FERTILIZER COMPRISING IMMEDIATE- AND SLOW-RELEASE AGENTS IN SOIL COMPLEX NUTRIENTS

Abstract

Disclosed is a fertilizer containing a mixture containing one or more of potassium phosphate, calcium sulfate, magnesium ammonium phosphate, and calcium ammonium phosphate. Methods of making and using the fertilizer granule are also disclosed.

Claims

1. A fertilizer composition comprising: a slow-release agent comprising calcium ammonium phosphate (CaNH.sub.4PO.sub.4), magnesium ammonium phosphate (MgNH.sub.4PO.sub.4), or a combination of CaNH.sub.4PO.sub.4 and MgNH.sub.4PO.sub.4; an immediate-release agent comprising calcium sulfate (CaSO.sub.4), potassium phosphate (K.sub.3PO.sub.4), and/or magnesium sulfate (MgSO.sub.4).

2. The fertilizer composition of claim 1, wherein the composition comprises a further slow-release agent comprising magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), nickel oxide (NiO), magnesium carbonate (MgCO.sub.3), calcium carbonate, (CaCO.sub.3), iron (II) carbonate (FeCO.sub.3), or a combination thereof.

3. The fertilizer composition of claim 1, wherein the immediate-release agent further comprises nickel sulfate (NiSO.sub.4), zinc sulfate (ZnSO.sub.4), iron (II) sulfate (FeSO.sub.4), or a combination thereof.

4. The fertilizer composition of claim 1, wherein the immediate-release agent comprises CaSO.sub.4, and the CaSO.sub.4 is comprised in waste gypsum and/or a recycled gypsum.

5. The fertilizer composition of claim 1, wherein the fertilizer does not comprise a binding agent separate from the CaNH.sub.4PO.sub.4, MgNH.sub.4PO.sub.4, or combination of CaNH.sub.4PO.sub.4 and MgNH.sub.4PO.sub.4.

6. The fertilizer composition of claim 1, wherein the fertilizer composition is a granular fertilizer and/or the fertilizer is homogenous.

7. The fertilizer composition of claim 1, comprising iron (II) phosphate (FePO.sub.4), KOH, K.sub.2CO.sub.3, KHCO.sub.3, and/or dolomite.

8. The fertilizer composition of claim 1, wherein the immediate-release agent and the slow-release agent are comprised at a weight ratio between approximately 3:1 to 1:5.

9. The fertilizer composition of claim 1, wherein the immediate-release agent comprises K.sub.3PO.sub.4.

10. The fertilizer composition of claim 1, wherein the slow-release agent comprises a combination of CaNH.sub.4PO.sub.4 and MgNH.sub.4PO.sub.4.

11. The fertilizer composition of claim 1, wherein the fertilizer composition comprises a nitrogen source, a phosphorus source, and a potassium source.

12. A method of producing a fertilizer composition, the method comprising the steps of: (a) contacting CaO, MgO, MgCO.sub.3, CaCO.sub.3, and/or dolomite with phosphoric acid (H.sub.3PO.sub.4) to generate a first reaction product comprising calcium hydrogen phosphate (CaHPO.sub.4) and/or magnesium hydrogen phosphate (MgHPO.sub.4); (b) contacting the first reaction product with an ammonia source to generate a second reaction product comprising CaNH.sub.4PO.sub.4 and/or MgNH.sub.4PO.sub.4; (c) contacting potassium hydroxide (KOH) with H.sub.3PO.sub.4 to generate a third reaction product comprising K.sub.3PO.sub.4; and (d) combining the second reaction product, the third reaction product, and CaSO.sub.4 to generate the fertilizer composition.

13. The method of claim 12, further comprising drying the fertilizer composition to form a solid fertilizer composition.

14. The method of claim 12, wherein the combining step (d) comprises combining the third reaction product with CaSO.sub.4 at a weight ratio of approximately 3:1 to 1:3.

15. The method of claim 12, wherein steps (a), (b), and/or (c) occurs at 55 to 75 C.

16. The method of claim 12, wherein the CaSO.sub.4 is red gypsum, phosphogypsum, and/or waste gypsum from production of H.sub.3PO.sub.4.

17. The method of claim 12, wherein the fertilizer composition comprises CaSO.sub.4, K.sub.3PO.sub.4, and one or both of CaNH.sub.4PO.sub.4 and MgNH.sub.4PO.sub.4.

