Fertilizer comprising nitrogen, phosphorous, potassium, and microorganisms

Abstract

Disclosed is a fertilizer containing a mixture containing calcium nitrate (Ca(NO3)2), urea phosphate (NH2CONH4HPO4), potassium phosphate (K3PO4), and a plurality of live microorganisms. Methods of making and using the fertilizer are also disclosed.

Description

FERTILIZER COMPRISING NITROGEN, PHOSPHOROUS, POTASSIUM, AND MICROORGANISMSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of European Application No. 23218156.0, filed December 19, 2023, the contents of which is incorporated into the present application by reference.BACKGROUND OF THE INVENTIONI. Field of the Disclosure

[0002] This disclosure generally concerns fertilizer compositions containing a slow-release agent. In particular embodiments, the disclosure concerns fertilizers containing calcium nitrate, urea phosphate, potassium phosphate, and a plurality of live microorganisms.II. Background

[0003] Soil nutrients, such as nitrogen, phosphorus, potassium, and sulfur, as well as trace elements such as iron, zinc, copper, calcium, and magnesium, are useful for achieving thriving agriculture and growth of plants. Upon repeated planting cycles, the quantity of these nutrients in the soil may be depleted, resulting in inhibited plant growth and decreased production. To counter this effect, fertilizers have been developed to help replace the depleted vital nutrients. Single-nutrient fertilizers and multi-nutrient fertilizers, such as fertilizer blends, have been developed to meet the varied needs of crop production worldwide.

[0004] Continuous use of fertilizers leads to loss of soil fertility and nutrient balance. To increase the crop yield and satisfy the growing need of increasing population, more fertilizers are being used. In addition, large application or usage of urea and urea’s rapid hydrolysis and nitrification in the soil is causing deterioration of soil health and environmental issues such as greenhouse emissions and ground water contamination.

[0005] Soil does not comprise just nutrients, it also comprises mineral substances, organic matter, and microorganisms. The role and activities of microorganisms in the soil is important for nutrient uptake by plants (e.g., via the root system), as beneficial microorganisms in the soil can directly participate in formation of soil fertility, e.g., conversion of substances and energyin the soil, formation and decomposition of humus and / or other organic material, release and / or fixation of trace elements and / or nutrients, fixation of nitrogen, etc.

[0006] However, in a purely natural state, the quantity of beneficial microorganisms in the soil may decrease and / or be insufficient for the agricultural yields anticipated by modem agrarian methods. Therefore, similar to the replenishment of soil using fertilizers comprising nutrients, soil may also need to be replenished with beneficial microorganisms.

[0007] Currently, most supplemental microorganisms are delivered to the soil for end use either: (i) directly in their commercial form (e.g., as a solid and / or liquid form fertilizer), (ii) in solution with irrigation water, (iii) coated to seeds under ambient temperature conditions, or (iv) coated on fertilizers. These delivery methods are limited in scope and also limit the type of microorganisms that can be utilized. There exists a need in the field to be able to widen the scope of microorganisms used and / or widen the scope of microorganism delivery methods when utilized in combination with various fertilizers. Some fertilizers, especially those highly acidic or basic, can be harmful to microorganisms by contact. In addition, high temperatures associated with fertilizer creation can render most microorganisms inactive and / or inefficient.SUMMARY OF THE INVENTION

[0008] A solution to at least some of the problems discussed above is disclosed herein, including a microbe-enhanced fertilizer composition containing urea phosphate, potassium phosphate, calcium nitrate, and a plurality of live microorganisms. In some aspects, the components of the fertilizer are combined so that the fertilizer has slow-release characteristics for nutrients therein. In some aspects, the sources of the ingredients can include by-products and green sources. Non-limiting examples include use of calcium nitrate derived from phosphate rock, potassium chloride originated from separation of seawater, and / or use of green nitric acid as a reactant to produce calcium nitrate. Further the microbe-enhanced fertilizer composition enables delivery of stable and live microorganisms along with each granule of fertilizer, where the microorganism is needed and / or over time as the fertilizer degrades. Additionally, the microbe-enhanced fertilizer composition can have an increased microorganism and / or fertilizer shelf-life. Further, the microbe-enhanced fertilizer composition may provide stability to a nitrogen source, such as urea phosphate, at high pH. The pH and nitrogen source in the microbe-enhanced fertilizer composition may be adjusted to the needs of storage, the crop, the soil, and / or the microbes.

[0009] In some aspects, the fertilizer composition comprises microorganisms, wherein the microorganisms comprise diazotrophic bacteria, Azospirillum species, Azotobacter species,Frateuria aurantia, Bacillus species, endophytes, nitrogen fixing microorganism, methylotrophs, comammox microorganism, phosphorus solubilizing microorganism, Nitrospira species, Methylobacterium species, and / or pink pigmented facultative methylotrophs (PPFM-trophs).

[0010] In some aspects, the calcium nitrate forms a continuous phase in the fertilizer composition. In some aspects, the calcium nitrate (Ca / NCh ) at least partially binds and / or at least partially surrounds the urea phosphate (NH2CONH4HPO4) and / or the potassium phosphate (K3PO4). In some aspects, at least a portion of the urea phosphate (NH2CONH4HPO4) and / or potassium phosphate (K3PO4) are absorbed on the surface of the calcium nitrate (Ca / NCh ). In some aspects, at least a portion of the microorganisms in the fertilizer composition may be comprised in a coating of the fertilizer composition. In some aspects, any one of a calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4) may be at least partially surrounded with the microorganism. In some aspects, the microorganism are at least partially surrounded with a calcium nitrate (Ca(NO3)2), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4).

[0011] In some aspects, the composition further comprises phosphoric acid (H3PO4), urea (NH2CONH2), calcium phosphate (Cas / PC ), potassium chloride (KC1), hydrochloric acid (HC1), and / or nitric acid (HNO3). In some aspects, the composition comprises phosphate rock that comprises at least a portion of the calcium phosphate. In some aspects, at least a portion of the phosphoric acid is derived from a natural source. In some aspects, at least a portion of the nitric acid is derived from a renewable energy source or a process that uses a renewable energy source. In some aspects, the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and / or biomass renewable energy source.

[0012] In certain aspects, the fertilizer composition contains at least any one of, at most any one of, equal to any one of, or between any two of 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 or 99.999 wt.% or any number or range therein of a combination of the calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and potassium phosphate (K3PO4), and / or at least any one of, at most any one of, equal to any one of, or between any two of 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or 1 wt. % or any number or range therein of the plurality of live microorganism based on the total weight of the fertilizer composition.

[0013] In some aspects, the fertilizer composition contains 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 or 25 wt. % of nitrogen, contains at least any one of, at most any one of, equalto any one of, or between any two of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 wt. % phosphorous (P) in an amount equivalent to wt.% P2O5, contains at least any one of, at most any one of, equal to any one of, or between any two of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt. % calcium, contains at least any one of, at most any one of, equal to any one of, or between any two of 3, 4, 5, 6, 7, 8, 9, or 10 wt. % potassium, and / or contains at least any one of, at most any one of, equal to any one of, or between any two of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition.

