Compound fertilizer comprising nitrogen, phosphorus and sulfur encapsulated in secondary calcium and magnesium nutrients

Abstract

Disclosed is a fertilizer comprising a mixture comprising i) calcium ammonium phosphate (CaNH4PO4), magnesium ammonium phosphate (MgNH4PO4), or a combination of CaNH4PO4 and MgNH4PO4, and ii) a mixture of calcium sulfate and ammonium sulfate ((NH4) 2Ca (SO4) 2), a mixture of magnesium sulfate and ammonium sulfate ((NH4) 2Mg (SO4) 2), or a combination of (NH4) 2Ca (SO4) 2 and (NH4) 2Mg (SO4) 2. Methods of making and using the fertilizers are also disclosed.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to European Application No. 22188759.9, filed on August 4, 2022, which is incorporated herein by reference in its entirety. Background of the invention I. Technical field

[0004] The present disclosure generally relates to fertilizer compositions containing a slow - release agent. In specific embodiments, the present disclosure relates to fertilizers containing a mixture of calcium ammonium phosphate and / or magnesium ammonium phosphate and calcium sulfate and ammonium sulfate and / or a mixture of magnesium sulfate and ammonium sulfate. II. Background art

[0005] Soil nutrients such as nitrogen, phosphorus, potassium, and sulfur, as well as trace elements such as iron, zinc, copper, and magnesium, contribute to agricultural prosperity and plant growth. After repeated growing cycles, the amounts of these nutrients in the soil may be depleted, resulting in inhibited plant growth and reduced yields. To counteract this effect, fertilizers have been developed to help replace the depleted essential nutrients. To meet the diverse needs of global crop production, single - nutrient fertilizers and multi - nutrient fertilizers such as blended fertilizers have been developed.

[0006] Applying fertilizers does not always provide the total amount of nutrients in the fertilizer to plants in a short period of time. Some fertilizers contain nutrients with compounds that are not easily absorbed and utilized by plants after application. In these cases, some fertilizers are applied long before planting the plants, or some are over - applied near the time of planting to provide sufficient nutrients to the plants initially. However, this is time - consuming and may require multiple treatments of the soil before or after planting and / or increase costs.

[0007] Plants, such as crop plants, require nutrients at least throughout the entire growth and maturation periods of the plants. However, many fertilizers disperse when applied to the soil, degrade, or are absorbed within a short time after application. To address this issue, the same plant can be fertilized multiple times or slow - release fertilizers can be used. Some methods of slow - release fertilizers include coating fertilizer cores with polymers. However, many polymer coatings are expensive and / or, after repeated applications, accumulate undesirably in the soil over time. Some methods of slow - release fertilizers include coating or mixing insoluble metal oxides such as MgO and CaO. However, these metal oxides do not provide much, if any, nutrients to plants. Summary of the invention

[0008] This disclosure provides solutions to at least some of the problems discussed above, including generating urea-free fertilizer products and generating fertilizer products with slow-release characteristics for their nutrients. 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 lies in providing a fertilizer containing calcium (Ca) and / or magnesium (Mg), nitrogen (N) present as ammonium, sulfur (S) present as sulfate, and phosphorus (P) present as phosphate. In some aspects, the fertilizer contains at least one metal ammonium phosphate compound, at least one metal sulfate compound, and ammonium sulfate. The metal ammonium phosphate compound can be used as a binder for other components in the fertilizer, such as metal sulfates and / or ammonium sulfate. In some embodiments, at least a portion of the fertilizer is synthesized by reacting metal oxides and / or metal carbonates such as calcium oxide (CaO), magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), and / or dolomite with sulfuric acid (H 2 SO 4 ) and phosphoric acid (H 3 PO 4 ). Non-limiting examples of the reactions can include the following reactions:

[0009] CaCO 3 + H 3 PO 4 + 2H 2 SO 4 → CaHPO 4 + Ca(HSO 4 ) 2 + 2H 2 O + 2CO 2

[0010] MgCO 3 + H 3 PO 4 + 2H 2 SO 4 → MgHPO 4 + Mg(HSO 4 ) 2 + 2H 2 O + 2CO 2

[0011] In some embodiments, at least a portion of the fertilizer is generated by reacting metal hydrogen phosphates such as CaHPO 4 and / or MgHPO 4 with an ammonia source such as ammonium hydroxide (NH 4 OH) and / or ammonia to produce compounds such as CaNH 4 PO 4 and / or MgNH4 PO 4 synthesized from metal ammonium phosphates. Non-limiting examples of the reaction may include the following reactions:

[0012] CaHPO 4 +NH 3 →CaNH 4 PO 4

[0013] MgHPO 4 +NH 3 →MgNH 4 PO 4

[0014] In some embodiments, at least a portion of the fertilizer is synthesized by reacting a metal bisulfate compound such as Ca(HSO 4 ) 2 and / or Mg(HSO 4 ) 2 with an ammonia source such as ammonium hydroxide (NH 4 OH) and / or ammonia to form a mixture of calcium sulfate (CaSO 4 ) and ammonium sulfate ((NH 4 ) 2 SO 4 ) ((NH 4 ) 2 Ca(SO 4 ) 2 ) and / or magnesium sulfate (MgSO 4 ) with ammonium sulfate ((NH 4 ) 2 SO 4 ) ((NH 4 ) 2 Mg(SO 4 ) 2 ). Non-limiting examples of the reaction may include the following reactions:

[0015] Ca(HSO 4 ) 2 +NH 3 →(NH 4 ) 2 Ca(SO 4 ) 2

[0016] Mg(HSO 4 ) 2 +NH 3 →(NH 4 ) 2 Mg(SO 4 ) 2

[0017] The final product may contain a mixture of the above chemical compositions, including but not limited to the compound CaNH 4 PO 4 / (NH 4 ) 2 Ca(SO 4 ) 2 , MgNH 4 PO 4 / (NH 4 ) 2 Mg(SO 4 ) 2 , or CaNH 4 PO 4 / (NH 4 ) 2 Ca(SO 4 ) 2 / MgNH 4 PO 4 / (NH 4 ) 2 Mg(SO 4 ) 2 or any one of them.

[0018] In some aspects, the chemical composition of the fertilizer and the reactions of the chemical components that produce the fertilizer can be described by the reaction formulas in Table 1.

[0019] Table 1

[0020]

[0021] The embodiments of the present disclosure are improvements over known fertilizers, including the use of a slow-release agent in fertilizers containing nitrogen (N), phosphorus (P), sulfur (S), and metals such as calcium (Ca) or magnesium (Mg). Current slow-release fertilizer products typically use physical interventions to slow down the release of fertilizers, such as coating fertilizers with polymer-insoluble materials to slow down the release of fertilizers. Current slow-release fertilizers can also employ enzyme inhibitors, such as urease inhibitors or nitrification inhibitors, to slow down the utilization of fertilizers. Although the fertilizers described herein may also include physical interventions and / or inhibitors, the fertilizers described herein do not always require these measures to produce a slow-release nutrient fertilizer composition.