18. The method of claim 12, wherein the combining step (d) comprises combining the third reaction product and CaSO.sub.4 with the second reaction product at a weight ratio of approximately 3:1 to 1:5 of a combination of the third reaction product and CaSO.sub.4:second reaction product.

19. The fertilizer composition of claim 1, wherein the immediate-release agent comprises CaSO.sub.4 and K.sub.3PO.sub.4.

20. The fertilizer composition of claim 19, wherein the CaSO.sub.4 and K.sub.3PO.sub.4 are comprised at a weight ratio of approximately 3:1 to 1:3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0071] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

[0072] FIG. 1: Example cross-sectional view of a fertilizer granule according to a non-limiting example of a fertilizer granule described herein.

[0073] FIG. 2: a schematic of a system and method for producing a fertilizer according to a non-limiting example of a system and method disclosed herein.

[0074] FIG. 3: a schematic of a system and method for producing a fertilizer according to another non-limiting example of a system and method disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

[0075] Certain aspects of the present disclosure provide benefits over existing fertilizers, including by having both immediate and slow-release characteristics for nutrients comprising the fertilizer. Certain aspects provided herein allow for the fertilizer to immediately release nutrients, such as those comprising phosphate, into the soil for use by plants, while also allowing for the fertilizer to slowly release nutrients, which may also comprise phosphate, into the soil over a period of time, such as throughout a growing cycle for a plant. This dual-release capability can be achieved, in some aspects, without the use of binders, inhibitors, or other interventions that add compounds beyond the fertilizer's nutrients. In some embodiments, the fertilizer comprises a double salt, such as a metal ammonium phosphate, such as calcium ammonium phosphate (CaNH.sub.4PO.sub.4), magnesium ammonium phosphate (MgNH.sub.4PO.sub.4), or a combination of CaNH.sub.4PO.sub.4 and MgNH.sub.4PO.sub.4; and an immediate-release agent comprising potassium phosphate (K.sub.3PO.sub.4), magnesium sulfate (MgSO.sub.4), calcium sulfate (CaSO.sub.4), nickel sulfate (NiSO.sub.4), zinc sulfate (ZnSO.sub.4), iron (II) sulfate (FeSO.sub.4), or a combination thereof, which may be one chemical composition and/or one homogenous mixture. The metal ammonium phosphate compound may act as a binder for the other components in the fertilizer

I. Fertilizer

[0076] Certain embodiments herein concern a complex fertilizer comprising a double salt, such as a metal ammonium phosphate, which may comprise CaNH.sub.4SO.sub.4 and/or MgNH.sub.4SO.sub.4, and a soluble composition, which may comprise CaSO.sub.4, MgSO.sub.4, and/or K.sub.3PO.sub.4. Certain aspects involve synthesis of the nutrient complex using natural sources of ingredients of the fertilizer, such as CaSO.sub.4, CaO, MgO, CaCO.sub.3, MgCO.sub.3, H.sub.3PO.sub.4, NH.sub.4OH, and KOH. In addition to these feed sources, ammonia also is used, in some embodiments.

[0077] The fertilizer, which may be a fertilizer granule, can contain a homogeneous mixture containing calcium (Ca), magnesium (Mg), potassium (K), nitrogen (N) present as ammonium, sulfur (S) present as sulfate. The ratio of elements present in the fertilizer may be tailored to specific applications. At least a portion of Ca can be present as calcium ammonium phosphate and/or calcium sulfate. In some aspects, at least 90 wt. %, or at least 95 wt. %, or 90 wt. % to 100 wt. %, or at least any one of, at most any one of, equal to any one of, or between any two of 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % of the Ca in the homogeneous mixture can be present as calcium ammonium phosphate and/or calcium sulfate, based on the total weight of Ca in the homogeneous mixture. In some embodiments, at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % of the Ca in the homogeneous mixture can be present as calcium ammonium phosphate. In some embodiments, at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % of the Ca in the homogeneous mixture can be present as calcium sulfate. In some aspects, the homogeneous mixture can contain i) CaNH.sub.4SO.sub.4 in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % based on the total weight of the homogeneous mixture and/or the fertilizer granule; ii) MgNH.sub.4SO.sub.4 in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. % based on the total weight of the homogeneous mixture and/or the fertilizer granule; iii) K.sub.3PO.sub.4 in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. % based on the total weight of the homogeneous mixture and/or the fertilizer granule; iv) CaSO.sub.4 in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. % based on the total weight of the homogeneous mixture and/or the fertilizer granule; and MgSO.sub.4 in an amount providing at least any one of, at most any one of, equal to any one of, or between any two of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. % based on the total weight of the homogeneous mixture and/or the fertilizer granule.

