STABILIZED UREA-BASED CORE-SHELL FERTILIZER PARTICLES

Abstract

Fertilizer particles containing a core and a shell is described. The core can contain urea, a pH buffering agent, and an urease inhibitor, and the shell can contain urea and can cover at least a portion of an outer surface of the core. The core can include 20 wt. % to 80 wt. % urea, based on the total weight of the core, and the shell can include 50 wt. % to 100 wt. % urea, based on the total weight of the core.

Claims

1. A core-shell fertilizer particle comprising: a core comprising urea, a pH buffering agent, and an urease inhibitor; and a shell comprising urea, wherein the shell covers at least a portion of an outer surface of the core.

2. The core-shell fertilizer particle of claim 1, wherein the core comprises 20 wt. % to 80 wt. % urea, based on the total weight of the core.

3. The core-shell fertilizer particle of claim 1, wherein the shell comprises 50 wt. % to 100 wt. % urea, based on the total weight of the shell.

4. The core-shell fertilizer particle of claim 1, wherein the core comprises 15 wt. % to 80 wt. % of the pH buffering agent based on the total weight of the core.

5. The core-shell fertilizer particle of claim 1, wherein the pH buffering agent is CaCO.sub.3, Na.sub.2CO.sub.3, K.sub.2CO.sub.3, MgO, KH.sub.2PO.sub.4, NaHCO.sub.3, or MgCO.sub.3, or any combination thereof.

6. The core-shell fertilizer particle of claim 1, wherein the urease inhibitor comprises a thiophosphoric triamide derivative.

7. The core-shell fertilizer particle of claim 1, wherein the core comprises 0.1 wt. % to 5 wt. % of the urease inhibitor, based on the total weight of the core.

8. The core-shell fertilizer particle of claim 1, wherein the core further comprises 0.1 wt. % to 7 wt. % of water, based on the total weight of the core.

9. The core-shell fertilizer particle of claim 1, wherein the core further comprises a polymer thickener and/or a filler.

10. The core-shell fertilizer particle of claim 9, wherein the polymer thickener comprises hydroxypropyl methylcellulose (HPMC), carboxymethyl cellulose, polyethylene glycol (PEG), guar gum, locust bean gum, xanthan gum, a natural gum, lignosulfonate, or hydroxyethylcellulose or any combination thereof.

11. The core-shell fertilizer particle of claim 9, wherein the core comprises 0.1 wt. % to 5 wt. % of the polymer thickener, based on the total weight of the core.

12. The core-shell fertilizer particle of claim 1, wherein the core further comprises a nitrification inhibitor.

13. The core-shell fertilizer particle of claim 12, wherein the nitrification inhibitor comprises dicyandiamide (DCD).

14. The core-shell fertilizer particle of claim 12, wherein the core comprises 5 wt. % to 35 wt. % of the nitrification inhibitor, based on the total weight of the core.

15. The core-shell fertilizer particle of claim 1, wherein 98 wt. % or higher of the core, based on the total weight of the core, is comprised in urea, CaCO.sub.3, one or more urease inhibitor, water, and optionally a nitrification inhibitor and/or a polymer thickener.

16. The core-shell fertilizer particle of claim 1, wherein: the core comprises, based on the total weight of the core: 45 wt. % to 60 wt. % or 65 wt. % to 75 wt. % of urea; 20 wt. % to 60 wt. %, preferably 20 wt. % to 45 wt. %, of CaCO.sub.3; 1 wt. % to 3 wt. % of the urease inhibitor, wherein the urease inhibitor is N-(n-butyl) thiophosphoric triamide (NBPT); 0.1 wt. % to 3 wt. % of water; and the shell comprises, based on the total weight of the shell: 85 wt. % to 100 wt. % urea.

17. The core-shell fertilizer particle of claim 16, wherein the core further comprises

0. 5 wt. % to 3 wt. % of hydroxypropyl methylcellulose (HPMC), based on the total weight of the core.

18. The core-shell fertilizer particle of claim 16, wherein the core further comprises 20 wt. % to 25 wt. % of dicyandiamide (DCD), based on the total weight of the core.

19. The core-shell fertilizer particle of claim 1, wherein the shell does not include CaCO.sub.3 or a urease inhibitor, or both.