[0022] The embodiments herein describe a mixture of nutrients and a method for preparing such a mixture, which accumulates fertilizers in the soil as a reservoir of nutrients for release over time. The fertilizer may include a quick-release aspect of the fertilizer, and the quick-release aspect of the fertilizer may comprise or consist of selected from MgSO 4 , CaSO 4 , K 3 PO 4 , CaCl 2, KCl, NiSO 4 , ZnSO 4 , FeCl 2 , FeSO 4 and any soluble salts of any combination thereof. The slow-release aspect of the fertilizer may comprise or consist of one or more double salts, such as calcium ammonium phosphate and magnesium ammonium phosphate, including any proportion thereof. In some cases, the slow-release aspect of the fertilizer may also comprise insoluble oxides or insoluble salts, including those insoluble oxides or insoluble salts containing Mg, Ca, Fe, Zn, Ni. The insoluble salts may comprise or consist of simple salts, such as MgCO 3 , CaCO 3 , FeCO 3 or combinations of these salts.

[0023] In some aspects, the fertilizer comprises or consists of a blend of a mixture of calcium ammonium phosphate with calcium sulfate and ammonium sulfate. In some aspects, the fertilizer comprises or consists of a blend of a mixture of magnesium ammonium phosphate with magnesium sulfate and ammonium sulfate. In some aspects, the fertilizer comprises or consists of a blend of calcium ammonium phosphate, calcium sulfate, magnesium ammonium phosphate, magnesium sulfate and ammonium sulfate.

[0024] The fertilizers involved in certain embodiments herein contain components that can be used to directly supplement the deficiencies of Mg, Ca, N and S in the soil in the form of readily soluble calcium sulfate, magnesium sulfate and / or ammonium sulfate, while also meeting the long-term Mg, Ca, N and P requirements by slowly releasing CaNH 4 PO 4 or MgNH 4 PO 4 .

[0025] Certain aspects relate to fertilizers comprising a homogeneous mixture comprising a nitrogen source, a phosphorus source, a sulfur source, and one or both of a calcium source and a magnesium source. In some aspects, the homogeneous mixture comprises a binder. The binder may comprise a slow-release agent. The slow-release agent may comprise calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 . In some aspects, the homogeneous mixture comprises a quick-release agent. The quick-release agent may comprise ammonium sulfate and one or both of calcium sulfate and magnesium sulfate.

[0026] Certain aspects relate to fertilizers comprising at least a portion of (NH 4 ) 2 Ca(SO 4 )2 and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 fertilizer. Certain aspects relate to fertilizers containing at least a portion of (NH 4 ) 2 Ca(SO 4 ) 2 and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 contained in the dried gel of calcium ammonium phosphate and / or magnesium ammonium phosphate. Certain aspects relate to fertilizers containing at least a portion of (NH 4 ) 2 Ca(SO 4 ) 2 and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 fertilizer.

[0027] In some aspects, the slow release agent further comprises magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), nickel oxide (NiO), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), iron(II) carbonate (FeCO 3 ), dolomite or a combination thereof.

[0028] In some aspects, the quick release agent comprises or consists of CaSO 4 , MgSO 4 and / or (NH 4 ) 2 SO 4 . In some aspects, the fertilizer does not contain a binder other than calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ) or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 . The fertilizer can be a granular fertilizer. In some aspects, the fertilizer contains dolomite.

[0029] In some aspects, the fertilizer contains, by weight %, nitrogen (N) of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, or 17 wt%, and phosphorus (P) equivalent to an amount of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 2 O 5 : 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, or 18 wt%, and sulfur (S) of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, or 16 wt%. In some aspects, the fertilizer contains calcium (Ca) of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, and magnesium (Mg) of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%. In some cases, the weight ratio of the quick - release agent to the slow - release agent included is from about 3:1 to about 1:5, such as 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, or 1:5.

[0030] In some aspects, at least a portion of (NH 4 ) 2 Ca(SO 4 ) 2 is in the hexa - hydrate form, and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 is in the hexa - hydrate form. In some aspects, the fertilizer does not contain ammonium nitrate, urea, and / or polymers. In some aspects, the fertilizer further contains ammonium nitrate, urea, and / or polymers.

[0031] Some aspects relate to methods of preparing fertilizers, including any of the fertilizers described herein. The method may include step (a) and / or step (b). In step (a), CaO, MgO, MgCO 3 , CaCO 3 , and / or dolomite may be combined with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4)Contact to generate a first reaction product, which comprises: calcium hydrogen phosphate (CaHPO 4 ) and / or magnesium hydrogen phosphate (MgHPO 4 );and calcium bisulfate (Ca(HSO 4 ) 2 ) and / or magnesium bisulfate (Mg(HSO 4 ) 2 ). In step (b), the first reaction product can be contacted with an ammonia source such as ammonium hydroxide (NH 4 OH) and / or ammonia (NH 3 ) to generate a second reaction product, which comprises: calcium ammonium phosphate (CaNH 4 PO 4 ) and / or magnesium ammonium phosphate (MgNH 4 PO 4 );and a mixture of calcium sulfate and ammonium sulfate (NH 4 ) 2 Ca(SO 4 ) 2 ) and / or a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2)。In some aspects, the method of preparing the fertilizer includes drying a fertilizer mixture to form a solid fertilizer composition. Step (a), step (b), step (c), and / or the drying can be carried out at about 55°C to about 150°C, such as at 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, and 150°C. In some aspects, step (a) and / or step (b) can be carried out at 55°C to 75°C or any temperature within this range. In some aspects, the fertilizer composition comprises or consists of: calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 ; and a mixture of calcium sulfate and ammonium sulfate ((NH 4 ) 2 Ca(SO 4 ) 2 ), a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2 ), or (NH 4 ) 2 Ca(SO 4 ) 2 and (NH 4 ) 2 Mg(SO 4 )2 Combination. In some aspects, the nitrogen source includes a solution of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide, and / or phthalimide.

[0032] The present invention also discloses the following aspects 1 to 40.

[0033] Aspect 1 is a fertilizer composition comprising: calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 ; and a mixture of calcium sulfate and ammonium sulfate ((NH 4 ) 2 Ca(SO 4 ) 2 ), a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2 ), or a combination of (NH 4 ) 2 Ca(SO 4 ) 2 and (NH 4 ) 2 Mg(SO 4 ) 2 .

[0034] Aspect 2 is the fertilizer composition according to aspect 1, wherein the composition comprises 10 wt% to 17 wt% of nitrogen (N), an amount of potassium (P) equivalent to 11 wt% to 18 wt% of P 2 O 5 , and 10 wt% to 16 wt% of sulfur (S).

[0035] Aspect 3 is the fertilizer composition according to any one of aspects 1 and 2, wherein the composition comprises 5 wt% to 10 wt% of calcium (Ca) and 5 wt% to 10 wt% of magnesium (Mg).

[0036] Aspect 4 is the fertilizer composition according to any one of aspects 1 to 3, wherein the composition further comprises calcium phosphate, magnesium phosphate, and / or ammonium phosphate ((NH 4 ) 3 PO 4 ).

[0037] Aspect 5 is the fertilizer composition according to aspect 4, wherein the composition comprises calcium sulfate (CaSO contained in waste gypsum and / or recycled gypsum4 )。

[0038] Aspect 6 is the fertilizer composition according to any one of Aspects 1 to 5, wherein the composition further comprises magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), nickel oxide (NiO), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), iron(II) carbonate (FeCO 3 ) or a combination thereof.

[0039] Aspect 7 is the fertilizer composition according to any one of Aspects 1 to 6, wherein the composition further comprises nickel sulfate (NiSO 4 ), zinc sulfate (ZnSO 4 ), iron(II) sulfate (FeSO 4 ) or a combination thereof.