[0078] In some aspects, the homogenous mixture comprises Ca, Mg, N, P, K, and/or S wherein i) the Ca content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, ii) the Mg content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, iii) the N content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, iv) the P content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, v) the K content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, based on the total weight of the homogeneous mixture and/or fertilizer, and vi) the S content of the homogenous mixture can be at least any one of, at most any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, and 100 wt. %, based on the total weight of the homogeneous mixture and/or fertilizer.

[0079] The Ca, Mg, N, P, K, and/or S can be present as and/or sourced as a water soluble compound or a water insoluble compound. In some instances, the Ca, Mg, N, P, K, and/or S can be present as a salt. In some aspects, the Ca, Mg, N, P, K, and/or S can be present as a water soluble salt. In some instances, the water soluble Ca salt can be CaSO.sub.4. In some instances, the water soluble P salt can be K.sub.3PO.sub.4. In some instances, the water soluble Mg salt can be MgSO.sub.4. The Ca, Mg, N, P, K, and/or S salt can be in a non-hydrate and/or one or more hydrate form.

[0080] Moisture content of the dried fertilizer can be less than 1 wt. %, such as 0.1 wt. % to 0.9 wt. %, or any one of or between any two of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt. %, or any range thereof, based on the weight of the fertilizer granule. As a non-limiting example, the moisture content can be measured by drying the sample at 50 C., for 25 min and measuring the amount of mass lost by the fertilizer after being dried.

[0081] In some particular aspects, the CaSO.sub.4 can contain and/or can be obtained from phosphogypsum and/or red gypsum.

[0082] The fertilizer can be of any suitable shape. Non-limiting shapes include spherical, cuboidal, cylindrical, puck shape, oval, and oblong shapes. In some aspects, the fertilizer granule can be of cylindrical shape with a circular, elliptical, ovular, triangular, square, rectangular, pentagonal, or hexagonal cross section, although cylindrical shaped core having a cross-section of other shapes can also be made. In some aspects, the fertilizer granule at its widest dimension can be 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm. In some particular aspects, the fertilizer granule can have a substantially spherical shape with an average diameter 0.5 mm to 6 mm, or 0.5 mm to 5 mm, preferably 1 mm to 4 mm, or at least any one of, at most any one of, equal to any one of, or between any two of 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, and 6 mm.

[0083] The fertilizer can be water and/or soil dispersible. In some aspects, a fertilizer granule having a size of 2 mm to 4 mm prior to adding to water, can disintegrate into particles having sizes less than 1 mm, less than 0.9 mm, less than 0.8 mm, less than 0.7 mm, less than 0.6 mm, less than 0.5 mm, less than 0.4 mm, or less than 0.3 mm, within 1 minute of adding the granule to water at a pH 7, under stirring at a rate 90 rpm to 110 rpm, at an ambient temperature.

[0084] The homogeneous mixture can have a compositional make-up that is substantially homogeneous. In some instances, a compositional make-up for a 1 mm1 mm1 mm cube at any position of the mixture can be similar (within 20%, or 10%, or 5%, or 3%, 2%, or 1%, or 0.5%) to that of a 1 mm1 mm1 mm cube at any other position of the mixture.

[0085] Referring to FIG. 1, a fertilizer granule 100 according to one example of the present invention is shown. The fertilizer granule 100 can contain an homogeneous mixture 101. The homogeneous mixture 101 can have compositions as described above. In some instances, the homogenous mixture 101 can have an optional coating 102 on the outer surface of the homogenous mixture 101. In some instances, the CaNH.sub.4PO.sub.4 and/or MgNH.sub.4PO.sub.4 can act as a binder in the fertilizer. In some instances the CaNH.sub.4PO.sub.4 and/or MgNH.sub.4PO.sub.4 is the only binder in the fertilizer. In some instances, the CaNH.sub.4PO.sub.4 and/or MgNH.sub.4PO.sub.4 form an amorphous phase, a continuous phase, and/or encapsulate other ingredients in the fertilizer. In some instances, the fertilizer comprises a matrix of CaNH.sub.4PO.sub.4 and/or MgNH.sub.4PO.sub.4 that at least partially surrounds and/or encapsulates at least a portion of the immediate-release agent(s). In some instances, the fertilizer comprises particles of the slow-release agent(s) and/or immediate-release agent(s).