20. The core-shell fertilizer particle of claim 1, comprised in a fertilizer blend or a compounded fertilizer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

[0058] FIG. 1 illustrates a cross section of a fertilizer particle embodiment.

DETAILED DESCRIPTION OF THE INVENTION

[0059] The fertilizer particles of the present invention can contain two discrete portions: a core having an outer surface and a shell in contact with at least a portion of the outer surface of the core. The core can contain urea, a pH buffering agent, and an urease inhibitor. The shell can contain urea. In some aspects, the core can further contain water, a polymer thickener, and/or a nitrification inhibitor. In some aspects, the core can contain at most 2 wt. %, or less than 1 wt. %, preferably substantially free of Plaster of Paris or bleached white flour or both. In some instances, the core can contain a binder. In some instances, the pH buffer can act as a binder as well as a pH buffer. Thus the fertilizer particles of the present invention provide a solution to at least some of the previously mentioned problems associated with using Plaster of Paris and/or flour (bleached white flour) during the production process of fertilizer particles. Still further, the fertilizer particles of the present invention provide for stabilization of the urease inhibitor in the core, which can serve to protect the urea in the core and the urea in the shell from hydrolysis.

[0060] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Core-Shell Fertilizer Particle

[0061] An illustrative cross-sectional view of an example of a core-shell fertilizer particle of the present invention is depicted in the FIG. 1. The fertilizer particle 10 can contain a core 2 and a shell 4. While the shape of the fertilizer particle 10 is depicted as being spherical, other shapes are contemplated (e.g., cylindrical shape, puck shape, oval shape, oblong shape, etc.). The overall shape of the fertilizer particle 10 can be influenced by the shape of the uncoated core (e.g., spherical, cylindrical, puck, oval, oblong, etc., core can result in a similarly shaped coated particle). The shell 4 can cover at least a portion of an outer surface 2a of the core 2. While for the core-shell fertilizer particle 10 depicted in the FIG. 1, the shell 4 covers entire outer surface of the core, core-shell fertilizer particles with shell covering a portion of the outer surface of the core can readily be made.

[0062] The core 2 can contain urea, a pH buffering agent, and an urease inhibitor. In some aspects, the core 2 can further contain water, a polymer thickener, a filler, and/or a nitrification inhibitor. In some aspects, the core can contain 20 wt. % to 80 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, and 80 wt. %, of urea, based on the total weight of the core. In some aspects, the core can contain 15 wt. % to 80 wt. %, or at least, equal to, or between any two of 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, and 80 wt. %, of a pH buffering agent, based on the total weight of the core. In some aspects, the core can contain 0.1 wt. % to 5 wt. % or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of an urease inhibitor, based on total weight of the core. In some aspects, the core can contain 0.1 wt. % to 7 wt. % or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 6 wt. %, and 7 wt. % of water, based on the total weight of the core. In some aspects, the core can contain 0.1 wt. % to 5 wt. % or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of an polymer thickener, based on the total weight of the core. In some aspects, the core can contain 5 wt. % to 35 wt. %, or at least, equal to, or between any two of 5 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, and 35 wt. % of a nitrification inhibitor based on the total weight of the core. In some aspects, the core can contain 0 wt. % to 60 wt. %, or at least, equal to, or between any two of 0 wt. %, 1 wt. %, 5 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, and 60 wt. % of a filler based on the total weight of the core. In some aspects, the combined wt. % of the urea, CaCO.sub.3, one or more urease inhibitor, water, and optionally a nitrification inhibitor and/or a polymer thickener in the core is 98 wt. % to 100 wt. %, or at least, equal to, or between any two 98 wt. %, 98.2 wt. % 98.4 wt. % 98.6 wt. % 98.8 wt. % 99 wt. % 99.2 wt. % 99.4 wt. % 99.6 wt. % 99.8 wt. % to 100 wt. %, based on the total weight of the core.

