WO2025030119A1

WO2025030119A1 - Fertilizer biodegradable coating

Info

Publication number: WO2025030119A1
Application number: PCT/US2024/040761
Authority: WO
Inventors: Edward Rosenthal; Ryan Toomey; Brian Patterson; Michael D. ROBESON; Andrew Luis MERCADO; Brandon Ellis WHITE
Original assignee: Profile Products LLC
Current assignee: Profile Products LLC
Priority date: 2023-08-02
Filing date: 2024-08-02
Publication date: 2025-02-06
Anticipated expiration: 2026-02-02

Abstract

A solid particulate fertilizer includes an internal nutrient core and an external biodegradable coating, enclosing the nutrient core, the coating including a fatty acid-modified cellulose, the coating forming about 0.5-20 wt.%, based on the total weight of the solid particulate fertilizer or the nutrient core, the coating being semi-permeable, structured to gradually release one or more nutrients from the nutrient core in a predetermined manner.

Description

FERTILIZER BIODEGRADABLE COATING CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. provisional application Serial No.63/517,263, filed August 2, 2023; U.S. provisional application Serial No.63/573,169, filed April 2, 2024; and U.S. Provisional application Serial No.63/646,307, filed May 13, 2024, the disclosures of which are hereby incorporated in their entirety by reference herein. TECHNICAL FIELD The present disclosure relates to a biodegradable coating for non-liquid fertilizers and methods of making and using the same. BACKGROUND With the global population on the rise, food production demands are growing worldwide. To achieve food security, agricultural producers strive to increase yields, and fertilizers have been assisting to accomplish this goal for centuries. At the same time, use of traditional liquid fertilizers presents numerous environmental challenges, subsiding their use. The liquid fertilizer replacements have had success, but the ever- increasing demand for alternative, clean, non-fossil-fuel based products in the agricultural industry is growing. SUMMARY In at least one embodiment, a solid particulate fertilizer includes a nutrient core, a biodegradable coating including fatty acids modified cellulose, the coating forming about 4-20 wt.%, based on the total weight of the solid particulate fertilizer or of the core. In another embodiment, a solid particulate fertilizer is disclosed. The fertilizer may include a nutrient core and a biodegradable coating. The biodegradable coating may enclose the nutrient core. The biodegradable coating may include a fatty acid-modified cellulose. The coating may form about 0.5-20 wt.%, based on the total weight of the solid particulate fertilizer or the nutrient core. The coating may be semi-permeable. The coating may be structured to gradually release one or more nutrients from the nutrient core in a predetermined manner. The biodegradable coating may be a multi-layer coating. The solid particulate fertilizer may further include a wax-based internal coating located between the nutrient core and the biodegradable coating. The biodegradable coating may be at least partially crosslinked. The solid particulate fertilizer may be a control release fertilizer. The fatty acid-modified cellulose may be a palmitoyl chloride-esterified cellulose. The fatty acid-modified cellulose may be a 16C modified cellulose. In another embodiment, a solid particulate fertilizer is disclosed. The fertilizer may include an internal nutrient core and an external biodegradable coating surrounding the internal nutrient core. The coating may include a fatty acid-modified cellulose and polymerized oil, the coating being semi-permeable, structured to gradually release one or more nutrients from the internal nutrient core through the coating. The polymerized oil may be a linseed oil. The degree of esterification of the fatty acid-modified cellulose may be about 40-70%. The external biodegradable coating may be hydrophobic. The nutrient core may include urea. The external biodegradable coating may have substantially uniform thickness. In yet another embodiment, a solid particulate fertilizer is disclosed. The fertilizer may include an internal nutrient core and at least one external coating surrounding the internal nutrient core. The at least one external coating may include a plurality of layers including a first layer having a wax and a second layer including a fatty acid-modified cellulose. The coating may be semi-permeable, structured to gradually release one or more nutrients from the internal nutrient core through the at least one external coating. The wax may be a beeswax. The second layer may further include a polymerized oil. The at least one external coating may further include a third layer including a wax. The at least one external coating may be a substantially uninterrupted coating covering an entire surface of the internal nutrient core. The fatty acid-modified cellulose may be a palmitoyl chloride- esterified cellulose. The first and second layers may be crosslinked. BRIEF DESCRIPTION OF THE DRAWINGS FIGURE 1 is a scanning electron microscope (SEM) image of a non- limiting example unmodified cellulose-coated urea prill with cracking; FIGURE 2 is a plot of water vapor permeability of modified and unmodified cellulose over a time period; FIGURE 3 is a plot of water vapor permeability of various samples including a control, unmodified cellulose, cellulose modified via a heterogenous reaction, and cellulose modified via heterogenous reaction over a time period; FIGURES 4A and 4B are SEM images of non-limiting example nutrient prills coated with 1 wt.