[0014] Certain aspects are directed to a method of making a fertilizer, including any fertilizer described herein. The method can include steps (a), (b), (c), and / or (d). In step (a), calcium phosphate is contacted with nitric acid to generate a first reaction product comprising calcium nitrate and phosphoric acid. In step (b), the first reaction product and / or phosphoric acid is contacted with urea to generate a second reaction product comprising urea phosphate. In step (c), the first reaction product, the second reaction product, and / or phosphoric acid is contacted with potassium chloride to generate a third reaction product comprising potassium phosphate and hydrochloric acid. In step (d) the third reaction product, the second reaction product, and / or the first reaction product is contacted with a plurality of live microorganisms. In some instances, step (b) comprises contacting the first reaction product with the urea. In some instances, step (c) comprises contacting the first reaction product and / or second reaction product with the potassium chloride. In some instances, step (d) comprises contacting the plurality of live microorganisms with a combination of the third reaction product, the second reaction product, and the first reaction product to at least partially coat the combination with the plurality of live microorganisms. In some instances, at least a portion of the phosphoric acid of step (c) and / or (b) is generated in step (a). In some instances, at least two of steps (a), (b), (c), and (d) are performed as a one pot synthesis. In some instances, the fertilizer further comprises unreacted calcium phosphate, nitric acid, urea, potassium chloride, hydrochloric acid, and / or phosphoric acid. In some instances, the fertilizer does not contain any one or more of calcium sulfate urea adduct, calcium sulfate, calcium phosphate, nitric acid, urea, potassium chloride, hydrochloric acid, and / or phosphoric acid.

[0015] In some instances, the concentration of phosphoric acid remaining in the final microbe-enhanced fertilizer composition is modified, such as by reacting with urea to form urea phosphate or by including more nitrate to make the composition more alkaline or adding more ammonium and / or urea to make the composition more acidic, to regulate the pH of the fertilizer composition. In some instances, the pH of the fertilizer composition is regulated toprovide a pH needed for the soil and / or crop. In some instances, the pH of the fertilizer composition is regulated to provide storage stability for the components of the fertilizer. In some instances, the pH of the fertilizer composition is regulated to reduce the death of microorganisms in the fertilizer. In some instances, the pH of the fertilizer composition is 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, or any range or number therein, such as a pH of 5 to 8, 4 to 9, 5 to 7, 4 to 7, 4 to 8, 5 to 9, 4 to 10, 5 to 10, 6 to 8, etc.

[0016] In certain aspects, the method of making the fertilizer comprises drying the fertilizer mixture to form the microbe-enhanced fertilizer composition. In some instances, at least a portion of the microorganisms are comprised in a coating of a solid fertilizer composition. Steps (a), (b), (c), (d), and / or drying may occur at approximately 20° C to 150° C, such as 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45,46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70,71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95,96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115,116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, and 150° C. In some aspects, steps (a), (b), (c), and / or (d) may occur at 20 to 75° C or any temperature or range therein.

[0017] Also disclosed are the following aspects 1 to 20 of the present invention.

[0018] Aspect 1 is a fertilizer composition comprising calcium nitrate (Ca(N 6)3)2), urea phosphate (NH2CONH4HPO4), potassium phosphate (K3PO4), and a plurality of live microorganisms.

[0019] Aspect 2 is the fertilizer composition of aspect 1, wherein the microorganisms comprise diazotrophic microorganisms, potassium- solubilizing bacteria, Bacillus species, endophytes, methylotrophs, comammox microorganism, and / or phosphorus-solubilizing microorganisms.

[0020] Aspect 3 is the fertilizer composition of any one of aspects 1 and 2, wherein the calcium nitrate forms a continuous phase.

[0021] Aspect 4 is the fertilizer composition of any one of aspects 1 to 3, wherein at least a portion of the microorganisms are comprised in a coating of the fertilizer composition.

[0022] Aspect 5 is the fertilizer composition of any one of aspects 1 to 4, wherein the calcium nitrate (Ca / NC ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4) at least partially surround the microorganism.

[0023] Aspect 6 is the fertilizer composition of any one of aspects 1 to 5, wherein the composition comprises 18 to 22 wt.% nitrogen (N), phosphorous (P) in an amount equivalent to 8 to 12 wt.% P2O5, 10 to 13 wt.% calcium (Ca), 5 to 8 wt.% of potassium (K), and / or 0.05 to 0.5 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition.

[0024] Aspect 7 is the fertilizer composition of any one of aspects 1 to 6, wherein the composition further comprises phosphoric acid (H3PO4), urea (NH2CONH2), calcium phosphate (Cas / PCU ), nitric acid (HNO3), potassium chloride (KC1), and / or hydrochloric acid (HC1).

[0025] Aspect 8 is the fertilizer composition of aspect 7, wherein the composition comprises phosphate rock that comprises at least a portion of the calcium phosphate.

[0026] Aspect 9 is the fertilizer composition of any one of aspects 7 to 8, wherein the phosphoric acid is derived from a natural source.

[0027] Aspect 10 is the fertilizer composition of any one of aspects 7 to 9, wherein at least a portion of the nitric acid is derived from a renewable energy source and / or from a process that uses a renewable energy source.

[0028] Aspect 11 is the fertilizer composition of aspect 10, wherein the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and / or biomass renewable energy.

[0029] Aspect 12 is the fertilizer composition of any one of aspects 1 to 11, wherein the composition does not comprise a binding agent separate from the calcium nitrate.

[0030] Aspect 13 is the fertilizer composition of any one of aspects 1 to 12, wherein at least a portion of the urea phosphate, potassium phosphate, and / or a plurality of live microorganisms are at least partially surrounded by calcium nitrate.

[0031] Aspect 14 is the fertilizer composition of any one of aspects 1 to 13, wherein the fertilizer is homogenous and / or comprises amorphous phases of fertilizer components.

[0032] Aspect 15 is the fertilizer composition of any one of aspects 1 to 14, wherein at least a portion of the urea phosphate, potassium phosphate, and / or a plurality of live microorganisms are encapsulated by the calcium nitrate.

[0033] Aspect 16 is the fertilizer composition of any one of aspects 1 to 15, wherein the fertilizer composition is a solid fertilizer.

[0034] Aspect 17 is a method of producing the fertilizer composition of any one of aspects 1 to 16, the method comprising the steps of:(a) contacting calcium phosphate with nitric acid to generate a first reaction product comprising calcium nitrate and phosphoric acid; and(b) contacting the first reaction product and / or phosphoric acid with urea to generate a second reaction product comprising urea phosphate;(c) contacting the first reaction product, the second reaction product, and / or phosphoric acid with potassium chloride to generate a third reaction product comprising potassium phosphate and hydrochloric acid; and(d) contacting the third reaction product, the second reaction product, and / or the first reaction product with a plurality of live microorganisms.