[0040] Aspect 8 is the fertilizer composition according to any one of Aspects 1 to 7, which further comprises iron(II) phosphate (FePO 4 ) and / or dolomite.

[0041] Aspect 9 is the fertilizer composition according to any one of Aspects 1 to 8, wherein the composition does not contain a binder different from calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), (NH 4 ) 2 Ca(SO 4 ) 2 or (NH 4 ) 2 Mg(SO 4 ) 2 .

[0042] Aspect 10 is the fertilizer composition according to any one of Aspects 1 to 9, wherein (NH 4 ) 2 Ca(SO 4 ) 2 comprises calcium ammonium sulfate hexahydrate and / or (NH 4 ) 2 Mg(SO 4 ) 2 comprises magnesium ammonium sulfate hexahydrate.

[0043] Aspect 11 is the fertilizer composition according to any one of Aspects 1 to 10, wherein at least a part of the ammonium sulfate is adsorbed on the surface of calcium ammonium phosphate and / or magnesium ammonium phosphate.

[0044] Aspect 12 is the fertilizer composition according to any one of Aspects 1 to 11, wherein the composition comprises CaNH 4 PO 4 and a combination of MgNH 4 PO 4 .

[0045] Aspect 13 is the fertilizer composition according to any one of Aspects 1 to 12, wherein the composition comprises (NH 4 ) 2 Ca(SO 4 ) 2 and a combination of (NH 4 ) 2 Mg(SO 4 ) 2 .

[0046] Aspect 14 is the fertilizer composition according to any one of Aspects 1 to 13, wherein the fertilizer composition comprises a nitrogen source, a phosphorus source, and a potassium source.

[0047] Aspect 15 is the fertilizer composition according to any one of Aspects 1 to 14, wherein the fertilizer is homogeneous.

[0048] Aspect 16 is the fertilizer composition according to any one of Aspects 1 to 15, wherein the composition comprises a gel.

[0049] Aspect 17 is the fertilizer composition according to any one of Aspects 1 to 15, wherein the composition comprises a dried gel.

[0050] Aspect 18 is the fertilizer composition according to any one of Aspects 1 to 17, wherein at least a portion of (NH 4 ) 2 Ca(SO 4 ) 2 and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 is encapsulated by calcium ammonium phosphate and / or magnesium ammonium phosphate.

[0051] Aspect 19 is the fertilizer composition according to any one of Aspects 1 to 18, wherein the fertilizer composition is a granular fertilizer.

[0052] Aspect 20 is the fertilizer composition according to any one of Aspects 1 to 19, wherein the composition does not contain ammonium nitrate.

[0053] Aspect 21 is the fertilizer composition according to any one of Aspects 1 to 20, wherein the composition does not contain urea.

[0054] Aspect 22 is the fertilizer composition according to any one of Aspects 1 to 21, wherein the composition does not contain polymers.

[0055] Aspect 23 is a method for producing a fertilizer composition, the method comprising the steps of: (a) contacting CaO, MgO, MgCO 3 , CaCO 3 and / or dolomite with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) to produce a first reaction product comprising: calcium hydrogen phosphate (CaHPO 4 ) and / or magnesium hydrogen phosphate (MgHPO 4 ); and calcium bisulfate (Ca(HSO 4 ) 2 ) and / or magnesium bisulfate (Mg(HSO 4 ) 2 ); (b) contacting the first reaction product with an ammonia source to produce a second reaction product comprising: calcium ammonium phosphate (CaNH 4 PO 4 ) and / or magnesium ammonium phosphate (MgNH 4 PO 4 ); and a mixture of calcium sulfate and ammonium sulfate ((NH 4 ) 2 Ca(SO 4 ) 2 ) and / or a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2 ).

[0056] Aspect 24 is the method according to aspect 23, further comprising drying the second reaction product to form a solid fertilizer composition.

[0057] Aspect 25 is the method according to any one of aspects 23 and 24, further comprising: (c) combining the second reaction product with CaSO 4 .

[0058] Aspect 26 is the method according to aspect 25, wherein the combining step (c) comprises combining the second reaction product with CaSO 4 in a weight ratio of from about 3:1 to about 1:3.

[0059] Aspect 27 is the method according to any one of aspects 25 and 26, wherein CaSO 4 comprises waste gypsum from red gypsum and / or H 3 PO 4 production.

[0060] Aspect 28 is the method according to any one of Aspects 23 to 27, wherein step (a) and / or step (b) is carried out at 55°C to 75°C.

[0061] Aspect 29 is the method according to any one of Aspects 23 to 28, wherein the ammonia source is ammonium hydroxide (NH 4 OH) and / or ammonia (NH 3 ).

[0062] Aspect 30 is the method according to any one of Aspects 23 to 29, wherein in step (a), dolomite is contacted with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ).

[0063] Aspect 31 is the method according to any one of Aspects 23 to 29, wherein in step (a), MgCO 3 and CaCO 3 are contacted with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ).

[0064] Aspect 32 is the method according to any one of Aspects 23 to 31, wherein in step (a), there is a stoichiometric excess of phosphoric acid (H 4 ) and sulfuric acid (H 4 ) required to form calcium hydrogen phosphate (CaHPO 4 ) and / or magnesium hydrogen phosphate (MgHPO 2 ) and calcium bisulfate (Ca(HSO 4 ) 2 ) and / or magnesium bisulfate (Mg(HSO 3 PO 4 ) and sulfuric acid (H 2 SO 4 ).

[0065] Aspect 33 is the method according to Aspect 32, wherein at least a part of the stoichiometric excess of phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) is contacted with the ammonia source in step (b) to form ammonium phosphate ((NH 4 ) 3 PO 4 ) and / or ammonium sulfate ((NH 4 ) 2 SO 4 ).

[0066] Aspect 34 is the method according to any one of aspects 23 to 33, wherein phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) have a weight ratio of 1:1 to 3:1 with CaO, MgO, MgCO 3 , CaCO 3 and / or dolomite.

[0067] Aspect 35 is the method according to any one of aspects 23 to 34, wherein the fertilizer composition is the fertilizer composition according to any one of aspects 1 to 22.

[0068] Aspect 36 is a fertilization method, which includes contacting a plant, soil, water or a combination thereof with the fertilizer composition according to any one of aspects 1 to 22.

[0069] Aspect 37 is a method for increasing the soil pH value, which includes contacting the soil with the fertilizer composition according to any one of aspects 1 to 22.

[0070] Aspect 38 is the method according to aspect 37, wherein the pH value of the contacted soil is less than 6.

[0071] Aspect 39 is the method according to any one of aspects 37 and 38, wherein the pH value of the soil is increased to 6 or greater than 6.

[0072] Aspect 40 is the method according to any one of aspects 37 to 39, wherein the pH value of the contacted soil is 3 to 4, and the pH value of the soil is increased to 6 to 8.

[0073] The term "fertilizer" is defined as a material applied to soil or plant tissue to provide one or more plant nutrients essential for or beneficial to plant growth, and / or a stimulant or enhancer that promotes or enhances plant growth.

[0074] The term "granule" may include solid materials. Granules can have various different shapes, non-limiting examples of which include spherical, disc-shaped, oval, rod-shaped, oblong or random shapes.

[0075] The term "particle" may include solid materials with a maximum size less than millimeters.

[0076] The term "particulate" or "powder" may include multiple particles.