[0063] The shell 4 can contain urea. In some aspects, the shell 4 can contain 50 wt. % to 100 wt. %, or at least, equal to, or between any two of 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, 85 wt. %, 90 wt. %, 95 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0064] In some aspects, the core 2 can contain: (1) 45 wt. % to 60 wt. %, or at least, equal to, or between any two of 45 wt. %, 46 wt. %, 47 wt. %, 48 wt. %, 49 wt. %, 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, and 60 wt. % of urea; (2) 22 wt. % to 45 wt. %, or at least, equal to, or between any two of 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. % and 45 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; and (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0065] In some aspects, the core 2 can contain: (1) 45 wt. % to 60 wt. %, or at least, equal to, or between any two of 45 wt. %, 46 wt. %, 47 wt. %, 48 wt. %, 49 wt. %, 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, and 60 wt. % of urea; (2) 22 wt. % to 45 wt. %, or at least, equal to, or between any two of 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. %, and 45 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; and (5) 20 wt. % to 25 wt. %, or at least, equal to, or between any two of 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, and 25 wt. % of a nitrification inhibitor, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0066] In some aspects, the core 2 can contain: (1) 45 wt. % to 60 wt. %, or at least, equal to, or between any two of 45 wt. %, 46 wt. %, 47 wt. %, 48 wt. %, 49 wt. %, 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, and 60 wt. % of urea; (2) 22 wt. % to 45 wt. %, or at least, equal to, or between any two of 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. % and 45 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; and (5) 0.5 wt. % to 5 wt. %, or at least, equal to, or between any two of 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of a polymer thickener, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0067] In some aspects, the core 2 can contain: (1) 45 wt. % to 60 wt. %, or at least, equal to, or between any two of 45 wt. %, 46 wt. %, 47 wt. %, 48 wt. %, 49 wt. %, 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, and 60 wt. % of urea; (2) 22 wt. % to 45 wt. %, or at least, equal to, or between any two of 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. %, and 45 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; (5) 20 wt. % to 25 wt. %, or at least, equal to, or between any two of 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, and 25 wt. % of a nitrification inhibitor; and (6) 0.5 wt. % to 5 wt. %, or at least, equal to, or between any two of 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of a polymer thickener, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell

[0068] In some aspects, the core 2 can contain: (1) 65 wt. % to 75 wt. %, or at least, equal to, or between any two of 65 wt. %, 66 wt. %, 67 wt. %, 68 wt. %, 69 wt. %, 70 wt. %, 71 wt. %, 72 wt. %, 73 wt. %, 74 wt. %, and 75 wt. % of urea; (2) 20 wt. % to 30 wt. %, or at least, equal to, or between any two of 20 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, 25 wt. %, 26 wt. %, 27 wt. %, 28 wt. %, 29 wt. %, and 30 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; and (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0069] In some aspects, the core 2 can contain: (1) 65 wt. % to 75 wt. %, or at least, equal to, or between any two of 65 wt. %, 66 wt. %, 67 wt. %, 68 wt. %, 69 wt. %, 70 wt. %, 71 wt. %, 72 wt. %, 73 wt. %, 74 wt. %, and 75 wt. % of urea; (2) 20 wt. % to 30 wt. %, or at least, equal to, or between any two of 20 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, 25 wt. %, 26 wt. %, 27 wt. %, 28 wt. %, 29 wt. %, and 30 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; and (5) 0.5 wt. % to 5 wt. %, or at least, equal to, or between any two of 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of a polymer thickener, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0070] In some aspects, the core 2 can contain: (1) 20 wt. % to 75 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, and 75 wt. % of urea; (2) 20 wt. % to 60 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, and 60 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; and (5) 0.5 wt. % to 5 wt. %, or at least, equal to, or between any two of 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of a polymer thickener, based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0071] In some aspects, the core 2 can contain: (1) 20 wt. % to 75 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, and 75 wt. % of urea; (2) 20 wt. % to 60 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, and 60 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; (5) 0.5 wt. % to 5 wt. %, or at least, equal to, or between any two of 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, and 5 wt. % of a polymer thickener; and (6) 20 wt. % to 25 wt. %, or at least, equal to, or between any two of 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, and 25 wt. % of a nitrification inhibitor based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0072] In some aspects, the core 2 can contain: (1) 20 wt. % to 75 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, and 75 wt. % of urea; (2) 20 wt. % to 60 wt. %, or at least, equal to, or between any two of 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, and 60 wt. % of a pH buffering agent; (3) 0.1 wt. % to 7 wt. %, or at least, equal to, or between any two of 0.1 wt. %, 0.5 wt. %, 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, 3 wt. %, 3.5 wt. %, 4 wt. %, 4.5 wt. %, 5 wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, and 7 wt. % of water; (4) 1 wt. % to 3 wt. %, or at least, equal to, or between any two of 1 wt. %, 1.5 wt. %, 2 wt. %, 2.5 wt. %, and 3 wt. % of an urease inhibitor; and (5) 20 wt. % to 25 wt. %, or at least, equal to, or between any two of 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, and 25 wt. % of a nitrification inhibitor based on the total weight of the core. The shell 4 can contain 85 wt. % to 100 wt. %, or at least, equal to, or between any two of 85 wt. %, 86 wt. %, 87 wt. %, 88 wt. %, 89 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, and 100 wt. %, of urea, based on the total weight of the shell.