[0086] In some aspects, additional fertilizer substances can be included or excluded in the fertilizer. If included, additional fertilizers can be chosen based on the particular needs of certain types of soil, climate, or other growing conditions to maximize the efficacy of the fertilizer in enhancing plant growth and crop yield. Additional additives may also be included or excluded in the fertilizer. Non-limiting examples of additives that can be included or excluded from the fertilizer of the present invention include additional nitrogen nutrients, additional phosphorus nutrients, additional potassium nutrients, additional micronutrients, and/or additional secondary nutrients. The micronutrient can be copper, iron, chloride, manganese, molybdenum, or nickel, or any combinations thereof. The nitrogen nutrient can be urea, ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride, and potassium nitrate. In some aspects, the additional secondary nutrients may include lime and/or superphosphate. In some instances, the additional fertilizer substances and/or the additional additives are contained in the optional coating of the fertilizer.

[0087] In some instances, the inhibitors include nitrification inhibitors and/or urease inhibitors. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, which is sold under the tradename Terrazole, by OHP Inc., USA, 2-amino 4-chloro 6-methyl pyrimidine (AM), 2-mercaptobenzothiazole (MBT), or 2-sulfanilamidothiazole (ST), and any combination thereof. In one aspect, a nitrification inhibitor can comprise DMPP, DCD, TU, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, AM, MBT, or ST, or a combination thereof. In some embodiments, a fertilizer composition can comprise NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, AM, MBT, ST, or a combination thereof.

[0088] In some instances, a binder includes a phosphate, a polyphosphate, a biodegradable polymer, or a wax, or a combination thereof. Suitable waxes include, but are not limited to, vegetable waxes, high melt waxes, ethylene bis(stearamide) wax, paraffin waxes, polyethylene based waxes, and olefin waxes. Suitable phosphates include, but are not limited to, diammonium phosphate, and monoammonium phosphate. Suitable polyphosphates include, but are not limited to, ammonium polyphosphate. Suitable biodegradable polymers include, but are not limited to, polyacrylamide, polyacrylic acid, polyacrylonitrile, biodegradable polylactic acid and other biodegradable polymeric material such as polylactic acid, poly(3-hydroxypropionic acid), polyvinyl alcohol, poly e-caprolactone, poly L-lactide, poly butylene succinate, and biodegradable starch based polymers. The binder can include plaster of Paris, flour, starch, gluten, kaolin, bentonite, colloidal silica, or combinations thereof. Suitable flours include, but are not limited to, rice flour, wheat flour, and bleached wheat flour. Suitable starches include, but are not limited to, dextrin modified starches.

[0089] In some instances, the pH buffers include MgO, KH.sub.2PO.sub.4, NaHCO.sub.3, chalk powder, aluminum, magnesium hydroxide, aluminum hydroxide/magnesium hydroxide co-precipitate, aluminum hydroxide/sodium bicarbonate co-precipitate, calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, dibasic sodium phosphate, dipotassium hydrogen phosphate, dipotassium phosphate, disodium hydrogen phosphate, magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate, potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, sodium gluconate, sodium hydrogen phosphate, sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, trisodium phosphate, and trometamol, and combinations thereof.

[0090] The fertilizer escribed herein can be comprised in a composition useful for application to soil. In some aspects, in addition to the fertilizer described herein, the composition may include other fertilizer compounds, micronutrients, primary nutrients, urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof. The fertilizer described herein can also be included in a blended composition comprising other fertilizers. The other fertilizer can be urea, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), monopotassium phosphate (MKP), triple super phosphate (TSP), rock phosphate, single super phosphate (SSP), ammonium sulfate, and the like.