[0035] Aspect 18 is the method of aspect 17, wherein step (b) comprises contacting the first reaction product with the urea and step (c) comprises contacting the first reaction product and / or second reaction product with the potassium chloride.

[0036] Aspect 19 is the method of any one of aspects 17 to 18, wherein step (c) comprises contacting the plurality of live microorganisms with a combination of the third reaction product, the second reaction product, and the first reaction product to at least partially coat the combination with the plurality of live microorganisms.

[0037] Aspect 20 is a method of fertilizing, the method comprising applying the fertilizer composition of any one of aspects 1 to 16 to a soil, a crop, water, or any combination thereof.

[0038] The term “fertilizer” is defined as a material applied to soils or to plant tissues to supply one or more plant nutrients essential or beneficial to the growth of plants and / or stimulants or enhancers to increase or enhance plant growth.

[0039] The term “granule” can include a solid material. A granule can have a variety of different shapes, non-limiting examples of which include a spherical, a puck, an oval, a rod, an oblong, or a random shape.

[0040] The term “particle” can include a solid material less than a millimeter in its largest dimension.

[0041] The terms “particulate” or “powder” can include a plurality of particles.

[0042] The terms “slow-release” and “slow release” fertilizers are fertilizer that release all of their plant nutrients over a period of weeks or more, instead of within a week or within hours

[0043] The terms “about” or “approximately” as used herein are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0044] The terms “wt. %,” “vol.%,” or “mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume ofmaterial, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt. % of component.

[0045] The use of the word “a” or “an” when used in conjunction with the term “comprising” may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0046] The phrase “and / or” means “and” or “or”. To illustrate, A, B, and / or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, “and / or” operates as an inclusive or.

[0047] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0048] The compositions and methods for their use can “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 limits the scope of the claim to the specified materials or steps which do not materially affect the basic and novel characteristic of the claimed invention.

[0049] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0050] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0051] 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.

[0052] FIG. 1: a depiction of an exemplary microbe-enhanced fertilizer composition.

[0053] FIG. 2 : a schematic flow-chart depicts an exemplary microbe-enhanced fertilizer production according to a non-limiting example of a method disclosed herein.DETAILED DESCRIPTION OF THE INVENTION

[0054] Certain aspects of the present disclosure provide benefits over existing fertilizers, including by having slow-release characteristics for nutrients comprising the fertilizer. Certain aspects provided herein allow for the fertilizer to slowly release nutrients into the soil over a period of time, such as throughout a growing cycle for a plant. This capability can be achieved, in some aspects, without the use of binders other than calcium nitrate, without the use of inhibitors, or without the use of other interventions that add compounds beyond the fertilizer’s nutrients. The calcium nitrate may act as a binder for the other components in the fertilizer.

[0055] Disclosed herein, among other things, is a microbe-enhanced fertilizer and a method of producing a microbe-enhanced fertilizer. In some embodiments, the fertilizer comprises a urea phosphate (NH2CONH4HPO4), calcium nitrate (Ca(NOs)2), potassium phosphate (K3PO4), and the plurality of live microorganisms, which may be one composition and / or one homogenous mixture. The sources of the ingredients can include waste products and green sources. The microbe-enhanced fertilizer composition enables delivery of microorganisms along with each granule of fertilizer, where the microorganism is needed and / or over time as the fertilizer degrades. Additionally, the microbe-enhanced fertilizer composition can have an increased microorganism and / or fertilizer shelf-life. Further, the microbe-enhanced fertilizer composition may provide stability to a nitrogen source, such as urea phosphate, at high pH. The pH and nitrogen sources (e.g., nitrate and ureic nitrogen sources) in the microbe-enhanced fertilizer composition may be adjusted to the needs of storage, the crop, the soil, and / or the microbes.

[0056] The methods and / or compositions of the current disclosure provide an economically efficient means to produce and / or utilize a stable and high quality microbe-enhanced fertilizer. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.I. Fertilizer Compositions

[0057] Certain embodiments herein concern a complex fertilizer composition comprising: a nitrogen compound, such as a urea phosphate (NH2CONH4HPO4) and / or calcium nitrate (Ca(NOs)2); a potassium compound such as potassium phosphate (K3PO4); and a calcium compound such as calcium nitrate (Ca / NCh ) and, a plurality of live microorganisms.

[0058] The fertilizer, which may be a fertilizer granule, can contain a mixture containing calcium (Ca), potassium (K), phosphorus (P) present as a phosphate, nitrogen (N) present as a nitrate and / or urea compound. The ratio of elements present in the fertilizer may be tailored to specific applications.

[0059] In some instances, the fertilizer production may use Cas / PC and HNO3 in amounts suitable for reaction stoichiometry to react all of the calcium phosphate, such as at least 6 moles of nitric acid to one mole of calcium phosphate. In some instances, the amount of urea and potassium chloride used may comprise the quantities required for reaction with the in-situ produced phosphoric acid to consume all of the urea and / or the phosphoric acid not consumed by the other reactions used to produce potassium phosphate (K3PO4). In some instances, the amount of potassium chloride used may comprise the quantities required for reaction stoichiometry between potassium chloride and a portion of in-situ produced phosphoric acid to consume all of the potassium chloride and / or the phosphoric acid not consumed by the other reactions used to produce urea phosphate. In some instances, the amount of urea and potassium chloride used corresponds to the amounts needed to consume the total amount of in-situ produced phosphoric acid. The ratio of urea to potassium chloride can be varied. In some instances, the ratio of urea to potassium chloride can be varied within the range of 0.5:0.5 to 0.5:2, such as 0.5:0.6, 0.5:0.7, 0.5:0.8, 0.5:0.9, 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.2, 0.5:1.3, 0.5:1.4, 0.5:1.5, 0.5:1.6, 0.5:1.7, 0.5:1.8, 0.5:1.9, or 0.5:2 depending on the desired levels of N and K in the fertilizer composition.

[0060] In some instances, the N content may vary within 10-25 wt %, while K content may vary within 5-10% wt basis. In some instances, the calcium content may vary within 10-13% wt basis. In some instances, the P content in fertilizer in the form of P2O5 may vary in the range of 18-24% wt. basis.