[0077] As used herein, the terms "about" or "approximately" are defined as being close to the degree understood by a person of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as being within 10%, preferably within 5%, more preferably within 1% and most preferably within 0.5% deviation.

[0078] The terms "weight %", "volume %" or "mole %" refer to the weight percentage, volume percentage or mole percentage of the component based on the total weight of the material containing the component, the total volume of the material or the total number of moles of the material, respectively. In a non-limiting example, 10 grams of a component in 100 grams of material is 10 weight %.

[0079] When an element is used together with the term "comprising / including" without a quantifier in front, it may mean "one", but it also conforms to the meaning of "one or more", "at least one" and "one or more than one".

[0080] The phrase "and / or" means "and" or "or". For example, A, B and / or C includes: A alone, B alone, C alone, the combination of A and B, the combination of A and C, the combination of B and C, or the combination of A, B and C. In other words, "and / or" is used as an inclusive "or".

[0081] As used in this specification and the claims, the words "comprise", "have", "include" or "contain" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0082] The compositions and their methods of use may "comprise", "consist essentially of" or "consist of" any of the ingredients or steps disclosed throughout the specification. Compositions and methods "consisting essentially of" any of the ingredients or steps disclosed limit the scope of the claims to the specific materials or steps that do not substantially affect the basic and novel features of the claimed invention.

[0083] It is contemplated that any embodiment discussed in this specification can be implemented corresponding to any method or composition of the present invention, and vice versa. In addition, the compositions of the present invention can be used to implement the methods of the present invention.

[0084] Other objects, features and advantages of the present invention will become apparent from the following detailed description. However, it should be understood that the detailed description and specific examples, while indicating specific embodiments of the present invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] The following figures form a part of this specification and further illustrate certain aspects of the present invention. The present invention can be better understood by referring to one or more of these figures in combination with the detailed description of specific embodiments given in this specification.

[0086] Figure 1 : Schematic diagram of a system and method for producing fertilizer according to a non - limiting example of the systems and methods disclosed herein.

[0087] Figure 2 : 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

[0088] Certain aspects of the present disclosure provide advantages over existing fertilizers, including that the nutrients contained in the fertilizer have slow - release characteristics. Certain aspects provided herein enable the fertilizer to slowly release nutrients into the soil over a period of time, such as throughout the entire growth cycle of a plant. In some aspects, this ability can be achieved without the intervention of adhesives, inhibitors, or other compounds added to the fertilizer nutrients. In some embodiments, the fertilizer comprises a double salt, such as a metal ammonium phosphate salt, such as calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 ; a mixture of calcium sulfate and ammonium sulfate ((NH 4 ) 2 Ca(SO 4 ) 2 ), a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2 ), or (NH 4 ) 2 Ca(SO 4 ) 2 and (NH 4 ) 2 Mg(SO 4 ) 2 in combination, which can be a chemical component and / or a homogeneous mixture. The metal ammonium phosphate salt compound can be used as an adhesive for other components in the fertilizer.

[0089] I. Fertilizer

[0090] Certain embodiments of the present disclosure relate to compound fertilizers, which include: double salts, such as metal ammonium phosphates, which may contain CaNH 4 SO 4 and / or MgNH 4 SO 4 ; and a mixture of calcium sulfate and ammonium sulfate ((NH 4 ) 2 Ca(SO 4 ) 2 ) and / or a mixture of magnesium sulfate and ammonium sulfate ((NH 4 ) 2 Mg(SO 4 ) 2 ). Certain aspects relate to the synthesis of nutrient complexes using components from natural sources of fertilizers such as CaO, MgO, MgCO 3 , CaCO 3 , H 3 PO 4 , H 2 SO 4 , NH 3 and NH 4 OH. In some aspects, the compound fertilizer is a mixture of homogeneous mixtures.

[0091] The fertilizer, which may be fertilizer granules, may contain a mixture of calcium (Ca), magnesium (Mg), phosphorus (P), nitrogen (N) in the form of ammonium, and sulfur (S) in the form of sulfate. The ratio of each element present in the fertilizer can be adjusted according to the specific application.

[0092] At least a portion of the Ca can be present in the form of calcium ammonium phosphate and / or calcium sulfate. In some aspects, based on the total weight of Ca in the mixture, at least 90 wt%, or at least 95 wt%, or from 90 wt% to 100 wt%, or any wt% that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following of the Ca in the mixture can be present in the form of calcium ammonium phosphate and / or calcium sulfate: 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.5 wt%, and 100 wt%. In some embodiments, any wt% that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following of the Ca in the mixture can be present in the form of calcium ammonium phosphate: 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%, 99.5 wt%, and 100 wt%.In some embodiments, the weight % of Ca that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following in the mixture may be present in the form of calcium sulfate: 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%, 99.5 wt% and 100 wt%.

[0093] At least a portion of the Mg may be present in the form of magnesium ammonium phosphate and / or magnesium sulfate. In some aspects, based on the total weight of Mg in the mixture, at least 90 wt%, or at least 95 wt%, or from 90 wt% to 100 wt%, or any wt% that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following of the Mg in the mixture may be present in the form of magnesium ammonium phosphate and / or magnesium sulfate: 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.5 wt%, and 100 wt%. In some embodiments, any wt% that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following of the Mg in the mixture may be present in the form of magnesium ammonium phosphate: 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%, 99.5 wt%, and 100 wt%.In some embodiments, the weight % of Mg that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following in the mixture may be present in the form of magnesium sulfate: 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%, 99.5 wt% and 100 wt%.

[0094] In some aspects, the mixture may contain i) CaNH provided in an amount of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight % based on the total weight of the mixture and / or the fertilizer granules 4 SO 4: 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%, 99.5 wt% and 100 wt%; ii) provided in an amount of wt% of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following, based on the total weight of the mixture and / or the fertilizer granules, MgNH 4 SO 4: 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%, 99.5 wt% and 100 wt%; iii) CaSO provided in an amount of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight % based on the total weight of the mixture and / or the fertilizer granules 4: 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%; iv) MgSO provided in an amount of wt% based on the total weight of the mixture and / or the fertilizer granules, at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 4: 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%; and v) provided in an amount of wt% based on the total weight of the mixture and / or the fertilizer granules, at least any one of the following, at most any one of the following, equal to any one of the following or between any two of the following (NH 4 ) 2 SO 4: 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%.

[0095] In some aspects, the homogeneous mixture contains Ca, Mg, N, P, and / or S, based on the total weight of the mixture and / or the fertilizer granules, wherein i) the Ca content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following weight percentages: 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%, 99.5 wt% and 100 wt%, ii) the Mg content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 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%, 99.5 wt% and 100 wt%, iii) the N content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 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%, 99.5 wt% and 100 wt%, iv) the P content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 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%, 99.5 wt% and 100 wt%, and v) the S content of the homogeneous mixture can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following by weight%: 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%, 99.5 wt% and 100 wt%.

[0096] Ca, Mg, N, P and / or S can be present and / or sourced in the form of water-soluble compounds or water-insoluble compounds. In some cases, Ca, Mg, N, P and / or S can be present as salts. In some aspects, Ca, Mg, N, P and / or S can be present as water-soluble salts. In some cases, the water-soluble Ca salt can be CaSO 4 . In some cases, the water-soluble Mg salt can be MgSO 4 . The Ca salt, Mg salt, N salt, P salt and / or S salt can be in non-hydrate form and / or one or more hydrate forms.