[0073] In some aspects, the urease inhibitor can include a thiophosphoric triamide derivative, and/or phenyl phosphorodiamidate (PPDA). In some aspects, the thiophosphoric triamide derivatives can be N-(n-butyl) thiophosphoric triamide (NBPT), and/or N-(n-propyl) thiophospshoric triamide (NPPT). In some aspects, the urease inhibitor can include NBPT.

[0074] In some aspects, the pH buffering agent can be CaCO.sub.3, MgO, KH.sub.2PO.sub.4, NaHCO.sub.3, 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. In some aspects, the pH buffering agent can be CaCO.sub.3. In some aspects, the CaCO.sub.3 can be included as chalk powder.

[0075] In some aspects, the filler can contain one or more of silica, dried distillers grains with solubles (DDGS), CaCO.sub.3, MgO, CaO, bone mill powder, or rice husk, or mixtures thereof. Other suitable fillers known in the art may also be used. In some aspects, a pH buffering agent can also function as a filler. For example, in some aspects, CaCO.sub.3 is used as both the filler and as the pH buffering agent. In some instances, no other fillers or pH buffering agents other than CaCO.sub.3 are included in the core particle.

[0076] In some aspects, the nitrification inhibitors can include 3,4-dimethylpyrazole phosphate (DMPP), thio-urea (TU), dicyandiamide (DCD), 2-Chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), 5- Ethoxy-3-trichloromethyl -1, 2, 4-thiadiazol (Terrazole), 2-Amino-4-chloro-6-methyl- pyrimidine (AM), 2-Mercapto-benzothiazole (MBT), or 2-Sulfanimalamidothiazole (ST) or any combination thereof, preferably DCD.

[0077] In some aspects, the polymer thickener can be hydroxypropyl methylcellulose (HPMC), carboxymethylcellulose, hydroxyethylcellulose, polyethylene glycol (PEG), guar gum, locust bean gum, xanthan gum, other natural gums, synthetic polymers based on acrylates, polyacrylamide (PAM), PVP, combinations of synthetic polymers, or carbomers, any combination thereof. In some aspects, polymer thickening agent can be HPMC.

[0078] A number of urease inhibitors and nitrification inhibitors have been developed to enhance the efficiency of urea fertilizer. But their application can be challenging due to stability problems of some the urease inhibitors and/or nitrification inhibitors under various conditions such as pH, temperature, precipitation, etc. For example, NBPT is known to be a good inhibitor of urease but it is unstable under acidic pH. NBPT also decomposes when exposed directly to high temperatures, such as the temperature of a urea melt (about 135-140° C.). In the case of nitrogen containing fertilizers, after application, the soil environment can become acidic. Accordingly, urease inhibitors and/or nitrification inhibitors that are sensitive to the acidic pH degrade and will not reach their full performance capability. Including a large excess of urease inhibitors and/or nitrification inhibitors to compensate for the loss due to pH variations may not be successful, since the fertilizers, which are present in a large excess (in comparison to the urease inhibitors and/or nitrification inhibitors), continue to alter the pH of the soil environment. Also, some commercial products, such as SuperU®, use organic solvents like NMP for adding urease inhibitors and/or nitrification inhibitors to the fertilizer composition.