[0061] In some instances, the fertilizer composition can comprised of 80 wt. % to 99 wt. % or at least any one of, equal to any one of, or between any two of 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. %, 99.9 wt. %, and 99.99 wt. % of a combination of calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and potassium phosphate (K3PO4). In some aspects, the composition can contain 40 wt. to 85 wt. % or at least any one of, equal to any one of, or between any two of 40 wt. %, 45 wt. %, 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, and 85 wt. % of the calcium nitrate. In some aspects, the composition can contain 40 wt. to 85 wt. % or at least any one of, equal to any one of, or between any two of 40 wt. %, 45 wt. %, 50 wt.%, 55 wt. %, 60 wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, and 85 wt. % of the urea phosphate. In certain aspects, the fertilizer composition can contain 2 wt. % to 20 wt. %, or at least any one of, at most any one of, equal to any one of, or between any two of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt. % of the potassium phosphate. In certain aspects, the fertilizer composition can contain 0.001 wt. % to 1 wt. %, or at least any one of, at most any one of, equal to any one of, or between any two of 0.001, 0.005, 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition based on the total weight of the composition.

[0062] In some aspects, the fertilizer composition may contain 10 to 25 wt. % of nitrogen (N) 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, or 25 wt. % of nitrogen. In some aspects, the fertilizer composition may contain 3 to 10 wt. % of potassium or at least any one of, at most any one of, equal to any one of, or between any two of 3, 4, 5, 6, 7, 8, 9, or 10 wt. % of potassium. In some aspects, the fertilizer composition may contain 5 to 15 wt. % calcium or at least any one of, at most any one of, equal to any one of, or between any two of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt. % calcium. In some aspects, the fertilizer composition may contain 15 to 25 wt. % of phosphorous in an amount equivalent to wt. % P2O5 or at least any one of, at most any one of, equal to any one of, or between any two of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt.% of phosphorous (P) in an amount equivalent to wt. % P2O5. In some aspects, the fertilizer composition may contain 0.05 to 0.5 wt. % of live microorganism or at least any one of, at most any one of, equal to any one of, or between any two of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition.

[0063] In some aspects, the sources of the ingredients can include waste products and green sources. Non-limiting examples include use of calcium nitrate derived from phosphate rock, potassium chloride originated from separation of seawater, and / or use of green nitric acid and / or phosphoric acid as a reactant. Additionally, the microbe-enhanced fertilizer composition can have an increased microorganism and / or fertilizer shelf-life.

[0064] In some aspects, the fertilizer composition comprises microorganisms, wherein the microorganisms comprise diazotrophic bacteria, Azospirillum species, Azotobacter species, Frateuria aurantia, Bacillus species, endophytes, nitrogen fixing microorganism, methylotrophs, comammox microorganism, phosphorus solubilizing microorganism,Nitrospira species, Methylobacterium species, and / or pink pigmented facultative methylotrophs (PPFM-trophs).

[0065] In some aspects, the calcium nitrate forms a continuous phase in the fertilizer composition. In some aspects, the calcium nitrate (Ca / NCh ) at least partially binds and / or at least partially surrounds the urea phosphate (NH2CONH4HPO4) and / or the potassium phosphate (K3PO4). In some aspects, at least a portion of the urea phosphate (NH2CONH4HPO4) and / or potassium phosphate (K3PO4) are absorbed on the surface of the calcium nitrate (Ca / NCh ). In some aspects, at least a portion of the microorganisms in the fertilizer composition may be comprised in a coating of the fertilizer composition. In some aspects, any one of a calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4) may be at least partially surrounded with the microorganism. In some aspects, the microorganism is at least partially surrounded with a calcium nitrate (Ca(NO3)2), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4).

[0066] In some aspects, the composition further comprises phosphoric acid (H3PO4), urea (NH2CONH2), calcium phosphate (Cas / PC ), potassium chloride (KC1), hydrochloric acid (HC1), and / or nitric acid (HNO3). In some aspects, the composition comprises phosphate rock that comprises at least a portion of the calcium phosphate. In some aspects, at least a portion of the phosphoric acid is derived from a natural source. In some aspects, at least a portion of the nitric acid is derived from a renewable energy source or a process that uses a renewable energy source. In some aspects, the renewable energy source comprises a solar, wind, hydro, tidal, geothermal, and / or biomass renewable energy.

[0067] In some other aspects, the fertilizer contains a coating layer that can form a coating over at least a portion of an outer surface of the fertilizer granules / powder / particles. In some aspects, at least a portion of the microorganisms are comprised in a coating of the fertilizer composition. In some aspects, calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4) are at least partially surrounded with the microorganism. In some aspects, the microorganism is at least partially surrounded by calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4).

[0068] In some embodiments, a microorganism that can be included in a microbe-enhanced fertilizer can be a bacteria, archaea, fungi, or a protist. In some instances, the microorganism can include an endophyte, rhizosphere microbe, and / or phyllosphere microbe. In some embodiments, the microorganism can included more than one species of microorganism. In some embodiments, more than one species, genus, phylum, class, and / or kingdom can berepresented in a group of microorganisms protected and / or included in a microbe-enhanced fertilizer. In some embodiments, a microorganism can be cultured and / or grown in a laboratory. In some embodiments, a microorganism can be obtained from a natural source. In some embodiments, a microorganism can be a spore / cyst forming microorganism. In some embodiments, a microorganism can be a spore / cyst forming bacteria.

[0069] In some aspects, the fertilizer further contains a binder. In some aspects, the binder is homogenously distributed throughout the fertilizer composition. In some aspects, the binder is at least partially surrounded by and / or at least partially bound by the calcium nitrate (Ca / NCh ). In some instances, the binder and the fertilizer are comprised at a weight ratio between approximately 0.1:10 to 5:10, such as 0.1:10, 0.2:10, 0.3:10, 0.4:10, 0.5:10, 0.6:10, 0.7:10, 0.8:10, 0.9:10, 1:10, 1.1:10, 1.2:10, 1.3:10, 1.4:10, 1.5:10, 2:10, 3:10, 4:10, or 5:10.

[0070] 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.

[0071] In some aspects, the mixture comprises Ca, N, K, and / or P wherein i) the Ca content of the 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, and 15 wt. %, ii) the N content of the 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, and 30 wt. %, iii) the K content of the 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, and 15 wt. %, and iv) the P content of the 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, and 30 wt. % based on the total weight of the mixture and / or fertilizer.

[0072] The Ca, N, K, and / or P can be present as and / or sourced as a water soluble compound or a water insoluble compound. In some instances, the Ca, N, K, and / or P can be present as a salt. In some aspects, the Ca, N, K, and / or P can be present as a water soluble salt. In some instances, the water soluble Ca and N salt can be Ca / NCh . In some instances, the water soluble N and P can be urea phosphate (NH2CONH4HPO4). In some instances, the water soluble K and P can be (K3PO4). The Ca, N, K, and / or P salt can be in a non-hydrate and / or one or more hydrate form.