% C8 modified cellulose and 3 wt.% C8 modified cellulose, respectively; FIGURE 5 is a photograph of a non-limiting example modified cellulose coating produced via a heterogenous reaction after 3 weeks; FIGURE 6 is a photograph of a non-limiting example modified cellulose coating produced via a homogenous reaction after 3 weeks; FIGURES 7A and 7B are photographs of non-limiting example C8 and C16, respectively, modified cellulose urea coated prills; FIGURE 8A shows four different non-limiting example prills coated with modified cellulose and having different weights and number of coatings; FIGURE 8B is a SEM image of the surfaces of the prills of Figure 8; FIGURES 9-12 are SEM images of non-limiting example urea prills coated with C16 modified cellulose in different amounts; FIGURE 13 is a SEM cross-sectional image of a non-limiting example urea- coated prill having a wax-based internal coating and modified cellulose coating; FIGURE 14 is a SEM cross-sectional image of a non-limiting example urea- coated prill having a wax-based internal coating, modified cellulose coating, and a wax- based outer coating; FIGURES 15A and 15B are photographs of coated fertilizer particles of Examples 24 and 25. DETAILED DESCRIPTION Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments may take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present embodiments. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures may be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations. Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the disclosure. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, “parts of,” and ratio values are by weight; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the disclosure implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed. The first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation. Unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property. It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components. As used herein, the term “substantially,” “generally,” or “about” means that the amount or value in question may be the specific value designated or some other value in its neighborhood. Generally, the term “about” denoting a certain value is intended to denote a range within +/- 5% of the value. As one example, the phrase “about 100” denotes a range of 100+/- 5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the disclosure can be obtained within a range of +/- 5% of the indicated value. The term “substantially” may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, “substantially” may signify that the value or relative characteristic it modifies is within ± 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic. It should also be appreciated that integer ranges explicitly include all intervening integers. For example, the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4, ..., 97, 98, 99, 100. Similarly, when any range is called for, intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1. to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits. Similarly, whenever listing integers are provided herein, it should also be appreciated that the listing of integers explicitly includes ranges of any two integers within the listing. In the examples set forth herein, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In a refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In another refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 10 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. As used herein, the term “and/or” means that either all or only one of the elements of said group may be present. For example, “A and/or B” means “only A, or only B, or both A and B”. In the case of “only A,” the term also covers the possibility that B is absent, i.e. “only A, but not B”. It is also to be understood that this disclosure is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present disclosure and is not intended to be limiting in any way. The term “comprising” is synonymous with “including,” “having,” “containing,” or “characterized by.” These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps. The term “including” or “includes” may encompass the phrases “comprise,” “consist of,” or “essentially consist of.” The phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps, plus those that do not materially