[0091] A fertilizer formed into a granule can have desirable physical properties such as desired levels of abrasion resistance, granule strength, pelletizability, hygroscopicity, granule shape, and size distribution. In some aspects, The fertilizer granule can have a crush strength above 1.5 kgf, such as above 1.8 kgf, such as 2 kgf to 6 kgf, or at least any one of, equal to any one of, or between any two of 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, and 6 kgf. Bulk density of the fertilizer granules can be 1 g/cc to 1.2 g/cc, or at least any one of, at most any one of, equal to any one of, or between any two of 1, 1.02, 1.04, 1.06, 1.08, 1.1, 1.12, 1.14, 1.16, 1.18, and 1.2 g/cc. In some aspects, 10 mg or more, such as 10 mg to 40 mg, or at least any one of, at most any one of, equal to any one of, or between any two of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 mg of the fertilizer granule can dissolve in 1 ml of water at a pH 7, under stirring at a rate 90 to 110 rpm, and at an ambient temperature. within 5 minutes of adding 100 mg of the fertilizer granules to the water. In some aspects, the fertilizer granule is capable of losing less than 0.13 wt. %, such as 0.02% to 0.12 wt. %, or at most any one of, equal to any one of, or between any two of 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, and 0.12 wt. % in an attrition loss test. Attrition loss can be measured using the following attrition loss test.

[0092] Attrition loss test: A plurality of sieved fertilizer granules with individual size 2 to 4 mm, and total volume 100 cm.sup.3 is weighed (W1) and is placed into the test drum along with the 50 stainless steel balls having a total weight of 100 gm. The drum is closed and rotated for 10 min at 30 rpm. Then, the steel balls are separated from the sample and the material is screened over 2 mm sieve using a sieve shaker. The total weight of the granules over 2 mm are then re-weighed (W2). Results are calculated in terms of % weight loss using the formula:

[00001]$\mathrm{Weight}\mathrm{loss}\mathrm{due}\mathrm{to}\mathrm{attrition}\left(\mathrm{wt}.\%\right)=\frac{\mathrm{weight}\mathrm{of}\mathrm{sample}\mathrm{remained}\mathrm{on}2\mathrm{mm}\mathrm{sieve}\left(\left(W2\right)\right)}{\mathrm{initial}\mathrm{weight}\mathrm{of}\mathrm{the}\mathrm{sample}\left(W1\right)}100$

II. Method of Making a Fertilizer

[0093] Referring to FIG. 2, a schematic of a system and method for making a fertilizer according to one example of the present invention is described. The system 200 can include a granulator 202 and a dryer 204. A feed mixture 206 can be granulated in the granulator 202 in the presence of water to form a wet granulated mixture 208. The water can be provided with the feed mixture 206, and/or can be added separately to the granulator 202. The wet granulated mixture 208 can be dried in the dryer 204 to obtain dry granulated mixture 210 containing the fertilizer.

[0094] Referring to FIG. 3, a schematic of a system and method for making a fertilizer according to another example of the present invention is described. The system 300 can include a mixer/reactor 312, though the mixer and the reactor can be two, three, four, or more components, such as two reactors and a mixer or a reactor and a mixer. The system 300 can include a granulator 302, a spheronizer 314, one or more size screens 316, and a dryer 304, or any combination thereof. The feed mixture ingredients 318, separately and/or at any possible combination can be added to the mixer/reactor 312. In the mixer/reactor 312, the feed ingredients can be reacted and/or mixed to form the feed mixture 306. Feed mixture 306 can be granulated in the granulator 302 in presence or absence of additional water to form a wet granulated mixture 320. Granules of the wet granulated mixture 320 can be spheronized in the spheronizer 314 to form a wet granulated mixture 322 containing substantially spherical granules. The wet granulated mixture 322 can be passed through one or more size screens 316 to separate granules having a size smaller or bigger than a desired size from the wet granulated mixture 322 and obtain a wet granulated mixture 324 containing granules of desired size. At least a portion of the granules separated 326 from the granulation mixture 324 containing granules of desired size can be recycled to the granulator 302. The wet granulated mixture 324 containing granules of desired size can be dried in the dryer 304 to obtain dry granulated mixture 310 containing the fertilizer granule. In some aspects, the mixer/reactor 312 can contain a ribbon mixer.