[0073] Referring to FIG. 1 a fertilizer granule 100 according to an example of the present invention is shown. The fertilizer granule (100) can contain a major portion of calcium nitrate (101) and urea phosphate (102) in the core, and a minor portion of potassium phosphate (103) and a plurality of live microorganisms (104). In Fig. 1, the microorganisms (104) are uniformly distributed throughout the fertilizer granules. In some instances, the fertilizer granule is homogenous. In some instances, the fertilizer granule is not homogenous. In some instances, the fertilizer granule is coated with a coating. In some instances, the fertilizer granule is coated with a coating containing any one of or a combination of calcium nitrate, urea phosphate, potassium phosphate, and / or live microorganisms. In some instances, the fertilizer is coated with the live microorganisms. In some instances, the fertilizer granules or the fertilizer compositions further comprise other fertilizers, micronutrients, primary nutrients, additional urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof.

[0074] The fertilizer granules can have desirable physical properties such as desired levels of abrasion resistance, granule strength, pelletizability, hygroscopicity, granule shape, and size distribution, which are important properties for the fertilizer core.

[0075] The fertilizer granules described herein can be comprised in a composition useful for application to soil, water, and / or a crop. In addition to the fertilizer granules, the composition may include other fertilizer compounds, micronutrients, primary nutrients, additional urea, additional nitrogen nutrients, insecticides, herbicides, or fungicides, or combinations thereof.

[0076] The fertilizer granules described herein can also be included in a blended composition comprising other fertilizer granules. The other fertilizer granules can be granules of 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.

[0077] 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.II. Microorganisms

[0078] In some embodiments, a microorganism that can be included in a microbe-enhanced fertilizer can be a bacteria, archaea, fungi, or a protist. In some instances, the microorganism can include an endophyte, rhizosphere microbe, and / or phyllosphere microbe. In some embodiments, the microorganism can included more than one species of microorganism. In some embodiments, more than one species, genus, phylum, class, and / or kingdom can be represented in a group of microorganisms protected and / or included in a microbe-enhanced fertilizer.

[0079] In some embodiments, a microorganism can be, but is not limited to, a diazotrophic bacteria, Azospirillum species, Azotobacter species, Frateuria aurantia, Bacillus species, endophytes, nitrogen fixing bacteria, methylotrophs, comammox (e.g., (COMplete AMMonia OXidation) an organism that can convert ammonia into nitrite and then into nitrate through the process of nitrification), phosphorus solubilizing, potassium solubilizing, nitrite oxidizing, Nitrospira species, Methylobacterium species, and / or pink pigmented facultative methylotrophs (PPFM-trophs).

[0080] In some embodiments, a microorganism can be cultured and / or grown in a laboratory prior to addition into the fertilizer. In some embodiments, a microorganism can be obtained from a natural source. In some embodiments, a microorganism can be concentrated prior to addition into the fertilizer.

[0081] In some embodiments, a microorganism can be a spore / cyst forming microorganism. In some embodiments, a microorganism can be a spore / cyst forming bacteria. In some embodiments, a microorganism can be induced to form spores / cysts prior to addition to the fertilizer. In some embodiments, a microorganism is not induced to form spores / cysts prior to and / or as part of a protection scheme. In some embodiments, a microorganism is not chemically induced to form spores / cysts prior to and / or as part of a protection scheme. In some embodiments, a microorganism has been selected for heat tolerance. In some embodiments, a microorganism has not been selected for heat tolerance.

[0082] In some embodiments, microorganisms can be cultured and / or concentrated to greater than, or equal to, approximately 104-1014cells per mL prior to addition to the fertilizer, such as at 104, 105, 106, 107, 108, 109, IO10, 1011, 1012, 1013, or 1014cells per mL In some embodiments, microorganisms can be cultured and / or concentrated to greater than, or equal to, approximately 108-109cells per mL prior to addition to the fertilizer. In some instances, the fertilizer composition contains the microorganisms at greater than, or equal to, approximately 104-1014cells per mL, such as at 104, 105, 106, 107, 108, 109, IO10, 1011, 1012, 1013, or 1014cells per mL. In some instances, the fertilizer composition contains the microorganisms at greater than, or equal to, approximately 104-1014colony forming units (CFU) per mL, such as at 104, 105, 106, 107, 108, 109, IO10, 1011, 1012, 1013, or 1014CFU per mL. In some instances, a coating on the fertilizer composition contains the microorganisms at greater than, or equal to, approximately 104-1014colony forming units (CFU) per mL, such as at 104, 105, 106, 107, 108, 109, IO10, 1011, 1012, 1013, or 1014CFU per mL.

[0083] Prior to contacting with a fertilizer to obtain a microbe-enhanced fertilizer, microorganisms may be protected. In some embodiments, microorganism protection may comprise any one or more of encapsulation, physical protection, and / or engineering methods. In some embodiments, microorganism protection is by contact with a protectant. In some instances, microorganism protection is by encapsulation in a protectant. In some embodiments, a protected microorganism is protected by addition of one or more physical protectants, engineering methods, encapsulating agents, water-soluble additives, stabilizer additives, and / or dispersants.

[0084] In some embodiments, microorganism protection can comprise encapsulation with a stabilizer protectant. In some embodiments, a stabilizer comprises one or more of clay, diatomaceous earth, starch, agar, alginate, chitosan, PEG, PVA, polyacrylic acid, ethanol, humic acid, humates, talc, clay, peat, lignite, vermiculite, perlite and / or chemically modified versions of the same.

[0085] In some embodiments, chemical modification of a stabilizer can comprise, but is not limited to, one or more of esterification, alkylation, acetylation, phosphorylation, hydrophobic modification, sulfation, sulfomethylation, methylation, amidation, amination, protonation, halogenation, nitration, copolymerization, and / or physical or covalent crosslinking.

[0086] In some embodiments, protection of a microorganism can also comprise addition of a water-soluble additive protectant. In some embodiments, a water soluble additive can be, but is not limited to, glycerol, carboxy methyl cellulose (CMC), polyvinyl pyrrolidone (PVP), gum Arabic, guar gum, and / or mono and / or disaccharide based CMC / Arabic gum / guar gum.

[0087] In some embodiments, microorganism protection can comprise improved stickiness, stabilization, surfactant, and dispersal abilities. In some embodiments, such characteristics can be provided by protectants / inducers and nutrients (e.g. alginates / glycerol / polyvinyl alcohol, PEG / PVP, clay / humate, mono and disaccharides, CMC / arabic gum / guar gum).

[0088] In some embodiments, protection can comprise inclusion of certain stabilizers and / or additives at set proportions, including but not limited to 1:0.05, 1:0.10, 1:0.15, 1:0.20, 1:0.25, 1:0.30, 1:0.35, 1:0.40, 1:0.45, 1:0.50, 1:0.55, 1:0.60, 1:0.65, 1:0.70, 1:0.75, 1:0.80, 1:0.85, 1:0.90, 1:0.95, 1:1, 1:1.05, 1:1.10, 1:1.15, 1:1.20, 1:1.25, 1:1.30, 1:1.35, 1:1.40, 1:1.45, 1:1.5, 1:1.55, 1:1.60, 1:1.65, 1:1.70, 1:1.75, 1:1.80, 1:1.85, 1:1.90, 1:1.95, 1:2, 1:3, 1:4, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:1,000, 1:10,000, 1:100,000, 1:1,000,000, or any range derivable therein.

