure 2 : A schematic diagram of a system and method for producing fertilizer, based on another non-limiting example of the systems and methods disclosed herein. Detailed Implementation

[0069] Certain aspects of this disclosure offer advantages over existing fertilizers, including the slow-release properties of the nutrients contained in the fertilizer. Some aspects provided herein allow the fertilizer to slowly release nutrients into the soil over a period of time, such as throughout the plant's growth cycle. In some aspects, this capability can be achieved without the use of binders, inhibitors, or other interventions such as adding compounds beyond the fertilizer nutrients. In some embodiments, the fertilizer comprises urea phosphates, such as urea phosphate (H3PO4·CO(NH2)2) and / or urea diphosphate ((H3PO4)2·CO(NH2)2), and water-soluble nutrients, such as calcium nitrate (Ca(NO3)2), which can be a composition and / or a homogeneous mixture. Calcium nitrate can act as a binder for the other components in the fertilizer.

[0070] I. Fertilizer

[0071] Some embodiments described herein relate to compound fertilizers comprising: urea compounds, such as urea phosphate (H3PO4·CO(NH2)2) and / or urea diphosphate ((H3PO4)2·CO(NH2)2); and calcium compounds, such as Ca(NO3)2. Some aspects involve the use of natural sources of fertilizer components, such as Ca3(PO4)2, HNO3, Ca(NO3)2, H3PO4, and NH2CONH2, to synthesize nutrient complexes. In some aspects, the compound fertilizer is a mixture, which is a homogeneous mixture. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises an amorphous phase composed of the fertilizer components.

[0072] Fertilizers, which can be granular, may contain a mixture of calcium (Ca), phosphorus (P) in the form of phosphate, and nitrogen (N) in the form of nitrate and / or urea compounds. The proportions of elements present in the fertilizer can be customized according to the specific application.

[0073] At least a portion of Ca can exist as calcium nitrate. In some aspects, based on the total weight of Ca in the mixture, at least 90% by weight, or at least 95% by weight, or from 90% to 100% by weight, or at least any one, at most any one, equal to any one, or between any two of 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100% by weight of Ca can exist as calcium nitrate. In some embodiments, the Ca in the mixture is 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, 5 At least one, at most one, equal to one, or in between of 7, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5 and 100% by weight may exist as calcium nitrate.

[0074] In some respects, compound fertilizers may contain i) urea phosphate (H3PO4·CO(NH2)2), the amount of which is provided based on the total weight of the mixture and / or fertilizer granules as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.ii) urea diphosphate ((H3PO4)2·CO(NH2)2), provided in amounts based on the total weight of the mixture and / or fertilizer granules, in the quantities of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43. 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99% by weight, at least any one, at most any one, equal to any one, or between any two; and iii) Ca(NO3)2, the amount of which is provided based on the total weight of the mixture and / or fertilizer granules in the following values: 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, 5 3, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100% by weight, at least any one, equal to any one, or between any two.

[0075] In some respects, the mixture contains Ca, N, and / or P, wherein i) the Ca content of the mixture can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5 and 100 weight ii) The N content of the mixture can be 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, 4 5, 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.iii) The P content of the mixture may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100% by weight, at least any one, at most any one, equal to any one, or between any two, based on the total weight of the mixture and / or fertilizer.

[0076] Ca, N, and / or P can exist as water-soluble or water-insoluble compounds and / or be derived from water-soluble or water-insoluble compounds. In some aspects, Ca, N, and / or P can exist as salts. In some aspects, Ca, N, and / or P can exist as water-soluble salts. In some cases, water-soluble Ca and N salts can be Ca(NO3)2. In some cases, water-soluble N can be (NH2CONH2). Ca, N, and / or P salts can be non-hydrated and / or one or more hydrated forms.

[0077] In some respects, calcium phosphate originates from or is contained within calcium phosphate rocks.

[0078] Based on the weight of fertilizer granules, the moisture content of dried fertilizer can be less than 1% by weight, such as 0.1% to 0.9% by weight, or any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1% by weight, or between any two, or any range thereof. As a non-limiting example, moisture content can be measured by drying the sample at 50°C for 25 min and measuring the amount of mass lost by the fertilizer after drying.