affect the basic and novel characteristic(s) of the claimed subject matter. With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” where one of these three terms is used herein, the presently disclosed subject matter can include the use of either of the other two terms. The term “one or more” means “at least one” and the term “at least one” means “one or more.” The terms “one or more” and “at least one” include “plurality” as a subset. The description of a group or class of materials as suitable for a given purpose in connection with one or more embodiments implies that mixtures of any two or more of the members of the group or class are suitable. Also, the description of a group or class of materials as suitable for a given purpose in connection with one or more embodiments implies that the group or class of materials can “comprise,” “consist of,” and/or “consist essentially of” any member or the entirety of that group or class of materials. First definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation. Unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property. As the world population grows, the demand to produce food is also increasing. Traditional food production such as growing crops in fields; however, is connected with numerous challenges such as effects on climate change, soil erosion, soil organic matter depletion, salinization, biodiversity loss, crop diseases, and many others. Agricultural producers are also tasked with using technologies which are environmentally friendly and sustainable, which poses additional challenges. Historically, traditional liquid fertilizer and uncoated granular fertilizer technologies have caused environmental harm such as water pollution, toxic algal blooms, reduction of oxygen in waterways, release of harmful greenhouse gases into the atmosphere, soil acidification, reduction of organic matter in the soil, altering pH of the soil, etc. A viable alternative has been found in non-liquid and coated alternatives such as slow release and control release fertilizers including a fertilizer core enclosed in a polymeric coating. Yet, polymeric coatings may include substances which may have negative effects on the environment such as petroleum-based persistent compounds which break down into microplastics. Microplastics are small pieces (less than 5 mm across) of plastic of various chemical composition originating from breakdown of persistent plastic materials. Many microplastics are generated by physical forces such as breaking away from larger plastic pieces that have fragmented over time. Others have been intentionally formed such as cosmetic microbeads or glitter. Petroleum-based products and microplastics may accumulate in the water, air, soil, plants, animals, as well as human tissues. While their effect on the environment and living organisms is not fully understood, it is suspected that the effects are mostly negative including damage to cardiovascular and nervous system. Thus, it is desirable to identify alternative materials for coating of the slow and control release fertilizers such that the amount of petroleum-based compounds and their accumulation in water and soils as microplastics is minimized. Additionally, petroleum-based compounds generally have long lifetimes and do not break down easily in natural environments. A concern for long-lasting materials has generated various regulations focusing on the use of biodegradable materials with a reasonable lifespan. The switch to materials which break down in a relatively fast manner in natural conditions may reduce the overall waste in various industries, including agriculture, and in turn minimize the amount of waste to plague landfills for decades to come. As such, there is an increased interest, followed by various legal regulations, requiring safe, non-petroleum-based products which interact with soils, water, and growing crops. Thus, there is a need to develop slow and control release fertilizers with a relatively short lifespan. Yet, many challenges remain as biodegradability of a material may correlate with low mechanical properties and limited material options. The coating of a control release fertilizer also has to fulfill challenging properties such as release of nutrients which is timed properly and works in different environments under different conditions such as humidity, temperature, and soil acidity. Production costs may be another challenging factor. In one or more embodiments disclosed herein, a biodegradable coating for a fertilizer is disclosed. Biodegradability relates to capacity of the material or product for biological degradation by living organisms down to the base innocuous substances. In other words, biodegradability relates to the extent to which a substance can be decomposed by living organisms such as bacteria and fungi. The biodegradable coating disclosed herein may naturally degrade, disintegrate, fall apart, break down, in a reasonable time span in natural