[0095] The feed mixture ingredients 318 can include i) a Ca source, e.g., calcium oxide and/or calcium carbonate, ii) a Mg source, e.g., magnesium oxide and/or magnesium carbonate, iii) a N source, e.g., NH.sub.4.sup.+ and/or NH.sub.3 iv) a P source, e.g., phosphoric acid, and iv) a K source, e.g., KOH. In some instances, a mixture ingredient provides more than one of Ca, Mg, N, P, K, and/or S substance. In certain aspects, one or more ingredients can be added as a water solution. In some instances, the mixture ingredients are provided as a powder. In some instances, one or more ingredients can be added as a gas. In some instances, the NH.sub.3 is provided at a pressure above 1 bar, such as at, or between, or of any range of 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 9, 10, 15, 20, 25, 30, 35, and 40 bar. In some instances, a portion of the mixture ingredients are provided as a powder.

[0096] The feed mixture 206, 306 can contain Ca, Mg, N, P, K, and/or S. In some aspects, the feed mixture 206, 306 can contain i) a metal oxide and/or metal carbonate, ii) phosphoric acid, iii) ammonium hydroxide, and/or iv) potassium hydroxide.

[0097] Water can be added to the feed mixture in the mixer/reactor 312 and/or in the granulator 202, 302. In certain aspects, 5 gm to 20 gm, or at least any one of, at most any one of, equal to any one of, or between any two 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 gm of water in total (e.g., added with one or more feed mixture ingredients and/or separately) can be added to the feed mixture, per 100 gm of feed mixture.

[0098] In some aspects, the granulator 202, 302 can be a drum granulator, pugmill granulator, pan granulator, solid mixer, abrasion drum, extruder, high-shear mixer granulator, roller granulator, mycromix, or a round bottom flask. In the granulator 202, 302 the feed mixture 206, 306 can be granulated by agglomeration, spray granulation, compaction, slurry granulation and/or high-shear mixer granulation. In some particular aspect, the feed mixture 206, 306 can be granulated in the granulator 202, 302 by compaction. In some aspects, the granulator 202, 302 can contain at least two rollers and compaction granulation can include compressing the feed mixture using the at least two rollers. In some aspects, the two rollers can be moved in counter current direction during compaction. In some aspects, the feed mixture can be compressed into shaped pellets, such as cylindrical pellets, by the at least two rollers. In some aspects, a surface of one roller can have desired holes to compress the feed mixture into the holes, and the surface of the other roller can push the feed mixture into the holes. Pressure during granulation, e.g. compaction granulation can be 1 bar to 40 bar, or at least any one of, at most any one of, equal to any one of, or between any two 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, and 40 bar. In certain aspects, the feed mixture can be granulated in the granulator 202, 302 at ambient temperature to 50 C., or at least any one of, at most any one of, equal to any one of, or between any two of 20, 15, 10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 C.

[0099] In some aspects, reacting of the feed mixture ingredients, mixing, and granulating the feed mixture can be performed in different containers, e.g., the mixer/reactor 312 and the granulator 302 can be different containers. In some aspects, reacting of the feed mixture ingredients, mixing, and granulating the feed mixture can be performed in the same container, e.g., the mixer/reactor 312 and the granulator 302 can be the same container (not shown).

[0100] In some aspects, the calcium hydrogen phosphate (CaHPO.sub.4), magnesium hydrogen phosphate (MgHPO.sub.4), CaNH.sub.4PO.sub.4, MgNH.sub.4PO.sub.4, and/or K.sub.3PO.sub.4 are formed at a temperature of at least, at most, equal to, or between any two of 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 C., such as between 20 and 75 C. or between 30 and 75 C., or between 55 to 75 C.

[0101] In some instances, the fertilizer can be extruded before drying. The extruder can extrude the fertilizer at pressures at least, at most, equal to, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 bar. The extruder can extrude the fertilizer at temperatures at least, at most, equal to, or between any two of 20, 15, 10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 C. The extrudate can be sliced or divided before drying, such as by a die.