[0079] Fertilizers can be any suitable shape. Non-limiting shapes include spherical, cubic, cylindrical, disc-shaped, elliptical, and rectangular shapes. In some aspects, fertilizer granules can be cylindrical with a circular, elliptical, ovular, triangular, square, rectangular, pentagonal, or hexagonal cross-section, although cylindrical cores with other cross-sectional shapes can also be prepared. In some aspects, fertilizer granules can be 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least, at most, equal to, 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. In some specific aspects, fertilizer granules may have a substantially spherical shape 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, at most any one, equal to any one, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm.

[0080] Fertilizers can be water- and / or soil-dispersible. In some respects, fertilizer granules with a size of 2 mm to 4 mm before being added to water can disintegrate into microparticles with sizes 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 granules to water at pH 7, under stirring at a rate of 90 rpm to 110 rpm, at ambient temperature. In some cases, fertilizer granules with a size of 2 mm to 4 mm, before being added to water, will not disintegrate into particles with 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 before being added to water at pH 7 for 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 2, 3, 4, 5, 6, 7, 8, 9, 10 hours, or more, under stirring at a rate of 90 rpm to 110 rpm at ambient temperature.

[0081] The mixture may have a substantially homogeneous composition. In some cases, the composition of a 1 mm × 1 mm × 1 mm cube at any location in the mixture may be similar to that of a 1 mm × 1 mm × 1 mm cube at any other location in the mixture (within ±20%, or ±10%, or ±5%, or ±3%, ±2%, or ±1%, or ±0.5%).

[0082] In some aspects, fertilizer granules may contain a homogeneous mixture. The homogeneous mixture may have the composition described above. In some cases, the homogeneous mixture may have an optional coating on its outer surface. In some cases, Ca(NO3)2 may act as a binder in the fertilizer. In some cases, Ca(NO3)2 is the only binder in the fertilizer. In some cases, Ca(NO3)2 forms an amorphous phase, a continuous phase, and / or encapsulates other components in the fertilizer. In some cases, the fertilizer contains a Ca(NO3)2 matrix that at least partially surrounds and / or encapsulates at least a portion of urea phosphate and / or urea diphosphate. In some cases, the fertilizer contains particles of Ca(NO3)2 and / or urea phosphate and / or urea diphosphate. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer contains an amorphous phase made from the components of the fertilizer.

[0083] In some aspects, additional fertilizer substances may or may not be included in the fertilizer. If included, additional fertilizers can be selected based on the specific needs of certain types of soil, climates, or other growing conditions to maximize the fertilizer's effectiveness in enhancing plant growth and crop yield. Additional additives may also be included or excluded from the fertilizer. Non-limiting examples of additives that may be included or excluded from the fertilizers of this invention include additional nitrogen nutrients, additional phosphorus nutrients, additional potassium nutrients, additional micronutrients, and / or additional secondary nutrients. Micronutrients may be copper, iron, chloride, manganese, molybdenum, or nickel, or any combination thereof. Nitrogen nutrients may be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride, and potassium nitrate. In some aspects, additional secondary nutrients may include lime and / or superphosphate. In some cases, additional fertilizer substances and / or additional additives are included in an optional coating of the fertilizer.

[0084] In some cases, the inhibitor includes nitrification inhibitors and / or urease inhibitors. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (chlorpyrifos, Nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (marketed under the trade name Terrazole® by OHP Inc., USA), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfonamidethiazole (ST), and any combination thereof. In one aspect, the nitrification inhibitor may comprise DMPP, DCD, TU, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or combinations thereof. In some embodiments, the fertilizer composition may comprise NBTPT, DMPP, TU, DCD, PPDA, chlorpyrifos, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST, or combinations thereof.