[0097] Based on the total weight of the fertilizer granules, the water content of the dried fertilizer can be less than 1 wt%, such as 0.1 wt% to 0.9 wt%, or at least any one of the following or between any two of the following wt%: 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%, or any range therebetween. As a non-limiting example, the water content can be determined by drying the sample at 50 °C for 25 minutes and measuring the amount of mass loss after drying the fertilizer.

[0098] The fertilizer can be of any suitable shape. Non-limiting shapes include spherical, cubic, cylindrical, globular, oval, and oblong. In some aspects, the fertilizer granules can be cylindrical with a cross-section that is circular, elliptical, oval, triangular, square, rectangular, pentagonal, or hexagonal, although cylindrical cores with cross-sections of other shapes can also be made. In some aspects, the fertilizer granules can be 0.5 mm to 6 mm or 0.5 mm to 5 mm in their widest dimension, preferably 1 mm to 4 mm, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following dimensions: 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, the fertilizer granules can be substantially spherical, with an average diameter of the sphere being 0.5 mm to 6 mm or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following diameters: 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.

[0099] The fertilizer can be water-dispersible and / or soil-dispersible. In some aspects, the fertilizer granules have a particle size of 2 mm to 4 mm before adding water, and when stirred at a rate of 90 rpm to 110 rpm at ambient temperature for 1 minute in water with a pH of 7, the fertilizer granules can disintegrate into fine particles with a particle size 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.

[0100] 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 (with a deviation within ±20%, or ±10%, or ±5%, or ±3%, or ±2%, or ±1% or ±0.5%).

[0101] In some aspects, the fertilizer granules may contain a homogeneous mixture. The homogeneous mixture may have the components as described above. In some cases, the homogeneous mixture may have an optional coating on its outer surface. In some cases, CaNH 4 PO 4 and / or MgNH 4 PO 4 may act as a binder in the fertilizer. In some cases, CaNH 4 PO 4 and / or MgNH 4 PO 4 is the only binder in the fertilizer. In some cases, CaNH 4 PO 4 and / or MgNH 4 PO 4 forms an amorphous phase, a continuous phase, and / or encapsulates other components in the fertilizer. In some cases, the fertilizer contains a matrix of CaNH 4 PO 4 and / or MgNH 4 PO 4 that at least partially surrounds and / or encapsulates at least a portion of calcium sulfate, magnesium sulfate, and / or ammonium sulfate. In some cases, the fertilizer contains microparticles of one or more slow-release agents and / or one or more quick-release agents.

[0102] In some aspects, other fertilizer substances may or may not be included in the fertilizer. If included, other fertilizers may be selected based on the specific needs of a particular type of soil, climate, or other growth conditions to maximize the effectiveness of the fertilizer in enhancing plant growth and crop yield. Other additives may or may not be included in the fertilizer. Non-limiting examples of additives that may or may not be included in the fertilizer of the present invention include other nitrogen nutrients, other phosphorus nutrients, other potassium nutrients, other trace element nutrients, and / or other secondary nutrients. Trace element nutrients may be copper, iron, chlorine, 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, other secondary nutrients may include lime and / or superphosphate. In some cases, other fertilizer substances and / or other additives are included in the optional coating of the fertilizer.

[0103] 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 of by OHP Inc., USA, 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfanilamido-thiazole (ST), and any combination thereof. In one aspect, the nitrification inhibitor can 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 can contain NBTPT, DMPP, TU, DCD, PPDA, Nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST, or a combination thereof.

[0104] In some cases, the binder includes phosphates, polyphosphates, biodegradable polymers, or waxes, or a combination thereof. Suitable waxes include, but are not limited to, plant waxes, high melting point waxes, ethylene bis(stearamide) wax, paraffin wax, polyvinyl 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 polymeric materials such as polylactic acid, poly(3-hydroxypropionic acid), polyvinyl alcohol, polycaprolactone, poly-L-lactide, polybutylene succinate, and biodegradable starch-based polymers. The binder can include gypsum, flour, starch, gluten, kaolin, bentonite, colloidal silica, or a combination thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin-modified starches.

[0105] In some cases, the pH buffer includes MgO, KH 2 PO 4 、NaHCO 3, chalk powder, aluminum hydroxide, magnesium hydroxide, aluminum hydroxide / magnesium hydroxide co-precipitate, aluminum hydroxide / sodium bicarbonate co-precipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate, potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, sodium gluconate, sodium hydrogen phosphate, sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate, and tromethamine, and combinations thereof.

[0106] The fertilizers described herein can be included in compositions for application to soil. In some aspects, in addition to the fertilizers described herein, the compositions can further include other fertilizer compounds, micronutrient nutrients, macronutrients, urea, other nitrogen nutrients, pesticides, herbicides or fungicides, or combinations thereof. The fertilizers described herein can also be included in blended compositions containing other fertilizers. The other fertilizers can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), monopotassium phosphate (MKP), triple superphosphate (TSP), rock phosphate, single super phosphate (SSP), ammonium sulfate, etc.

[0107] The granulated fertilizer can have desired physical properties, such as a desired level of abrasion resistance, particle strength, granulatability, hygroscopicity, particle shape, and particle size distribution. In some aspects, the fertilizer particles can have a compressive strength of more than 1.5 kgf, such as more than 1.8 kgf, such as 2 kgf to 6 kgf, or a compressive strength that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 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 particles can be 1 g / cc to 1.2 g / cc, or a bulk density that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 1 g / cc, 1.02 g / cc, 1.04 g / cc, 1.06 g / cc, 1.08 g / cc, 1.1 g / cc, 1.12 g / cc, 1.14 g / cc, 1.16 g / cc, 1.18 g / cc, and 1.2 g / cc. In some aspects, with stirring at 90 rpm to 110 rpm and at ambient temperature, within 5 minutes after adding 100 mg of fertilizer particles to water, 10 mg or more than 10 mg, such as 10 mg to 40 mg, or a mass of fertilizer that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following can dissolve in 1 ml of water with a pH of 7: 10 mg, 11 mg, 12 mg, 13 mg, 14 mg, 15 mg, 16 mg, 17 mg, 18 mg, 19 mg, 20 mg, 21 mg, 22 mg, 23 mg, 24 mg, 25 mg, 26 mg, 27 mg, 28 mg, 29 mg, 30 mg, 31 mg, 32 mg, 33 mg, 34 mg, 35 mg, 36 mg, 37 mg, 38 mg, 39 mg, and 40 mg. In some aspects, in the abrasion loss test, the fertilizer particles can lose less than 0.13 wt%, such as 0.02 wt% to 0.12 wt%, or a wt% that is at most any one of the following, equal to any one of the following, or between any two of the following: 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, and 0.12 wt%. The abrasion loss can be measured by the following abrasion loss test.

[0108] Abrasion loss test: Weigh multiple sieved particles with a single particle size of 2 mm to 4 mm and a total volume of 100 cm 3Fertilizer granules (W1), and place them together with 50 stainless steel balls with a total weight of 100 g into a test drum. Seal the drum and rotate it at 30 rpm for 10 minutes. Then, separate the steel balls from the sample and sieve the material through a 2-mm sieve using a vibratory sieve shaker. Then reweigh the total weight (W2) of the particles larger than 2 mm on the sieve. Calculate the weight % loss due to abrasion according to the following formula:

[0109]

[0110] II. Method for preparing fertilizer

[0111] Reference Figure 1 , a schematic diagram of a system and method for preparing fertilizer according to an embodiment of the present invention is described herein. The system 100 may include a granulator 102 and a dryer 104. The feed mixture 106 may be granulated in the granulator 102 in the presence or absence of water to form a wet granule mixture 108. If water is present, the water may be provided together with the feed mixture 106, and / or the water may be added separately to the granulator 102. The wet granule mixture 108 may be dried in the dryer 104 to obtain a dry granule mixture 110 containing fertilizer.