[0079] The core-shell fertilizer particles of the present invention provide a solution to at least some of these issues. The urea and pH buffering agent in the core and urea in the shell results in a core-shell structure that can protect the urease inhibitor(s) and/or the nitrification inhibitor(s) from degradation during the manufacture of the core (e.g., protection from high temperatures, high pressures, acidic pH conditions, etc.).

[0080] The urea in the shell can first come in contact with the soil, protecting the urease inhibitor and nitrification inhibitor in the core, which will get released gradually. The core can contain urea and a pH buffering agent. The pH buffering agent can neutralize the acidity caused by urea hydrolysis, thereby preventing the urease inhibitors, such as, for example, NBPT, from degrading when placed in soil with an acidic pH. Thus, the pH buffering agent can increase the efficacy of urease inhibitors, for example, NBPT, and also maintains soil pH. In some aspects, certain pH buffering agent can also function as a thermal masking material for other ingredient in the core, such as NBPT, and act as an filler. For example, in some embodiments, CaCO.sub.3 can used as pH buffering agent and filler. The urea in the fertilizer core can protect the urease inhibitor and the nitrification inhibitor, from being exposed to high temperatures during the core manufacturing process (e.g., granulation process), thereby reducing the likelihood of the urease inhibitor and the nitrification inhibitor from decomposing in the manufacturing process. CaCO.sub.3 in the core can also reduce the likelihood of NBPT degradation during the core manufacturing process (e.g., granulation process). CaCO.sub.3 can function as both pH buffering agent and a filler material and can improve the physical properties of the core, such as crush strength, homogeneity, and the release kinetics of inhibitors from the core particle. The polymer thickener can function as a plasticizer and promote desired continuous and uniform flow characteristics of a mixture used in forming the core.

[0081] The core of the core-shell fertilizer particles of the present invention can contain no more than 2 wt. %, or less than 1 wt. %, or less than 0.5 wt. %, or less than 0.1 wt. % or substantially free of Plaster of Paris (POP), flour(s) such as wheat flour such as bleached wheat flour (BWF), starch, gluten, kaolin, bentonite, colloidal silica, polyethylene glycol, and/or polycaprolactone.

[0082] In some aspects, additional fertilizer substances besides urea can be included or excluded in the core and/or shell of the core-shell fertilizer particles. 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 particle in enhancing plant growth and crop yield. Additional additives may also be included or excluded in the fertilizer particles. Non-limiting examples of additives that can be included or excluded from the fertilizer particles of the present invention include micronutrients, additional nitrogen nutrients, and/or secondary nutrients. A micronutrient is a botanically acceptable form of an inorganic or organometallic compound such as boron, copper, iron, chloride, manganese, molybdenum, nickel, or zinc. An additional nitrogen nutrient is a nutrient other than urea can deliver nitrogen to a plant. In some aspects, the additional nitrogen nutrient can include ammonium nitrate, ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-formaldehyde, ammonium chloride, and potassium nitrate. A secondary nutrient is a substance that can deliver calcium, magnesium, and/or sulfur to a plant. In some aspects, the secondary nutrients may include lime, gypsum, superphosphate, or a combination thereof.

[0083] The core of the core-shell fertilizer particles can have desirable physical properties such as desired levels of abrasion resistance, particle strength, pelletizability, hygroscopicity, particle shape, and size distribution, which are important properties for the fertilizer core.

[0084] The fertilizer particles described herein can be comprised in a composition useful for application to soil. In addition to the fertilizer particles, the composition may include other fertilizer compounds, micronutrients, primary nutrients, additional urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof.

[0085] The fertilizer particles described herein can also be included in a blended composition comprising other fertilizer granules. The other fertilizer granules can be granules of urea, Single Super Phosphate (SSP), Triple Super Phosphate (TSP), ammonium sulfate and the like.

B. Method of Making a Fertilizer Particle

[0086] The core can be formed by a pelletizing process such as a pelletizing press process, a compacting process, an extrusion process, or a granulating process.