[0085] In some cases, binders include phosphates, polyphosphates, biodegradable polymers, or waxes or combinations thereof. Suitable waxes include, but are not limited to, vegetable waxes, high-melting-point waxes, vinyl bis(stearamide) waxes, paraffin waxes, polyvinyl waxes, and olefin waxes. Suitable phosphates include, but are not limited to, diammonium phosphate and monoammonium phosphate. Suitable polyphosphates include, but are not limited to, ammonium polyphosphates. Suitable biodegradable polymers include, but are not limited to, polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid, and other biodegradable polymeric materials such as polylactic acid, poly(3-hydroxypropionic acid), polyvinyl alcohol, poly(ε-caprolactone), poly(L-lactide), polybutylene succinate, and biodegradable starch-based polymers. Binders may include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silica, or combinations thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin-modified starch.

[0086] In some cases, pH buffers include MgO, KH₂PO₄, NaHCO₃, chalk powder, 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, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, and 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.

[0087] The fertilizers described herein can be included in compositions that can be applied to soil. In some aspects, in addition to the fertilizers described herein, the compositions may include other fertilizer compounds, micronutrients, major nutrients, urea, additional nitrogen nutrients, pesticides, herbicides, or fungicides, or combinations thereof. The fertilizers described herein may also be included in blend compositions containing other fertilizers. Other fertilizers may be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), potassium dihydrogen phosphate (MKP), triple superphosphate (TSP), phosphate rock, single superphosphate (SSP), ammonium sulfate, etc.

[0088] Fertilizers forming granules can possess desired physical properties, such as desired levels of abrasion resistance, granule strength, granulation properties, hygroscopicity, granule shape, and size distribution. In some aspects, fertilizer granules can have a crushing strength greater than 1.5 kgf, such as greater than 1.8 kgf, such as 2 kgf to 6 kgf, or at least, equal to, or between any two of 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, and 6 kgf. The bulk density of fertilizer granules can be from 1 g / cc to 1.2 g / cc, or at least, at most, equal to, or between any two of 1, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18, and 1.2 g / cc. In some respects, fertilizer granules of 10 mg or more, such as 10 mg to 40 mg, or 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40 mg, at least any one, at most any one, equal to any one, or between any two, can be dissolved in 1 ml of water at pH 7, with stirring at a rate of 90 to 110 rpm and at ambient temperature, within 5 minutes of adding 100 mg of fertilizer granules to water, or only 10, 20, 30, 40, 50, 60 minutes, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 15 hours or 24 hours after adding 100 mg of fertilizer granules to water. In some respects, during abrasion loss testing, fertilizer particles can lose less than 0.13% by weight, such as 0.02% to 0.12% by weight, or at most any one, equal to, or between any two of 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, and 0.12% by weight. Abrasion loss can be measured using the following abrasion loss test.

[0089] Wear and tear test: Multiple individual sizes ranging from 2 to 4 mm, with a total volume of 100 cm³. 3 The sieved fertilizer granules were weighed (W1) and placed into a test drum along with 50 stainless steel balls, each weighing 100 gm. The drum was then closed and rotated at 30 rpm for 10 minutes. The steel balls were then separated from the sample, and the material was sieved using a vibrating sieve on a 2 mm sieve. The total weight of granules larger than 2 mm was then re-weighed (W2). The result was calculated as a percentage of weight loss using the following formula:

[0090]

[0091] II. Methods for preparing fertilizers

[0092] refer to Figure 1 The diagram illustrates a system and method for preparing fertilizer according to an embodiment of the present invention. System 100 may include a granulator 102 and a dryer 104. A feed mixture 106 may be granulated in the granulator 102 with or without water to form a wet granulated mixture 108. Water (if present) may be provided with the feed mixture 106 and / or may be added separately to the granulator 102. The wet granulated mixture 108 may be dried in the dryer 104 to obtain a dry granulated mixture 110 containing fertilizer.