environment such as water, carbon dioxide, soil, or both. The coating may be a control release fertilizer (CRF) coating, slow release fertilizer coating, timed release fertilizer coating, particle fertilizer coating, particulate fertilizer coating, non-liquid fertilizer coating, solid particle or particulate fertilizer coating, semi-solid fertilizer coating, or fertilizer coating. The coating may be cellulose-based. Cellulose is a non-petrochemical, non- petroleum-based, plant-based compound. Cellulose is an organic compound with the formula of a polysaccharide consisting of a linear chain of several hundred to many thousands of β linked D-glucose units. It is a complex carbohydrate, a polysaccharide including chains of glucose monomers. Cellulose is a structural component of primary cell walls of green plants and vegetable fibers. Cellulose is a natural polymer or biopolymer and the most abundant biomass resource on Earth. Cellulose has been used to make plastic compounds for almost two centuries. While the aim in the past decades was to develop long-lasting materials to increase longevity of plastic products, cellulose was abandoned in view of other, more persistent products. Cellulose-based materials such as cellulose acetate are more biodegradable than petroleum resins. Unlike petroleum-based plastics, cellulose can be broken down by many types of organisms under various conditions. Cellulose-based biopolymers are thus inherently biodegradable in natural environments including water and soil. For example, cellulose acetate is degraded into cellulose and acetic acid via hydrolysis with water and biodegradation by esterase. The cellulose main chain is subsequently biodegraded by cellulase and eventually converted into water and carbon dioxide. Cellulose-based plastic is thus not a persistent plastic. Additionally, unlike petroleum-based plastics, cellulose does not break down into microplastics, but rather into strands or fibers. Since cellulose is a natural material, virtually present in any environment, the breakdown into fibers is also natural and does not present new entities in the environment. Various microbes continue break-down of the cellulose fibers, thus degrading the material further while, in contrast, petroleum- based microplastics may linger in the environment, not being consumed by any microbial bodies. The coating may include modified cellulose. To modify the cellulose, a process disclosed herein and a composition including one or more of the following components may be used: (A) cellulose base, (B) cellulose modifier, (C) solvent, (D) precipitant, (E) acid scavenger, and (F) dehydration component. The cellulose base material (A) may include a plant-based cellulose. The source of the cellulose may be any plant such as fruit, vegetable, trees such as cell wall of bark, phloem, leaves, roots, seeds, stalks, straw, skin, husk, or stems. Non-limiting source of cellulose may be cotton, flex, hemp, sisal, jute, kenaf, bamboo, wood such as beach, pine, spruce, maple, straw, alfalfa, seaweed, algae, bacteria, or a combination thereof. The cellulose may be organic, naturally occurring, or synthetically derived, man-made. Regardless of its origin, cellulose has the same molecular structure. Given the abundance and biodegradability of cellulose, it is a suitable base material. The cellulose may be plant-based, synthesized, purified, removed from other components present in the cellulose source such as lignin, polysaccharides, pectins, the like, or a combination thereof present in the plant. The cellulose may be modified with one or more cellulose modifiers (B) to adjust one or more properties of the cellulose base material (A). For example, the cellulose base material (A) may be modified to improve ductility, reduce brittleness, or both. Ductility is a mechanical property of material’s amenability to drawing defined by the degree to which a material can sustain elastic (and plastic) deformation under tensile stress before failure. While ductile materials stretch and show deformation under pressure, brittle materials break rather than stretch. Brittleness may cause cracks in the coating which in turn could negatively affect controlled release of nutrients from fertilizer prills coated with cellulose. Fig.1 shows a photograph of a non-limiting example of an unmodified cellulose coating featuring cracks. Additionally, while cellulose is naturally a hydrophilic and hygroscopic material, modified cellulose may be hydrophobic. A hydrophobic property is suitable for a control release coating, assisting with desired longevity of the coating in a humid environment. The -OH groups (hydroxyl groups) of the cellulose may be modified to arrive at different cellulose derivatives. Modified cellulose may include any modified cellulose such as methylcellulose, ethylcellulose, cellulose acetate, hydroxylethyl cellulose, hydroxypropyl cellulose, palmitoate cellulose, or the like. Yet traditional modifications of