[0087] In some aspects, the pelletizing press process of core formation can include, forming a powdered composition by mixing the core ingredients such as urea, a pH buffering agent, an urease inhibitor, and optionally a nitrification inhibitor, a filler, and/or a polymer thickener in dry form and pressing the powdered composition through a die to form a pelletized core of a desired shaped. The pelletizing press process can be done using a pelletizing press known in the art. In some aspects, core ingredients can be mixed in a mixer, such as a turbo mixer to form the powdered composition, the powdered composition from the mixer can be fed to a screw feeder connected to a pelletizing press. In some aspects, the powdered composition can be fed to the screw feeder at a rate 40 kg/hr to 100 kg/h, or 50 kg/hr to 80 kg/h. In some aspects, the pelletizing press can include twin rollers rotating at a speed 150 to 200 RPM and the powdered composition can be pressed through the die by the rollers.

[0088] In some aspects, the compacting process of core formation can include, forming a powdered composition by mixing the core ingredients such as urea, a pH buffering agent, an urease inhibitor, and optionally a nitrification inhibitor, a filler, and/or a polymer thickener in dry form, compacting the powdered composition to form a compacted composition and crushing, grinding and/or granulating the compacted composition to form the core of desired shape and size. The compacting process can be done using a roller compactor known in the art. In some aspects, the powdered composition can be compacted by feeding the powdered composition into a roller compactor containing a rotating roller and a roller in immobile phase, and forming a compacted composition in form of a sheet from the powdered composition.

[0089] In some aspects, the granulation process of core formation can include preparing a powder composition containing a pH buffering agent, an urease inhibitor, and, optionally a nitrification inhibitor, a filler, and/or a polymer thickener and contacting the powder composition with a molten urea composition under conditions sufficient to form a plurality of solid particles containing the powder composition embedded within a solid urea matrix. In some aspects, the contacting condition of the powder composition and the molten urea composition can include spraying the molten urea composition onto the powder composition. In some aspects, the molten urea composition can be an aqueous urea melt solution (e.g., 90 wt. % -96 wt. % urea)

[0090] In some aspects, the extrusion process of core formation can include, forming a extrudable composition containing urea, a pH buffering agent, an urease inhibitor, and optionally a nitrification inhibitor, a filler and/or a polymer thickener, and extruding the extrudable composition. The method may also include a drying step after extruding to remove solvent that may have been added to make the composition extrudable. In some aspects, the extrudable composition can be formed by mixing urea, a pH buffering agent, an urease inhibitor, and optionally a nitrification inhibitor, a filler and/or a polymer thickener in dry form, adding any solvent, if needed. In some aspects, the solvent can be water. The extrusion can be done using suitable extruder apparatus known in the art and can be performed at a temperature between 0° C. and 150° C. and a screw speed from 1 to 500 rpm, wherein the extruder comprises a multi-feeder comprising extrusion components including a main drive, shaft, screw, barrel, and/or die.

[0091] The core can then be contacted with an urea solution or melted urea to form a urea-based shell, thereby forming a core-shell fertilizer particle. The contacting can include spraying the urea solution or urea melt onto the core particle at a temperature 100° C. to 145° C. or at least, equal to, or between any two of 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., and 145° C. As the urea solution or urea melt is sprayed onto the core particle, it can be cooled and dried to form a solidified outer coating or shell on at least a portion of an outer surface of the core, which can result in a core-shell fertilizer particle of the present invention. The resulting fertilizer particle can be of various sizes and shapes. In some aspects, the urea solution can be aqueous urea solution containing 80 wt. % to 98 wt. % or at least, equal to, or between any two of 80 wt. %, 95 wt. %, 90 wt. %, 91 wt. %, 92 wt. %, 93 wt. %, 94 wt. %, 95 wt. %, 96 wt. %, and 98 wt. % of urea.

C. Methods of Using Fertilizer Particles

[0092] The core-shell fertilizer particles of the present invention can be used in methods of increasing the amount of nitrogen in soil and of enhancing plant growth. Such methods can include applying to the soil an effective amount of a composition comprising the core-shell fertilizer particles 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 soybeans. The method can include applying core-shell fertilizer particles of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc.