[0093] refer to Figure 2 This diagram illustrates a system and method for preparing fertilizer according to another embodiment of the invention. System 200 may include a mixer / reactor 212, but the mixer and reactor may be two, three, four or more components, such as two reactors and (one) mixer or (one) reactor and (one) mixer. System 200 may include a granulator 202, a rounding mill 214, one or more sized sieves 216, and a dryer 204, or any combination thereof. Feed mixture components 218 may be added individually and / or in any possible combination to the mixer / reactor 212. In the mixer / reactor 212, the feed components may react and / or mix to form a feed mixture 206. Feed mixture 206 may be granulated in granulator 202 with or without additional water to form a wet granulated mixture 220. The particles of wet granulated mixture 220 may be rounded in rounding mill 214 to form a wet granulated mixture 222 containing substantially spherical particles. The wet granulation mixture 222 can be passed through one or more size sieves 216 to separate particles smaller than or larger than a desired size from the wet granulation mixture 222, and obtain a wet granulation mixture 224 containing particles of the desired size. At least a portion 226 of the particles separated from the granulation mixture 224 containing particles of the desired size can be recycled to the granulator 202. The wet granulation mixture 224 containing particles of the desired size can be dried in a dryer 204 to obtain a dry granulation mixture 210 containing fertilizer particles. In some aspects, the mixer / reactor 212 may include a belt mixer.

[0094] The feed mixture component 218 may include i) a Ca source, such as calcium phosphate, ii) an N source, such as nitric acid and urea, and iii) a P source, such as calcium phosphate. In some cases, the mixture component provides more than one of Ca, N, and / or P. In some cases, the mixture component provides additional nutrients and / or micronutrients, such as K, S, Mg, Fe, and / or Si. In some aspects, one or more components may be added as an aqueous solution. In some cases, the mixture component is provided as a powder. In some cases, one or more components may be added as a gas. In some cases, a portion of the mixture of components is provided as a powder.

[0095] Feed mixtures 106 and 206 may contain Ca, N, and / or P. In some respects, feed mixtures 106 and 206 may contain H3PO4·CO(NH2)2, (H3PO4)2·CO(NH2)2, Ca3(PO4)2, HNO3, Ca(NO3)2, H3PO4, and / or NH2CONH2.

[0096] Water may be added to the feed mixture in mixer / reactor 212 and / or granulators 102, 202. In some respects, a total of 5 gm to 20 gm, or at least any one, at most any one, equal to any one, or in between any two of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 gm of water may be added to the feed mixture (e.g., added together with one or more feed mixture components and / or added separately).

[0097] In some aspects, granulators 102, 202 may be drum granulators, mixer granulators, disc granulators, solid mixers, grinding drums, extruders, high-shear mixer granulators, roller granulators, high-shear mixing granulators (mycromix), or round-bottom bottles. In granulators 102, 202, feed mixtures 106, 206 may be granulated by agglomeration, spray granulation, compaction, slurry granulation, and / or high-shear mixer granulation. In some specific aspects, feed mixtures 106, 206 may be granulated in granulators 102, 202 by compaction. In some aspects, granulators 102, 202 may contain at least two rollers, and compaction granulation may include compressing the feed mixture using at least two rollers. In some aspects, the two rollers may move in a countercurrent direction during compaction. In some aspects, the feed mixture may be compressed into shaped pellets, such as cylindrical pellets, by at least two rollers. In some aspects, the surface of one roller may have desired orifices to compress the feed mixture into the orifices, and the surface of another roller may push the feed mixture into the orifices. The pressure during granulation (e.g., compaction granulation) may be from 1 bar to 40 bar, or at least any one, at most any one, equal to any one, or between any two of 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, and 40 bar. In some aspects, the feed mixture may be granulated in granulators 102, 202 at an ambient temperature up to 50°C, or at least any one, at most any one, equal to any one, or between any two of -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50°C.

[0098] In some aspects, the reaction of the feed mixture components, the mixing of the feed mixture, and granulation 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 of the feed mixture components, the mixing of the feed mixture, and granulation 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. In some cases, urea phosphate (H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2) and Ca(NO3)2 are formed in one container. In some cases, urea phosphate (H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2) and H3PO4 are formed in one container. In some cases, urea phosphate (H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2) forms in one container, and Ca(NO3)2 and H3PO4 form in another container. In some cases, H3PO4 and Ca(NO3)2 form in one container, and urea phosphate (H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2) forms in two different containers. In some cases, urea phosphate (H3PO4·CO(NH2)2 and (H3PO4)2·CO(NH2)2), Ca(NO3)2, and H3PO4 form in one container.