[0102] In certain aspect, the desired size of a final fertilizer product, such as a granule, can be 0.5 to 5 mm, or 1 to 4 mm, and having a size lower than 0.5 mm or 1 mm, and/or having a size bigger than 4 mm or 5 mm can be separated from the wet granulated mixture 322 in the one or more size screens 316. In certain aspects, the wet granulated mixture can be rounded and/or spheronized in a spheronizer. In some instances, the wet granulated mixture is contacted with a spheronizer for at least any one of, at most any one of, equal to any one of, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 50, or 60 seconds. The spheronizer in some instances has a rotating or rotatable disk capable of rotating at least any one of, at most any one of, equal to any one of, or between any two of 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000 rpm. In certain aspects, the wet granulated mixture can be dried in the dryer 204, 304 at a temperature 40 C. to 85 C., or at least any one of, at most any one of, equal to any one of, or between any two of 40, 45, 50, 55, 60, 65, 70, 75, 80 and 85 C. In some aspects, the dryer 204, 304 can be a fluid bed dryer, drum dryer, or flash dryer. In some aspects, the wet granulated mixture can be dried in the dryer 204, 304 with an hot air flow having a flow rate of at least any one of, at most any one of, equal to any one of, or between any two of 100, 150, 200, 250, 300, 350, 400, 450, and 500 m.sup.3/hr and/or a rotation of at least any one of, at most any one of, equal to any one of, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 rpm.

III. Methods of Using the Fertilizer

[0103] The fertilizer, including fertilizer granules, compositions containing the fertilizer, and fertilizer blends containing the fertilizer of the present disclosure can be used in methods of increasing the amount of one or more plant nutrients in soil and of enhancing plant growth. Such methods can include applying to the soil an effective amount of a composition and/or blend containing the fertilizer of the present invention. The method may include increasing the growth and yield of crops, trees, ornamentals, etc., such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and/or soybeans. The method can include applying the fertilizer blend of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc. The composition(s) and/or fertilizer blends(s) containing the fertilizer can be applied to plants and/or soil as a top dressing fertilizer, basal fertilizer, and/or through any suitable method of application.

[0104] Non-limiting examples of plants that can benefit from the fertilizer of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and/or Pteridophytes.

[0105] The effectiveness of compositions comprising the fertilizer of the present invention can be ascertained by measuring the amount of phosphorus and optionally other nutrients in the soil at various times after applying the fertilizer composition to the soil. It is understood that different soils have different characteristics, which can affect the stability of the nutrients in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.

EXAMPLES

[0106] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

Production of a Slow-Release and Immediate-Release Fertilizer Composition

[0107] A stoichiometric reaction of CaO and H.sub.3PO.sub.4 at 65 C. can produce CaHPO.sub.4 according to reaction (1):

##STR00004##

[0108] A stoichiometric amount of NH.sub.4OH and/or NH.sub.3 can react with the intermediate product CaHPO.sub.4 to produce CaNH.sub.4PO.sub.4 according to reaction (2):

##STR00005##

[0109] A stoichiometric amount of KOH and H.sub.3PO.sub.4 can react at 65 C. to produce K.sub.3PO.sub.4 according to reaction (3):

##STR00006##

[0110] CaSO.sub.4, selected from any resource, can be mixed with the product of reaction (3) at a ratio of 3:1 to generate a CaSO.sub.4 and K.sub.3PO.sub.4 mixture. The CaSO.sub.4 and K.sub.3PO.sub.4 mixture can be mixed with the product of the reaction (1) or the products of reaction (2) at a ratio of 1:2. The mixture can be dried slowly at 40 C., then the dried material can be pelleted to a particle size of 34 mm.

[0111] A stoichiometric reaction of MgO and H.sub.3PO.sub.4 at 65 C. can produces MgHPO.sub.4 according to reaction (4):

##STR00007##

[0112] A stoichiometric amount of NH.sub.4OH and/or NH.sub.3 can react with the intermediate product MgHPO.sub.4 to produce MgNH.sub.4PO.sub.4 according to reaction (5):

##STR00008##

[0113] The CaSO.sub.4 and K.sub.3PO.sub.4 mixture can be mixed with the product of the reaction (4) or the products of reaction (5) at a ratio of 1:2. The mixture can be dried slowly at 40 C., then the dried material can be pelleted to a particle size of 34 mm.

[0114] A fertilizer comprising both calcium ammonium phosphate and magnesium ammonium phosphate can also be prepared by combining the steps above. The ratio of calcium sulfate and K.sub.3PO.sub.4 to total CaNH.sub.4PO.sub.4+MgNH.sub.4PO.sub.4 can be 1:2 or can be 1 K.sub.3PO.sub.4 to 2 CaNH.sub.4PO.sub.4 and 1 K.sub.3PO.sub.4 to 2 MgNH.sub.4PO.sub.4.

[0115] All of the methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.