[0093] 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. The Gymnosperms may include plants from the Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae, and Ginkgoaceae families. The Angiosperms may include plants from the Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Capparidaceae, Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae, Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Grossulariaceae, Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae, Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Muntingiaceae, Myoporaceae, Myricaceae, Myrsinaceae, Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oxalidaceae, Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporaceae, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Styracaceae, Surianaceae, Symplocaceae, Tamaricaceae, Theaceae, Theophrastaceae, Thymelaeaceae, Tiliaceae, Ulmaceae, Verbenaceae, and/or Vitaceae family.

[0094] The effectiveness of compositions comprising the core-shell fertilizer particles of the present invention can be ascertained by measuring the amount of nitrogen 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 nitrogen 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.

[0095] In one aspect, the core-shell fertilizer particles of the present invention can have a density that is greater than water. This can allow the particles to sink in water rather than float. This can be especially beneficial in instances where application is intended to a crop that is at least partially or fully submerged in water. A non-limiting example of such a crop is rice, as the ground in a rice paddy is typically submerged in water. Thus, application of core-shell fertilizer particles to such crops can be performed such that the core-shell fertilizer particles are homogenously distributed on the ground that is submerged under water. By comparison, particles that have a density that is less than water would have a tendency to remain in or on the water surface, which could result in washing away of the particles and/or coalescence of the particles, either of which would not achieve homogenous distribution of the particles to the ground that is submerged under water.

EXAMPLES

[0096] 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

Methods of Making Fertilizer Particles

[0097] Materials: Technical grade urea was obtained from SABIC (Riyadh, Kingdom of Saudi Arabia). Chalk powder was used as a source for CaCO.sub.3. Hydroxypropylmethylcellulose (HPMC) was obtained from Loba Chemie Pvt. Ltd. (Mumbai, India). N-(n-butyl) thiophosphoric triamide (NBPT) was purchased from Samich (HK) Ltd. (Hangzhou, China). DCD was obtained from Sigma Aldrich.

[0098] Procedure for Preparing the Core: Four sample core compositions are shown in Table 1. The cores were prepared with a pellet press by the following method. Core ingredients were mixed using a turbo-mixer MTI in dry powder form for about 30 seconds. The dry mixed powder was discharged out from the mixer and fed into a screw feeder, which was connected to a pelletizing press. Then the mixture was fed into the press at 50 to 80 kg/hour. The press contained twin rollers that were rotating at 150 to 200 RPM. The dry mass was pressed through a die with 1 mm holes, and compressed into cylindrical strands. Further, these strands were cut into pellets by knives placed under the die. Then the cylindrical pellets were cooled in an air suction chamber. The core pellets were substantially cylindrical shape with a length of 0.7 mm to 1.6 mm and a diameter of 0.8 mm to 1.2 mm.

TABLE-US-00001 TABLE 1 Composition of the core Urea Chalk HPMC NBPT DCD (wt. Powder (wt. (wt. (wt. %) (wt. %) %) %) %) Sample 1 94.8 0 3 2.2 0 (Comparative sample) Sample 2 50.8 25 0 2.2 22 Sample 3 71.3 25 1.5 2.2 0 Sample 4 56.3 40 1.5 2.2 0

[0099] Procedure for Coating the Core: The core pellets were coated with an aqueous urea melt solution (90-96% urea) in a granulator. The solution was then dried to form a solidified urea shell on the outer surface of the pellets to form the core-shell fertilizer particles. The granulator bed temperature was 80° C. to 110° C.

Example 2

Method for Quantifying the NBPT and DCD Inhibitors by HPLC

[0100] NBPT and DCD quantification in the core particles: Core particles were stored at room conditions and analyzed for inhibitor content after 21, 44, 63, 101, 151 and 236 days of preparation. Approximately 1 g of the core particles described in Table 1 were weighted into a mortar and crushed with a pestle to make powder. 200 mg of the powdered sample was added (in triplicate) into polypropylene tubes with 10 mL of a diluent (acetonitrile:water, 50:50). The samples were sonicated for 30 mins with intermediate shaking and vortexed for 1 hr using a vortex shaker. The vortexed sample was filtered using a 0.45 μm syringe filter into a High Performance Liquid Chromatography (HPLC) vial and analyzed by HPLC. See Tables 2 and 3. For DCD samples, filtered solution was diluted 10× prior to HPLC analysis. Inhibitor quantification was obtained using a calibration curve. Results are presented in Table 4. The results show formulations of the current invention stabilize the inhibitors.