cellulose typically include undesirable components. For example, ethylcellulose is typically produced by a reaction between cellulose and chloroethane, which is non-bio-derived and toxic. Thus, the cellulose base disclosed herein may be instead modified with one or more bio-derived, non-toxic components such as fatty acids and side groups. The cellulose modifier (B) may thus include one or more fatty acids. Fatty acids are carboxylic acids including a hydrocarbon chain and a terminal carboxyl group. The hydrocarbon, aliphatic chain may be saturated or unsaturated. Fatty acids form part of lipids in plants, animals, and microorganisms. Fatty acids may be naturally derived compounds, for example from natural animal fats or vegetable oils. Fatty acids are thus suitable candidates for cellulose modification and as cellulose modifiers (B). Non-limiting example compounds used for a cellulose modifier (B) may be cottonseed oil with about 25-90% saturated fatty acid, coconut oil with about 82% saturated fatty acid content, palm seed oil with about 45-90% saturated fatty acid content, palmitic acid, 4-toluenesulfonyl chloride, palmitoyl chloride, 10-undecenoyl chloride, cellulose ester such as 10C cellulose ester, the like, or a combination thereof. The cellulose may be an unsaturated fatty acid modified cellulose. Table 1 shows non-limiting examples of long chain saturated and unsaturated fatty acids obtainable from animal fats or vegetable oils. Table 1 – Non-limiting examples of fatty acids for cellulose modification Fatty Acid Name Fatty Acid Chain Fatty Acid Formula

The fatty acids used for the cellulose modification may have a varied number of carbons, determining chain lengths and melt temperature, among other properties. The fatty acids may be thus chosen according to the processing requirements and desirable properties of the coating. For example, a fatty acid with 8 carbons may have a melt temperature of 16.7°C and a fatty acid with 16 carbons may have a melt temperature of 62.9°C. The fatty acid may include unsaturated vinyl groups (double bonds) which may provide the modified cellulose with the ability to crosslink the coating. The fatty acids may be used for esterification of the cellulose. Esterification is a process of combining an organic acid with an alcohol to form an ester and water. During esterification, the carboxylic acid of the fatty acid and the -OH group of the cellulose may react in a presence of an acid catalyst and heat. The esterification may be provided via heterogenous or homogenous reaction. The result of the esterification may be modified cellulose. The degree of esterification may vary and be at 0-100%. The degree of esterification may be about, at least about, up to about, or no more than about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100%. The fatty acid chain length may influence one or more properties of the modified cellulose, for example modified cellulose chain length. It was observed that increasing both the fatty acid chain length and degree of esterification results in reduced water permeability. Thus, the degree of esterification affects water vapor permeability among other properties. Water permeability may be reduced as the degree of esterification is increased. Fig. 2 shows a comparison of modified versus unmodified cellulose and the effect of esterification on water vapor permeability. As can be seen in Fig.2, caprylic acid with about 30% esterification has about four times lower water vapor permeability than unmodified cellulose. The kinetics of the esterification process may be controlled by the presence of a heterogenous or homogenous catalysts. A heterogenous or homogenous reaction procedure may be used for the esterification process. The degree of esterification may be tuned, modified, controlled via the choice of the catalyst. It was observed that homogeneous reactions may yield greater degrees of esterification, up to about 60 or 70%. In contrast, typical degree of esterification with heterogenous reaction may be about 30- 35%. Fig.3 is a plot of water vapor permeability in time for various cellulosic compounds subjected to esterification in comparison to unmodified cellulose and a commercially available CRF as a control. Contrast between modified cellulose produced via homogenous and heterogenous reactions is also shown in Fig.3. The degree of esterification may be also tuned, modified, controlled via reaction temperature. The reaction temperature may be kept at about 15-200, 50-150, or 100-110°C. Higher temperatures may lead to greater degrees of substitution (above 70%). Too high of a degree of substitution may negatively affect properties of the modified cellulose, specifically hydrophobicity, water permeation, mechanical strength, ductility, stretchability, flow characteristics, the like, or a combination thereof. For example, cellulose with degree of esterification of about 30% may lead to an insoluble product while cellulose with degree of esterification of about 70% may lead to a product readily soluble in organic solvents and other compounds such as one or more types of oil. The cellulose base (A), the cellulose modifier (B), or both may be provided in a powder form. The amount of the cellulose base (A) may be about 0.2-8, 1-5, or 2-3 wt.