[0089] In some embodiments, physical protection and / or engineering methods facilitate pelleting and / or layering of microorganisms as a liquid solution at the core or around a core of a fertilizer granule. In some embodiments, a bolus of concentrated microbes in a liquid carrier are protected with a soluble additive, such as in a slurry.

[0090] In some embodiments, physical protection of microorganisms may comprise addition of protectants that are molecules and / or enzymes derived from thermophiles (e.g., heat tolerant bacteria), these molecules and / or enzymes may contribute to the thermo-protection phenotypes observed in thermophiles (see e.g., Pedro Lamosa et al., Thermo stabilization of Proteins by Diglycerol Phosphate, a New Compatible Solute from Hyperthermophile Archaeoglobus fulgidus. Applied and Environmental Microbiology, Vol. 66, No. 5, 01 May 2000). Molecules and / or enzymes derived from thermophiles include proteins, lipids, saccharides, nucleic acids, small molecules, and / or inorganic compounds. Thermophiles may include bacteria, archaea, protists, and / or fungi. Thermophile microorganisms may includemicroorganisms that can thrive, divide, and / or survive at temperatures of 50 °C or greater. A non-limiting example of a thermophile is Archaeoglobus fulgidus.

[0091] In some embodiments, engineering methods for the protection of microorganisms may comprise spray drying and / or freeze-drying of the microorganisms. Freeze-drying can be performed by freezing the microorganisms or a composition containing the microorganisms, exposing the frozen microorganism or composition containing the microorganism to pressures below atmospheric pressures, and removing ice from or surrounding the frozen microorganism or composition. The composition containing the microorganism can contain, in some instances, a cryoprotectant, encapsulating agent, water-soluble additive, stabilizer additive, and / or a dispersant.

[0092] In some embodiments, a microorganism is contacted with a protectant using a spray, liquid stream, semi-solid, or solid (such as a powder) comprising said protectant. In some embodiments, a protectant is contacted with a microorganism using a spray, liquid stream, semi-solid, or solid (such as a powder) comprising said microorganism.

[0093] In some embodiments, a protected microorganism is concentrated (e.g., settlement, centrifugation, affinity capture, selective growth media, etc.) prior to contact with a protectant and / or prior to protecting. In some embodiments, a protected microorganism is contacted with the protectant or with the fertilizer at a concentration of higher than 1012cells per gram of the protectant. In some embodiments, a protectant is comprised in a liquid, suspension, and / or dried powder.

[0094] In some embodiments, a protected microorganism can contain low amounts of moisture. In some embodiments, a free-moisture content of a protected microorganism can be less than 0.6 wt.%, less than 0.5 wt.% water or 0.25 wt.% to less than 0.6 wt.% water. In some instances, the free moisture content is 0.5, 0.4, 0.3, 0.2, 0.1, or 0 wt.%.III. Method of Making a Fertilizer

[0095] A method of producing the fertilizer composition comprising calcium nitrate (Ca(NOs)2), urea phosphate (NH2CONH4HPO4), potassium phosphate (K3PO4), and a plurality of live microorganisms is disclosed. In some aspects, the method comprises one or more of the following steps:(a) contacting calcium phosphate with nitric acid to generate a first reaction product comprising calcium nitrate and phosphoric acid; and(b) contacting the first reaction product and / or phosphoric acid with urea to generate a second reaction product comprising urea phosphate;(c) contacting the first reaction product, the second reaction product, and / or phosphoric acid with potassium chloride to generate a third reaction product comprising potassium phosphate and hydrochloric acid; and(d) contacting the third reaction product, the second reaction product, and / or the first reaction product with a plurality of live microorganisms.

[0096] In step a, the first reaction product comprises calcium nitrate (Ca / NCh ) and phosphoric acid (H3PO4), these can be formed by contacting phosphate rock that comprises at least a portion of the calcium phosphate with nitric acid (equation (1)). Non-limiting example reactions can include the following:Ca3(PO4)2+ 6HNO3 3Ca(NO3)2+ 2H3PO4( 1 )

[0097] In some aspects, the reaction of nitric acid with calcium phosphate (e.g., phosphate rock) can include 10 wt. % to 40 wt. % or at least any one of, equal to any one of, or between any two of 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 35 wt. %, and 40 wt. %, of water / moisture. In some aspects, the nitric acid and calcium phosphate can be contacted at 40 °C to 90 °C, or at least any one of, equal to any one of, or between any two of 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, and 90 °C. In certain aspects, the mixture can be dried at 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C or greater, or any temperature or range thereof or there between to form a dried mixture, such as between 35 °C and 50 °C. The amount of water, e.g., moisture, in the dried mixture can be less than 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.%, or less, or any amount or range thereof or there between.

[0098] In step b, the urea (NH2CONH2) can contact the formed first reaction product to form a second reaction product (equation (2)) comprising urea phosphate (NH2CONH4HPO4). In some instances, the second reaction product further comprises calcium nitrate (Ca(NO3)2) generated in step (a). Non-limiting example reactions can include the following:H3PO4+ NH2CONH2 NH2CONH4HPO4(2)

[0099] In certain aspects, the second reaction product forms particles, granules, or a gel, or any combination thereof.

[0100] In step c, contacting the first reaction product, the second reaction product, and / or phosphoric acid with potassium chloride generates a third reaction product comprising potassium phosphate and hydrochloric acid (equation (3)). Non-limiting example reactions can include the following:3KC1 + H3PO4K3PO4+ 3HC1 (3)

[0101] In, step d, contacting the third reaction product, the second reaction product, and / or the first reaction product with a plurality of live microorganisms forms a microbe-enhanced fertilizer composition. In some instances, the reaction forms a fertilizer paste. The fertilizer paste can then be pelletized, such as a pellet with a size of 2 x 3 mm. The pellets may be dried at 65 °C to 95 °C, or at least any one of, equal to any one of, or between any two of 65, 70, 75, 80, 85, 90, and 95 °C for a period of time, such as 24 hours to form a solid microbe- enhanced fertilizer composition.

[0102] The microbe- enhanced fertilizer composition formed in this method may comprise at least a partial coating of live microorganisms on the third reaction product or on the second reaction product and / or on first reaction product.

[0103] In some aspects, the phosphoric acid produced in the production of calcium nitrate is at least partially used to produce the urea phosphate and / or the potassium phosphate. In some aspects, the reactions are performed in one or more than one container. In some aspects, the reactions are performed simultaneously or sequentially or a mixture of both. In some instances, the first reaction product, the second reaction product, and the third reaction product are formed in three different containers. In some instances, the first reaction product, the second reaction product, and the third reaction product are formed in the same container. In some instances, the first reaction product is formed in a first container and the second reaction product and the third reaction product are formed in a second container.