[0112] Reference Figure 2, a schematic diagram of a system and method for preparing fertilizers according to another embodiment of the present invention is described herein. System 200 may include a mixer / reactor 212, although the mixer and reactor may be two, three, four, or more than four components, such as two reactors and one mixer or one reactor and one mixer. System 200 may also include a granulator 202, a spheronizer 214, one or more screens 216, and a dryer 204, or any combination thereof. The feed mixture components 218 may be added to the mixer / reactor 212 individually and / or in any possible combination. In the mixer / reactor 212, the feed components may be reacted and / or mixed to form a feed mixture 206. The feed mixture 206 may be granulated in the granulator 202, with or without additional water, to form a wet particulate mixture 220. The particles of the wet particulate mixture 220 may be spheronized in the spheronizer 214 to form a wet particulate mixture 222 containing substantially spherical particles. The wet particulate mixture 222 may be passed through one or more screens 216 to separate particles having a particle size less than or greater than the desired particle size from the wet particulate mixture 222 and obtain a wet particulate mixture 224 containing particles of the desired particle size. At least a portion of the particles 226 separated from the granulated mixture 224 containing particles of the desired particle size may be recycled to the granulator 202. The wet particulate mixture 224 containing particles of the desired particle size may be dried in the dryer 204 to obtain a dry particulate mixture 210 containing fertilizer particles. In some aspects, the mixer / reactor 212 may include a ribbon mixer.

[0113] The feed mixture components 218 may include: i) a Ca source, such as calcium carbonate, ii) a Mg source, such as magnesium carbonate, iii) an N source, such as NH 4 + and / or NH 3 , iv) a P source, such as phosphoric acid, and v) an S source, such as sulfuric acid. In some cases, the mixture components may provide more than one of Ca, Mg, N, P, and / or S. In some cases, the mixture components provide other nutrients and / or trace element nutrients, such as Fe and / or Si. In certain aspects, one or more components may be added as an aqueous solution. In some cases, the mixture components are provided in powder form. In some cases, one or more components may be added as a gas. In some cases, NH is provided at a pressure above 1 bar, such as at or within any range below or at the following 3: 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, a portion of the mixture components is provided in powder form.

[0114] The feed mixture 106, feed mixture 206 may contain Ca, Mg, N, P, and / or S. In some aspects, the feed mixture 106, feed mixture 206 may contain i) metal carbonate, ii) phosphoric acid, iii) ammonium hydroxide, iv) metal oxide, v) CaNH 4 PO 4 , vi) MgNH 4 PO 4 , vii) sulfuric acid, viii) dolomite, ix) MgHPO 4 , x) CaHPO 4 , xi) CaSO 4 , xii) MgSO 4 and / or xiii) (NH 4 ) 2 SO 4 .

[0115] Water may be added to the feed mixture in the mixer / reactor 212 and / or the granulator 102, granulator 202. In certain aspects, a total amount of 5 g to 20 g of water may be added per 100 g of the feed mixture, or at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following (e.g., added together with one or more feed mixture components or added separately): 5 g, 6 g, 7 g, 8 g, 9 g, 10 g, 11 g, 12 g, 13 g, 14 g, 15 g, 16 g, 17 g, 18 g, 19 g, and 20 g.

[0116] In some aspects, granulator 102 and granulator 202 can be drum granulators, pugmill granulators, pan granulators, solid mixers, attrition drums, extruders, high shear mix granulators, roller granulators, Mycromix, or round-bottom flasks. In granulator 102 and granulator 202, the feed mixtures 106 and 206 can be granulated by agglomeration, spray granulation, compaction, slurry granulation, and / or high shear mix granulation. In some specific aspects, the feed mixtures 106 and 206 can be granulated by compaction in granulator 102 and granulator 202. In some aspects, granulator 102 and granulator 202 can include at least two rollers, and compaction granulation can include using at least two rollers to compress the feed mixture. In some aspects, during the compaction process, the two rollers can move in a countercurrent direction. In some aspects, the feed mixture can be compressed into granules of a specific shape, such as cylindrical granules, by at least two rollers. In some aspects, the surface of one roller can have desired holes to compress the feed mixture into the holes, while the surface of the other roller can push the feed mixture into the holes. The pressure during granulation, such as compaction granulation, can be from 1 bar to 40 bar, or can be at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following pressures: 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 102 and granulator 202 at ambient temperature to 50°C, or at a temperature that is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: -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.

[0117] In some aspects, the reaction and mixing of the feed mixture components and the granulation of the feed mixture can be carried out in different containers. For example, mixer / reactor 212 and granulator 202 can be different containers. In some aspects, the reaction and mixing of the feed mixture components and the granulation of the feed mixture can be carried out in the same container. For example, mixer / reactor 212 and granulator 202 can be the same container (not shown). In some aspects, mixer / reactor 212 and granulator 202 can be more than two containers. As a non-limiting example, in some cases, MgHPO 4 and CaHPO 4 are formed in two different containers. In some cases, MgHPO 4 and CaHPO 4 are formed in one container. In some cases, CaNH4 PO 4 and MgNH 4 PO 4 are formed in two different containers. In some cases, CaNH 4 PO 4 and MgNH 4 PO 4 are formed in one container. In some cases, MgHPO 4 and CaHPO 4 are formed in two different containers, and CaNH 4 PO 4 and MgNH 4 PO 4 are formed in one container. In some cases, MgHPO 4 and CaHPO 4 are formed in two different containers, and CaNH 4 PO 4 and MgNH 4 PO 4 are formed in two different containers. In some cases, MgHPO 4 and CaHPO 4 are formed in one container, and CaNH 4 PO 4 and MgNH 4 PO 4 are formed in another container. In some cases, MgHPO 4 and CaHPO 4 are formed in one container, and CaNH 4 PO 4 and MgNH 4 PO 4 are formed in the same container as MgHPO 4 and CaHPO 4 In some cases, MgSO 4 and CaSO 4 are formed in two different containers. In some cases, MgSO 4 and CaSO 4 are formed in one container. In some cases, CaNH 4 PO 4 and MgNH 4 PO 4 are formed in two different containers, and MgSO 4 and CaSO 4 are formed in one container. In some cases, CaNH 4 PO 4 and MgNH4 PO 4 are formed in two different containers, and MgSO 4 and CaSO 4 are formed in two different containers. In some cases, CaNH 4 PO 4 and MgNH 4 PO 4 are formed in one container, and MgSO 4 and CaSO 4 are formed in one container. In some cases, CaNH 4 PO 4 and MgNH 4 PO 4 are formed in one container, and MgSO 4 and CaSO 4 are formed in the same container as CaNH 4 PO 4 and MgNH 4 PO 4 .

[0118] In some aspects, MgHPO 4 , CaHPO 4 , CaNH 4 PO 4 , MgNH 4 PO 4 , MgSO 4 , CaSO 4 and / or (NH 4 ) 2 SO 4is formed at at least the following temperature, at most the following temperature, equal to the following temperature, or at a temperature between any two of the following temperatures: 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°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C and 150°C, such as 40°C to 150°C, or 100°C to 150°C, or 75°C to 150°C, or 55°C to 75°C.