%, based on total weight of the composition. The amount of the cellulose base (A) may be about, at least about, or at most about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.25, 4.5, 4.75, 5, 5.25, 5.5, 5.75, 6, 6.25, 6.5, 6.75, 7, 7.25, 7.5, 7.75, or 8 wt.%, based on total weight of the composition. The amount of the cellulose modifier (B) may be about 2-25, 7-22, or 15- 20 wt.%, based on total weight of the composition. The amount of the cellulose base (B) may be about, at least about, or at most about 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.25, 4.5, 4.75, 5, 5.25, 5.5, 5.75, 6, 6.25, 6.5, 6.75, 7, 7.25, 7.5, 7.75, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt.%, based on total weight of the composition. The composition may further include a solvent (C) to dissolve the cellulose powder, the modifier (B), or both. The solvent may be an organic compound. The solvent may be an organic-based solvent such as N,N-dimethylacetamide (DMAc), or the like. The amount of the solvent (C) may be about 40-90, 50-85, or 60-70 wt.%, based on total weight of the composition. The amount of the solvent (C) may be about, at least about, or at most about 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, or 90 wt.%, based on total weight of the composition. The composition may further include a precipitant (D). The precipitant may be used to precipitate the modified cellulose from a cellulose and solvent solution. The precipitant may be used to transform the dissolved cellulose into a solid. The precipitant may include an alcohol or other chemical precipitant such as ethanol, methanol, water, acetone, the like, or their combination. The precipitant (D) may be optional. The amount of the solvent (D) may be about 0-45, 10-40, or 20-35 wt.%, based on total weight of the composition. The amount of the solvent (D) may be about, at least about, or at most about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 wt.%, based on total weight of the composition. The composition may further include an acid scavenger (E). The acid scavenger may be implemented to remove an acid from the reaction. The acid scavenger may include any acid seeking reagent including anhydrous pyridine, 4-toluenesulfonyl chloride, triethylamine, the like, or their combination. Alternatively, the scavenger may be omitted, and a different mechanism may be implemented to remove an acid from the reaction such as vacuum. The scavenger (E) may be an optional component. The amount of the solvent (E) may be about 0-15, 5-12, or 7-10 wt.%, based on total weight of the composition. The amount of the solvent (E) may be about, at least about, or at most about 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or 15 wt.%, based on total weight of the composition. The composition may further include a dehydration component (F). The dehydration component may be used to remove water from the reaction. The dehydration component may be a desiccant or a material that serves to promote dryness and eliminate humidity. The dehydration component may include an anhydrous component. The dehydration component may include any water seeking component including an anhydrous lithium chloride, activated charcoal, calcium sulfate, calcium chloride, zeolites, the like, or their combination. Component (F) should be inert, non-toxic, water-insoluble, or a combination thereof. The dehydration component (F) may be an optional component. The amount of the dehydration component (F) may be about 0-10, 1-8, or 2-7 wt.%, based on total weight of the composition. The amount of the dehydration component (F) may be about, at least about, or at most about 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 wt.%, based on total weight of the composition. In one or more embodiment, a fertilizer is disclosed. The fertilizer may include the biodegradable cellulose-based coating disclosed herein. The fertilizer may be thus likewise biodegradable. The fertilizer may be a control release fertilizer, slow-release fertilizer, or the like. The fertilizer may include a plurality of particles, prills, granules structured to have a nutrient core and the coating disclosed herein. The fertilizer may be a 60-day, 90-day, 180-day, 270-day, 365-day release fertilizer, or the like. Once the cellulose is modified and precipitated as a modified cellulose, it may be dried and stored for a prolonged periods of time in a solid form. To use the modified cellulose for the formation of a coating on a fertilizer prill, the modified cellulose may be mixed with a dissolving component or a second solvent. The dissolving solution may be different from component (C) named above. The