[0104] In some aspects, calcium nitrate and / or binder forms a continuous phase in the matrix of the fertilizer. In some aspects, the fertilizer does not comprise a binding agent separate from the calcium nitrate, urea phosphate, and / or potassium phosphate. The fertilizer can be a granular fertilizer.

[0105] In some aspects, at least a portion of the live microorganisms, urea phosphate, and / or potassium phosphate in the fertilizer is encapsulated by the calcium nitrate. In some aspects, at least a portion of the calcium nitrate, urea phosphate, and / or potassium phosphate in the fertilizer is encapsulated by the plurality of live microorganisms. In some aspects, at least a portion of the calcium nitrate, urea phosphate, and / or potassium phosphate in the fertilizer is encapsulated by a binder. In some aspects, the mixture and / or fertilizer is a homogenous mixture and / or fertilizer. In some aspects, the fertilizer is a multiphase complex. In some aspects, the fertilizer comprises amorphous phases made of components of the fertilizer. In some instances, the fertilizer comprises a coating containing at least a portion of the live microorganisms.

[0106] In certain aspects, the fertilizer does not contain a polymer. In certain aspects, the fertilizer further comprises a polymer.

[0107] FIG. 2 shows a flow chart of a method 200 for making a fertilizer granule according to one example of the present invention. Referring to FIG. 2, a nitric acid 201 can be contacted with a calcium phosphate (phosphate rock) 202 to form a first reaction product comprising calcium nitrate (Ca(NOs)2) and phosphoric acid (H3PO4) 203, the first reaction product 203 can be contacted with urea (NH2CONH2) solution 204 to form a second reaction product comprising urea phosphate (NH2CONH4HPO4), calcium nitrate (Ca(NOs)2), and phosphoric acid (H3PO4) 205. The second reaction product 205 can be contacted with potassium phosphate 206 to form a third reaction product mixture comprising calcium nitrate, urea phosphate, and potassium phosphate 207, the mixture 207 can be combined, such as coated, with a plurality of live microorganisms 208 to form a final microbe- enhanced fertilizer composition 209.

[0108] In some embodiments, microbe-enhanced fertilizers of the present disclosure comprise any granulatable fertilizer (e.g., granular fertilizer). In some embodiments, a microbe- enhanced fertilizer comprises or excludes one or more granular fertilizers, preferably but not limited to, one or more of urea, single super phosphate (SSP), triple super phosphate (TSP), ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), muriate of potash (MOP), sulfate of potash (SOP), potassium sulfate, binary NP fertilizers, binary NK fertilizers, binary PK fertilizers, and / or a nitrogen phosphorus potassium (NPK) mix.

[0109] In some embodiments, fertilizer granulation comprises chemically reacting reactants to form the fertilizer. In some embodiments, the fertilizer is formed from or is provided in a solution. In some embodiments, the fertilizer is formed or is provided in a fertilizer melt. The fertilizer melt can be formed, in some instances by evaporating a fertilizer solution. In some instances, the fertilizer is formed from or is provided in a solidified fertilizer. The solidified fertilizer can be formed, in some instances by cooling a fertilizer melt. In some instances, the fertilizer is formed from or is provided in a granulated fertilizer. The granulated fertilizer can be formed, in some instances by granulating the solidified fertilizer melt or a cooling fertilizer melt.

[0110] As described herein, in some embodiments, a microbe-enhanced fertilizer is produced when a microorganism is contacted with the fertilizer before or during granulation.

[0111] In some embodiments, water or an aqueous solution, such as steam and / or a scrubber solution, can be combined with a fertilizer composition in granulator to facilitate granulation of a fertilizer composition.

[0112] In some embodiments, a microorganism or a protected microorganism is contacted with a fertilizer by spraying onto a fertilizer particle and / or granule, by mixing into a fertilizer, by spraying a fertilizer onto the microorganism, by coating a fertilizer, by being coated by a fertilizer, by being encapsulated in a fertilizer matrix, by encapsulating a fertilizer to form a matrix of the microorganism, etc.

[0113] In some embodiments, a microorganism or a protected microorganism is contacted with a fertilizer using a spray, liquid stream, semi-solid, or solid (such as a powder) comprising said microorganism. In some embodiments, a microorganism is contacted with a fertilizer using a dosage pump or a spray head.

[0114] In some embodiments, a microorganism or a protected microorganism is concentrated (e.g., settlement, centrifugation, affinity capture, selective growth media, etc.) prior to contact with a fertilizer to form a microbe-enhanced fertilizer. In some embodiments, the microorganism is contacted with the fertilizer at a concentration of 104-1014cells per gram of the fertilizer. In some preferred embodiments, a microorganism or a protected microorganism is contacted with the fertilizer at a concentration of 108-109cells per gram of the fertilizer. In some embodiments, a microorganism is comprised in a liquid, suspension, and / or dried powder.

[0115] In some embodiments, a microbe-enhanced fertilizer particle can have a crush strength of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 kgf / particle, or more, or any amount there between, preferably 2 kgf / particle to 5 kgf / particle.

[0116] In some embodiments, a microbe-enhanced fertilizer can contain a coating on the surface of one or more particles. In some instances, the coating can include nutrients for a plant, inhibitors of urea hydrolysis and / or nitrification, agents to slow or increase the rate of degradation of the granule and / or fertilizers, agents to repel moisture and / or provide a hydrophobic layer, agents that decrease or increase the reactivity of the granule and / or fertilizers, agents that provide additional benefits to plants, agents that increase the stability and / or crush strength of the granule and / or fertilizers, pH buffering agents, drying agents, etc. or any combination thereof. The coating can be a commercially available coating, an oil, a fertilizer, a micronutrient, talc, a seaweed and / or seaweed extract, a wax, etc. In some instances, the coating can contain surfactants. In some instances, the coating contains a wax, surfactants, and / or an amine-based compound.IV. Methods of Using the Fertilizer

[0117] In some embodiments, a microbe-enhanced fertilizer compositions of the present disclosure can be used in methods of increasing the amount of one or more nutrients and one or more microorganisms in soil, and of enhancing plant growth. In some embodiments, methods can include applying to the soil an effective amount of a composition microbe- enhanced fertilizers of the present disclosure. In some embodiments, methods 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. In some embodiments, methods can include applying microbe-enhanced fertilizer of the present disclosure to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc. (e.g., a target substrate).