[0119] In some cases, the fertilizer can be extruded before drying. The extruder can extrude the fertilizer at at least the following pressure, at most the following pressure, equal to the following pressure, or at a pressure between any two of the following pressures: 1 bar, 2 bar, 3 bar, 4 bar, 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, 31 bar, 32 bar, 33 bar, 34 bar, 35 bar, 36 bar, 37 bar, 38 bar, 39 bar and 40 bar. The extruder can extrude the fertilizer at at least the following temperature, at most the following temperature, equal to the following temperature, or at a temperature 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 segmented before drying, such as by slicing or segmenting through a die.

[0120] In some aspects, the desired particle size of the final fertilizer product, such as granules, can be from 0.5 mm to 5 mm, or from 1 mm to 4 mm, and particles with a particle size less than 0.5 mm or less than 1 mm, and / or particles with a particle size greater than 4 mm or greater than 5 mm can be separated from the wet particle mixture 222 through one or more sieves 216. In some aspects, the wet particle mixture can be rounded and / or spheronized in a spheronizer. In some cases, the wet particle mixture is in contact with the spheronizer for at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following 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 spheronizer has a rotatable disk that can rotate at a rotational speed of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 200 rpm, 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm, 5000 rpm. In some aspects, the wet particle mixture can be dried in dryer 104, dryer 204 at a temperature of 40°C to 85°C, or at a temperature of at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following: 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, and 85°C. In some aspects, dryer 104, dryer 204 can be a fluidized bed dryer, a drum dryer, or a pneumatic dryer. In some aspects, the wet particle mixture can be dried in dryer 104, dryer 204 using a hot air stream, and the flow rate of the hot air stream is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following flow rates: 100 m 3 / h, 150 m 3 / h, 200 m 3 / h, 250 m 3 / h, 300 m 3 / h, 350 m 3 / h, 400 m 3 / h, 450 m 3 / h, and 500 m 3 / h, and / or the rotational speed of the dryer is at least any one of the following, at most any one of the following, equal to any one of the following, or between any two of the following rotational speeds: 5 rpm, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm, 35 rpm, 40 rpm, 45 rpm, and 50 rpm.

[0121] III. Method of Using Fertilizer

[0122] The fertilizers of the present disclosure, including fertilizer granules, compositions containing the fertilizers, and blended fertilizers containing the fertilizers, can be used in methods for increasing the amount of one or more plant nutrients in soil and methods for promoting plant growth. Such methods can include applying an effective amount of a composition and / or blend containing the fertilizer of the present invention to the soil. The methods can 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 methods can include applying the blended fertilizer of the present invention to at least one of soil, organisms, liquid carriers, liquid solvents, etc. One or more compositions containing the fertilizer and / or one or more blended fertilizers can be applied to plants and / or soil as top dressing fertilizers, base fertilizers, and / or by any suitable application method.

[0123] Non-limiting examples of plants that can benefit from the fertilizers of the present invention include vines, trees, shrubs, straw plants, ferns, etc. Plants can include orchard crops, vines, ornamental plants, food crops, trees, and harvested plants. Plants can include Gymnosperms, Angiosperms, and / or Pteridophytes.

[0124] At different times after applying the fertilizer composition to the soil, the effectiveness of the composition containing the fertilizer of the present invention can be determined by measuring the amount of phosphorus and optionally other nutrients in the soil. It should be understood that different soils have different properties, which 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 making a side-by-side comparison in the same soil under the same conditions.

[0125] Examples

[0126] The present invention will be described in more detail by specific examples. The following examples are for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize that various non-critical parameters can be changed or adjusted to produce substantially the same results.

[0127] Example 1

[0128] Conceived production of a compound fertilizer containing nitrogen, phosphorus, and sulfur encapsulated in secondary calcium nutrients and secondary magnesium nutrients using dolomite

[0129] 368 g MgCO 3 / CaCO 3 Dolomite is reacted with 196 g H 3 PO 4 and 394 g H 2 SO 4The mixture reacts at 75 °C to produce 125 g of CaHPO 4 , 131 g of MgHPO 4 , 238 g of Mg(HSO 4 ) 2 and 215 g of Ca(HSO 4 ) 2 .

[0130] 34 g of NH 3 reacts with 125 g of CaHPO 4 and 131 g of MgHPO 4 at 75 °C to produce 140 g of CaNH 4 PO 4 and 148 g of MgNH 4 PO 4 .

[0131] NH 3 reacts with 215 g of Ca(HSO 4 ) 2 and 238 g of Mg(HSO 4 ) 2 at 75 °C to produce 244 g of (NH 4 ) 2 Ca(HSO 4 ) 2 and 272 g of (NH 4 ) 2 Mg(HSO 4 ) 2 .

[0132] The mixture can be slowly dried at 40 °C, and then the dried material is granulated to a particle size of 3 mm × 4 mm.

[0133] By combining the above steps, it is also possible to prepare a fertilizer containing all of CaNH 4 PO 4 , MgNH 4 PO 4 , (NH 4 ) 2 Ca(HSO 4 ) 2 and (NH 4 ) 2 Mg(HSO 4 ) 2 .

[0134] The final product may contain 11% N, 11.5% P expressed as P 2 O 5 and 15.5% S. The contents of N, P and S can vary with H3 PO 4 and H 2 SO 4 varies according to the ratio. By increasing the ratio of H 3 PO 4 / H 2 SO 4 to 1.5, the contents of N and P expressed as P 2 O 5 can be increased to 16.5% and 17.2% respectively.

[0135] Example 2

[0136] Use CaCO 3 and MgCO 3 to produce a compound fertilizer containing nitrogen, phosphorus and sulfur encapsulated in secondary calcium nutrients and secondary magnesium nutrients

[0137] Mix 10 g of CaCO 3 and 10 g of MgCO 3 in a 1000 ml beaker. Add 9.5 g of phosphoric acid with a concentration of 85% to the beaker and mix. Subsequently, add 20 ml of distilled water to the beaker and stir at a temperature of 25°C to 45°C. After stirring for 1 hour, gradually add 9.5 g of sulfuric acid with a concentration of 95% and stir for another 2 hours. After 2 hours, add 24 g of NH 4 OH with a concentration of 30% to the beaker and stir at a temperature of 45°C to 70°C while gradually evaporating the water until a thick gel is formed. Generate particles with a particle size of 3 mm × 4 mm from the thick gel through a funnel. Dry the particles at 92°C for 12 hours. After analysis, it is found that the stoichiometric nutrient content is: 4.2 wt% nitrogen, 7.6 wt% sulfur, 21.4 wt% phosphorus in terms of P 2 O 5 equivalent, 12.3% calcium and 7.1 wt% magnesium. The fertilizer produced is a CaMgNPS-compound fertilizer.

[0138] Example 3

[0139] Use CaCO 3 and MgCO 3 to additionally produce a compound fertilizer containing nitrogen, phosphorus and sulfur encapsulated in secondary calcium nutrients and secondary magnesium nutrients

[0140] Except for the differences in the concentrations of ammonium hydroxide, sulfuric acid and phosphoric acid, the reaction conditions in this example are the same as those in Example 2.