[0099] In some respects, (H3PO4·CO(NH2)2, (H3PO4)2·CO(NH2)2), Ca(NO3)2 and H3PO4 are at least, at most, or equal to 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 1 34, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149 or 150°C or any two of these temperatures, such as between 20 and 80°C, or between 100 and 150°C, or between 75 and 150°C, or between 55 and 75°C, or between 20 and 150°C.

[0100] In some cases, fertilizer can be extruded before drying. The extruder can extrude fertilizer at pressures of at least, and at most, equal to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 bar, or between any two of these. The extruder can extrude fertilizer at temperatures of at least, and at most, equal to, -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 °C, or between any two of these. The extrudate can be sliced ​​or separated before drying, for example, through a die.

[0101] In some aspects, the desired size of the final fertilizer product, such as granules, may be 0.5 to 5 mm, or 1 to 4 mm, and those with dimensions less than 0.5 mm or 1 mm, and / or those with dimensions greater than 4 mm or 5 mm, may be separated from the wet granulation mixture 222 in one or more size sieves 216. In some aspects, the wet granulation mixture may be rounded and / or spherical in a sphericalizer. In some cases, the wet granulation mixture is contacted with the sphericalizer for at least, at most, equal to, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 50, or 60 seconds. In some cases, the sphericalizer has a rotating or rotatable disc capable of rotating at at least, at most, equal to, or between any two of 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000 rpm. In some aspects, the wet granulation mixture can be dried in dryers 104 and 204 at a temperature of 40°C to 150°C, or at least, at most, equal to, or between any two of the following: 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, and 150°C. In some aspects, dryers 104 and 204 can be fluidized bed dryers, drum dryers, or flash dryers. In some aspects, the wet granulation mixture can be dried in dryers 104 and 204 with a hot air stream having a velocity of 100, 150, 200, 250, 300, 350, 400, 450, and 500 m³. 3 Flow rates of at least one, at most one, equal to one, or between any two of / hr and / or rotation rates of at least one, at most one, equal to one, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 rpm.

[0102] III. Methods of Using Fertilizers

[0103] Fertilizers, including fertilizer granules, compositions containing fertilizers, and fertilizer blends 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. Such methods may include applying an effective amount of the composition and / or blend containing the fertilizer of the present invention to the soil. These methods may include increasing the growth and yield of crops, trees, ornamental plants, such as palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. These methods may include applying the fertilizer blend of the present invention to at least one of soil, organism, liquid carrier, liquid solvent, etc. The fertilizer-containing composition (one or more) and / or fertilizer blend (one or more) may be applied to plants and / or soil as top dressing, basal fertilizer, and / or by any suitable application method.

[0104] Non-limiting examples of plants that can benefit from the fertilizer of this invention include vines, trees, shrubs, stalked plants, ferns, etc. Plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. Plants may include gymnosperms, angiosperms, and / or ferns.

[0105] The effectiveness of compositions containing the fertilizers of this invention can be determined by measuring the amounts of phosphorus and optionally other nutrients in the soil at different times after the fertilizer composition has been applied to the soil. It should be understood that different soils have different characteristics that can affect the stability of nutrients in the soil. The effectiveness of the fertilizer composition can also be directly compared with other fertilizer compositions by performing side-by-side comparisons under the same conditions in the same soil.

[0106] Example

[0107] The invention will be described in more detail with the aid of specific embodiments. The following embodiments are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize that various non-critical parameters can be changed or modified to produce substantially the same results.

[0108] Example 1

[0109] Fertilizer preparation

[0110] 20 g of calcium phosphate was added to 48 g of 70% nitric acid and stirred to dissolve the calcium phosphate in the nitric acid. 14 g of urea was gradually added to the resulting solution to form a first gel. The formed gel was passed through a funnel to form a granular mixture. The granular mixture was dried at 92°C for 48 hours. The dried granules contained 48 g of calcium nitrate, and 28.8 g of phosphoric acid was expected to be produced as an intermediate component, which was then reacted with urea.