[0118] In some embodiments, a microbe-enhanced fertilizer can be stored. In some embodiments, the microbe-enhanced fertilizer can be stored for any amount of time, such as 1 minute, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, 1 day, 2 days, 5 days, 1 week, 2 weeks, 3 weeks, 4 weeks, 1 month, 2 months, 3 months, 4 months, 5 months, 6 months, 1 year, 2 years, 3 years, 4 years, 5 years or more, or any amount of time or range thereof or there between without 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, or 100 % of the microorganisms in the micro-enhanced fertilizer dying. In some embodiments, the microorganisms and / or fertilizer components of the microbe- enhanced fertilizer composition have an extended shelf life relative to microbe-enhanced fertilizers created through traditional methods.

[0119] In some embodiments, once a microbe-enhanced fertilizer is applied to a target substrate, microorganism protection materials degrade under field conditions and release the protected microorganisms to deliver their bio-effects.

[0120] Non-limiting examples of plants that can benefit from the microbe-enhanced fertilizer of the present invention include vines, trees, shrubs, stalked plants, fems, 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.

[0121] In some embodiments, the effectiveness of compositions comprising microbe- enhanced fertilizers of the present invention can be ascertained by measuring the amount of particular nutrients in the soil at various times after applying the microbe-enhanced fertilizer composition to the soil. In some embodiments, the effectiveness of compositions comprising microbe-enhanced fertilizers of the present invention can be ascertained by measuring the amount of the microorganism in the soil at various times after applying the microbe-enhanced fertilizer composition to the soil. It is understood that different soils have different characteristics, which can affect the stability nutrients and microorganisms in the soil. In some embodiments, effectiveness of a microbe-enhanced fertilizer composition can be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.

[0122] In some embodiments, microbe-enhanced fertilizers according to the present disclosure can have a density that is greater than water. This can allow the granules and / or fertilizers 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 nonlimiting example of such a crop is rice, as the ground in a rice paddy is typically submerged in water. Thus, application of microbe-enhanced fertilizers to such crops can be performed such that the granules and / or fertilizer are homogenously distributed on the ground that is submerged under water.EXAMPLES

[0123] 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 Preparation of a fertilizer

[0124] 48 g HNO3 (70%) was added to a beaker with a volume of 1000 ml. Gradually 20 g of calcium phosphate was added to the beaker. The mixture was stirred at 190 rpm at a room temperature. The mixture was stirred for 2 hours and then 10 grams of urea was added. The mixture continued stirring for an hour and then 4g KC1 was added to the mixture that produced a gel containing potassium phosphate. Hydrochloric acid gas was allowed to leave the reaction system. Microorganisms were added to the gel at a concentration of 0.01 wt. % relative to the total weight of the fertilizer.

[0125] The final product contained the following amount of nutrients in wt. % based on the weight of the final product: N- 20.7%, P -10% (or 22.91% in an amount equivalent to wt.% P2O5), Ca- 11.9%, K- 7%, and microorganisms -0.09%.* * *

[0126] 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.

Claims

WHAT IS CLAIMED IS:

1. A fertilizer composition comprising calcium nitrate (Ca(NOs)2), urea phosphate (NH2CONH4HPO4), potassium phosphate (K3PO4), and a plurality of live microorganisms, wherein the fertilizer composition comprises 18 to 22 wt.% nitrogen (N), phosphorous (P) in an amount equivalent to 8 to 12 wt.% P2O5, 10 to 13 wt.% calcium (Ca), 5 to 8 wt.% of potassium (K), and / or 0.05 to 0.5 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition.

2. The fertilizer composition of claim 1, wherein the microorganisms comprise diazotrophic microorganisms, potassium-solubilizing bacteria, Bacillus species, endophytes, methylotrophs, comammox microorganism, and / or phosphorus-solubilizing microorganisms.

3. The fertilizer composition of any one of claims 1 and 2, wherein the calcium nitrate forms a continuous phase.

4. The fertilizer composition of any one of claims 1 to 3, wherein: at least a portion of the microorganisms are comprised in a coating of the fertilizer composition; and / or the calcium nitrate (Ca / NCh ), urea phosphate (NH2CONH4HPO4), and / or potassium phosphate (K3PO4) at least partially surround the microorganism.

5. The fertilizer composition of any one of claims 1 to 4, wherein at least a portion of the urea phosphate, potassium phosphate, and / or a plurality of live microorganisms are at least partially surrounded by calcium nitrate.

6. The fertilizer composition of any one of claims 1 to 5, wherein the fertilizer composition further comprises phosphoric acid (H3PO4), urea (NH2CONH2), calcium phosphate (Ca3(PO4)2), nitric acid (HNO3), potassium chloride (KC1), and / or hydrochloric acid (HC1).

7. The fertilizer composition of claim 6, wherein: at least a portion of the calcium phosphate is comprised in phosphate rock; the phosphoric acid is derived from a natural source; and / orat least a portion of the nitric acid is derived from a renewable energy source and / or from a process that uses a renewable energy source, preferably a solar, wind, hydro, tidal, geothermal, and / or biomass renewable energy source.

8. The fertilizer composition of any one of claims 1 to 7, wherein the fertilizer composition does not comprise a binding agent separate from the calcium nitrate.

9. The fertilizer composition of any one of claims 1 to 8, wherein at least a portion of the urea phosphate and potassium phosphate are encapsulated by the calcium nitrate.

10. The fertilizer composition of any one of claims 1 to 9, wherein the fertilizer is homogenous and / or comprises amorphous phases of fertilizer components.

11. The fertilizer composition of any one of claims 1 to 10, wherein the fertilizer composition is a solid fertilizer.

12. A method of producing the fertilizer composition of any one of claims 1 to 11, the method comprising the steps of:(a) contacting calcium phosphate with nitric acid to generate a first reaction product comprising calcium nitrate and phosphoric acid; and(b) contacting the first reaction product and / or phosphoric acid with urea to generate a second reaction product comprising urea phosphate;(c) contacting the first reaction product, the second reaction product, and / or phosphoric acid with potassium chloride to generate a third reaction product comprising potassium phosphate and hydrochloric acid; and(d) contacting the third reaction product, the second reaction product, and / or the first reaction product with a plurality of live microorganisms to produce the fertilizer composition, wherein the fertilizer composition comprises 18 to 22 wt.% nitrogen (N), phosphorous (P) in an amount equivalent to 8 to 12 wt.% P2O5, 10 to 13 wt.% calcium (Ca), 5 to 8 wt.% of potassium (K), and / or 0.05 to 0.5 wt. % of the plurality of live microorganism based on the total weight of the fertilizer composition.

13. The method of claim 12, wherein step (b) comprises contacting the first reaction product with the urea and step (c) comprises contacting the first reaction product and / or second reaction product with the potassium chloride.

14. The method of any one of claims 12 to 13, wherein step (c) comprises contacting the plurality of live microorganisms with a combination of the third reaction product, the second reaction product, and the first reaction product to at least partially coat the combination with the plurality of live microorganisms.

15. A method of fertilizing, the method comprising applying the fertilizer composition of any one of claims 1 to 11 to a soil, a crop, water, or any combination thereof.

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