[0141] Mix 10 g of CaCO 3 and 10 g of MgCO 3. Add 10 g of 85% phosphoric acid to a beaker and mix. Subsequently, add 20 ml of distilled water to the beaker and stir at a temperature of 25 °C to 45 °C. After stirring for 1 hour, gradually add 14.2 g of 95% sulfuric acid and stir for an additional 2 hours. After 2 hours, add 72 g of 30% NH 4 OH, and stir at a temperature of 45 °C to 70 °C while gradually evaporating the water until a thick gel is formed. Generate particles with a particle size of 3 mm × 4 mm from the thick gel through a funnel. Dry the particles at 92 °C for 12 hours. After analysis, it is found that the stoichiometric nutrient content is: 11.5 wt% nitrogen, 11.6 wt% sulfur, 21.7 wt% phosphorus in terms of P 2 O 5 equivalent, 9.7 wt% calcium, and 7.1 wt% magnesium. The fertilizer produced is a CaMgNPS-compound fertilizer.

[0142] These examples show that by adjusting the ratio of NH 4 OH, H 3 PO 4 and H 2 SO 4 , the contents of nitrogen, phosphorus, and sulfur can be changed. Increasing NH 4 OH can further increase the nitrogen content in the fertilizer.

[0143] ***

[0144] According to the present disclosure, all the 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 accordance with preferred embodiments, it will be apparent to those skilled in the art that changes can be made to the methods and the steps or the order of steps of the methods described herein without departing from the concept, spirit, and scope of the present invention. More specifically, it is apparent that certain chemically related and physiologically related reagents can be substituted for the reagents described herein and achieve the same or similar results. All such similar substitutions and modifications that are obvious to those skilled in the art are considered to fall within the spirit, scope, and concept of the present invention as defined by the appended claims.

Claims

1. A fertilizer composition, comprising: Calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), or a combination of CaNH 4 PO 4 and MgNH 4 PO 4 ; and A mixture of calcium sulfate and ammonium sulfate ((NH 4 )) 2 Ca(SO 4 ) 2 ), a mixture of magnesium sulfate and ammonium sulfate ((NH 4 )) 2 Mg(SO 4 ) 2 ), or a combination of (NH 4 ) 2 Ca(SO 4 ) 2 and (NH 4 ) 2 Mg(SO 4 ) 2 .

2. The fertilizer composition according to claim 1, wherein the composition comprises: 10% to 17% by weight of nitrogen (N), phosphorus (P) equivalent to 11% to 18% by weight 2 O 5 an amount of potassium (P), and 10% to 16% by weight of sulfur (S); and / or 5% to 10% by weight of calcium (Ca) and 5% to 10% by weight of magnesium (Mg).

3. The fertilizer composition according to any one of claims 1 and 2, wherein the composition further comprises calcium phosphate, magnesium phosphate, ammonium phosphate ((NH 4 )) 3 PO 4 ), magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), nickel oxide (NiO), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), iron(II) carbonate (FeCO 3 ), nickel sulfate (NiSO 4 ), zinc sulfate (ZnSO 4 ), iron(II) sulfate (FeSO 4 ), iron(II) phosphate (FePO 4 ) and / or dolomite.

4. The fertilizer composition according to any one of claims 1 to 3, wherein the composition does not contain a binder different from calcium ammonium phosphate (CaNH 4 PO 4 ), magnesium ammonium phosphate (MgNH 4 PO 4 ), (NH 4 ) 2 Ca(SO 4 ) 2 or (NH 4 ) 2 Mg(SO 4 ) 2 .

5. The fertilizer composition according to any one of claims 1 to 4, wherein: At least a portion of ammonium sulfate is adsorbed on the surface of calcium ammonium phosphate and / or magnesium ammonium phosphate; At least a portion of (NH 4 ) 2 Ca(SO 4 ) 2 and / or at least a portion of (NH 4 ) 2 Mg(SO 4 ) 2 is encapsulated by calcium ammonium phosphate and / or magnesium ammonium phosphate; The fertilizer is homogeneous; and / or The composition comprises a dried gel.

6. The fertilizer composition according to any one of claims 1 to 5, wherein the composition comprises: CaNH 4 PO 4 and MgNH 4 PO 4 combinations; and / or (NH 4 ) 2 Ca(SO 4 ) 2 and (NH 4 ) 2 Mg(SO 4 ) 2 combination 7. The fertilizer composition according to any one of claims 1 to 6, wherein the fertilizer composition is a granular fertilizer.

8. The fertilizer composition according to any one of claims 1 to 7, wherein the composition does not comprise one or more of ammonium nitrate, urea, and / or polymers.

9. A method for producing a fertilizer composition, the method comprising the steps of: (a) Contact CaO, MgO, MgCO 3 , CaCO 3 and / or dolomite with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) to produce a first reaction product comprising: Calcium hydrogen phosphate (CaHPO 4 ) and / or magnesium hydrogen phosphate (MgHPO 4 ); and Calcium bisulfate (Ca(HSO 4 )) 2 ) and / or magnesium bisulfate (Mg(HSO 4 )) 2 ); (b) contacting the first reaction product with an ammonia source to produce a second reaction product, comprising: Calcium ammonium phosphate (CaNH 4 PO 4 ) and / or magnesium ammonium phosphate (MgNH 4 PO 4 ); and Mixture of calcium sulfate and ammonium sulfate ((NH 4 )) 2 Ca(SO 4 )) 2 ) and / or mixture of magnesium sulfate and ammonium sulfate ((NH 4 )) 2 Mg(SO 4 )) 2 ); and Optionally, drying the second reaction product to form a solid fertilizer composition.

10. The method according to claim 9, which further comprises: (c) Combine the second reaction product with CaSO 4 in combination, preferably in a weight ratio of from about 3:1 to about 1:3; and / or The phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ) in step (a) and the weight ratio of CaO, MgO, MgCO 3 , CaCO 3 and / or dolomite is 1:1 to 3:

1.

11. The method according to any one of claims 9 to 10, wherein step (a) and / or step (b) is carried out at 55°C to 75°C.

12. The method according to any one of claims 9 to 11, wherein: The ammonia source is ammonium hydroxide (NH 4 OH) and / or ammonia (NH 3 ); In step (a), dolomite is contacted with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ); and / or In step (a), MgCO 3 and CaCO 3 are contacted with phosphoric acid (H 3 PO 4 ) and sulfuric acid (H 2 SO 4 ).

13. The method according to any one of claims 9 to 12, wherein in step (a), there is a stoichiometric excess of phosphoric acid (H 4 ) and / or sulfuric acid (H 4 ) required to form calcium hydrogen phosphate (CaHPO 4 ) and / or magnesium hydrogen phosphate (MgHPO 2 ) and calcium bisulfate (Ca(HSO 4 ) 2 ) and / or magnesium bisulfate (Mg(HSO 3 PO 4 ), and a part of the stoichiometric excess of phosphoric acid (H 2 SO 4 ) contacts the ammonia source in step (b) to form ammonium phosphate ((NH 3 ) 4 PO 2 ) and / or ammonium sulfate ((NH 4 ) 4 ) 3 PO 4 ) and / or ammonium sulfate ((NH 4 ) 2 SO 4 ).

14. A method of fertilizing, the method comprising contacting a plant, soil, water, or a combination thereof with the fertilizer composition according to any one of claims 1 to 8.

15. A method of increasing the pH value of soil, the method comprising contacting the soil with the fertilizer composition according to any one of claims 1 to 8.

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