[0111] The following reactions occur:

[0112] Ca3(PO4)2+ 6HNO3 = Ca(NO3)2+ 2H3PO4

[0113] NH2CONH2+ H3PO4 = NH2CONH4HPO4

[0114] The final product contains Ca(NO3)2 / NH2CONH4HPO4.

[0115] Example 2

[0116] Fertilizer preparation

[0117] Example 2 was carried out as in Example 1, except that 28g of urea was used. The resulting material consisted of Ca(NO3)2 / CO(NH4HPO4)2.

[0118] Based on this disclosure, all methods disclosed and claimed herein can be manufactured and performed without excessive experimentation. While the compositions and methods of the invention have been described according to preferred embodiments, it will be apparent to those skilled in the art that variations may be made to the methods and steps or order of steps described herein without departing from the concept, spirit, and scope of the invention. More specifically, it will be apparent that certain chemically and physiologically relevant reagents can be substituted for those described herein while achieving the same or similar results. All such similar substitutions and modifications that are apparent to those skilled in the art are considered to be within the spirit, scope, and concept of the invention as defined by the appended claims.

Claims

1. A fertilizer composition comprising a matrix of calcium nitrate (Ca(NO3)2) that at least partially surrounds one or both of urea phosphate (H3PO4·CO(NH2)2) and / or urea diphosphate ((H3PO4)2·CO(NH2)2), wherein the composition comprises 10 to 20% by weight nitrogen (N), phosphorus (P) in an amount equivalent to 30 to 35% by weight P2O5 and 8 to 12% by weight calcium (Ca).

2. The fertilizer composition according to claim 1, wherein the calcium nitrate forms a continuous phase in the matrix.

3. The fertilizer composition according to claim 1 or 2, wherein the composition further comprises phosphoric acid (H3PO4) and / or urea (NH2CONH2).

4. The fertilizer composition according to any one of claims 1 to 3, wherein the composition further comprises calcium phosphate (Ca3(PO4)2) and / or nitric acid (HNO3), and optionally wherein the composition comprises phosphate rock containing at least a portion of the calcium phosphate.

5. The fertilizer composition according to claim 3 or 4, wherein the phosphoric acid is derived from a natural source.

6. The fertilizer composition according to claim 4 or 5, wherein at least a portion of the nitric acid is derived from renewable energy sources, optionally including solar, wind, hydro, tidal, geothermal, and / or biomass renewable energy sources.

7. The fertilizer composition according to any one of claims 1 to 6, wherein the composition does not contain a binder separate from the calcium nitrate.

8. The fertilizer composition according to any one of claims 1 to 7, wherein: At least a portion of the urea phosphate and / or urea diphosphate is absorbed on the surface of the calcium nitrate; and / or The fertilizer composition further comprises a potassium source; and / or The fertilizer is a homogeneous and / or an amorphous phase containing fertilizer components; and / or At least a portion of the urea diphosphate and / or urea phosphate is encapsulated by the calcium nitrate.

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

10. A method for producing the fertilizer composition according to any one of claims 1 to 9, the method comprising the following steps: (a) Contact calcium phosphate with nitric acid to generate a first reaction product containing calcium nitrate and phosphoric acid; and (b) Contact the first reaction product with urea to generate a second reaction product comprising urea phosphate and / or urea diphosphate. The second reaction product further includes calcium nitrate generated in step (a).

11. The method of claim 10, wherein steps a and b are performed in a one-pot synthesis manner.

12. The method according to claim 10 or 11, wherein no calcium phosphate remains in the first reaction product prior to contact with the urea in step b.

13. The method according to any one of claims 10 to 12, wherein step a is carried out for at least 45 minutes before the first reaction product in step b is contacted with the urea.

14. The method according to any one of claims 10 to 13, the method further comprising drying the second reaction product to form a solid fertilizer composition.

Images