[0101] NBPT and DCD quantification in the core-shell particles: Core-shell particles were stored at room conditions and analyzed for inhibitor content after 90, 162, and 195 days of preparation. Approximately 4 g of core-shell fertilizer particles prepared as described in Example 1, using cores as described in Table 1, were added into polypropylene tubes and 20 mL of a diluent was added (in triplicate). The samples were sonicated for 30 mins with intermediate shaking and vortexed for 1 hr using a vortex shaker. The vortexed sample was filtered using a 0.45 μm syringe filter into a HPLC vial and analyzed by HPLC. See Tables 2 and 3. For DCD samples, filtered solution was diluted 20× prior to HPLC analysis. Inhibitor quantification was obtained using a calibration curve. Results are presented in Table 4. The results show formulations of the current invention stabilize the inhibitors.

TABLE-US-00002 TABLE 2 Chromatographic conditions for NBPT quantification Method name NBTPT + DCD.1cm Column Phenomenex, Luna Pnenyl hexyl 250*4.6, 5 μ Column oven 35° C. temperature Injection Vol. 5 μL Flow rate 1.00 mL/min Mobile Phase Reservoir A: Milli-Q Water, Reservoir C: Acetonitrile Isocratic: Milli-Q water: Acetonitrile (80:20 v/v) Run Time 15 mins Wavelength 207 nm

TABLE-US-00003 TABLE 3 Chromatographic conditions for DCD quantification Method name DCD_7.1cm Wash method DCD_7_Wash Method.1cm Column Zorbax NH2, 150 × 4.6 mm, 5 micron Column oven 30° C. temperature Injection Vol. 5 μL Flow rate 1.50 mL/min Mobile Phase Reservoir A: Milli Q Water Reservoir B: Methanol Reservoir C: Acetonitrile Wavelength 217 nm Milli Q Time(mL) water Methanol Acetonitrile Gradient 0.01 1 2 97 program 4.00 8 2 90 4.50 8 2 90 8.00 3 2 95 14.00 1 2 97 15.00 1 2 97 15.00 Controller Stop

[0102] Results: Results presented in Table 4 show NBPT in the core particle with mostly urea (Sample 1) degrades faster compared to that in core particles containing chalk power with urea (Samples 2, 3, and 4). Thus chalk power included in the core stabilizes the inhibitors in the core. Similarly results presented in Table 5 show chalk power included in the core stabilizes the inhibitors in the core of the core-shell particles. NBPT for a core-shell particle using the core of Sample 1 (control) is expected to be substantially lower than for the cores of Samples 2, 3, and 4, due at least in part to degradation that is expected because of exposure of the core to the high heat of the urea melt used to coat the core.

TABLE-US-00004 TABLE 4 Inhibitor recovery from core particles stored at room conditions Core % DCD Particle % NBPT Recovery Recovery Age (Days) Sample 1 Sample 2 Sample 3 Sample 4 Sample 2 21 91.2 97.0 93.9 95.0 Not Done 44 92.6 99.6 94.1 91.4 94.7 63 87.7 97.7 89.1 89.9 96.0 101 91.8 94.7 92.0 93.8 94.5 151 81.6 93.5 90.0 93.9 99.7 236 60.9 88.0 83.1 90.9 87.5

[0103] The amount of inhibitor recovered on 0 day (granulation day) was considered as 100% for the recovery calculations. The Sample numbers correlate with the Samples shown in Table 1.

TABLE-US-00005 TABLE 5 Inhibitor recovery in the core-shell particles stored at room conditions Core-Shell DCD particles age NBPT Recovery, % Recovery, % (days) Sample 2 Sample 3 Sample 4 Sample 2  90 days 96.8 103.7 93.6 93.5 162 days 96.5 102.5 94.0 91.5 195 days 80.7 90.2 93.5 90.5
The amount of inhibitor recovered on 0 day (granulation day) was considered as 100% for the recovery calculations. The Sample numbers correlate with the Sample numbers for cores of Table 1 used in forming the core-shell particles.