dissolving solution or component may be implemented to dissolve the solid modified cellulose, make the composition flowable such that the modified cellulose may be applied as a coating. The dissolving solution may be an organic compound. The dissolving solution may include a heterocyclic compound. The compound may be a cyclic ether. The dissolving solution may be a traditional solvent such as an oxolane such as tetrahydrofuran (THF), or the like. Alternatively, it was surprisingly discovered that using a non-traditional composition as a dissolving solution may be beneficial. For example, the dissolving solution may include an oil. The oil may be a natural or synthetic oil such as linseed oil, flax seed oil, palm oil, or their combination. The linseed oil may be boiled linseed oil (BLO). When the oil is used to liquify the modified cellulose in its solid form, not only is the resulting biodegradable composition flowable, but the oil polymerizes, forming a polymerized oil. The polymerized oil remains in the modified cellulose coating once applied and dried. The oil may be thus used to replace the need to use a wax internal coating, as is described below. The polymerization may be initiated by one or more mechanisms, for example increased temperature or compounds such as citric acid, oxalic acid, or both. The resulting modified cellulose coating may be a control-release coating. The coating may be hydrophobic or partially hydrophobic. The coating may be predominantly or partially impervious to water permeation. The coating may be semi- permeable, structured to gradually release a substance through the coating. The released substance may include one or more types of nutrients contained in a fertilizer prill. The release may be provided via one or more structures and/or mechanisms. The structures, mechanisms may be incorporated in the coating. The structures/mechanisms may include diffusion through more or less tortuous pathways including pores, passages, reverse osmosis, the like, or a combination thereof. The pores may be formed by inclusion of pore formers, calcium deposits such as clay, gaseous carbon dioxide, the like, or a combination thereof. The modified cellulose coating may be applicable onto a fertilizer prill to form a fertilizer with a biodegradable coating. The fertilizer prill is a compact conglomeration or individual nutrient particles or substrate fertilizer. The particles form a core. The core may be round and compact. The individual nutrient particles may have the same or different chemistry. For example, the nutrient particles may include microparticles of ammonium sulfate, ammonium chloride, ammonium nitrate, urea, potassium chloride, potassium sulfate, potassium nitrate, sodium nitrate, ammonium phosphate, potassium phosphate, calcium phosphate, and composite fertilizers thereof. The modified cellulose coating includes such composition that a fertilizer nutrient prill may be coated with the coating such that the coating forms a substantially uniform, uninterrupted coating. The coating may be undulating, conforming to the shape of the prill. One or more coatings may be applied onto a single prill to enable substantially uninterrupted coverage of the entire surface of the prill. The coating may be substantially free of defects, cracks, bumps, protrusions, indentations, holes, the like, or a combination thereof. The modified cellulose coating composition may be applied onto a fertilizer prill and annealed at an elevated temperature which is above the glass transition temperature but below the melt temperature of the nutrient component. Alternatively, or in addition, the coating composition may be melt processed. The biodegradable coating may include wax or binder coatings before and/or after cellulose coatings, an internal coating, cellulose-based coating, outer coating, or their combination. The internal coating may be formed by application of an internal coating composition. The cellulose-based coating may be formed by application of a cellulose-based coating composition. The outer coating may be formed by application of an outer coating composition. The cellulose-based coating composition may be applied directly onto the nutrient portion or prill. Alternatively, the nutrient prill may be precoated with one or more compounds of an internal coating composition forming the internal coating. The internal coating may be continuous or discontinuous. The internal coating may include one or more waxes or other compounds. The waxes may include a natural wax such as soy wax, palm wax, honeybee wax, carnauba wax, coconut wax, candelilla wax, rapeseed wax, olive wax, bayberry wax, lanolin, jojoba wax, castor wax, sunflower wax, microcrystalline wax, paraffin, petroleum-based wax, synthetic wax, hydrogenated triglycerides, the like, or a combination thereof. The wax pre-coating or internal coating may eliminate coating defects by providing an immediate layer between the nutrient core/prill and the cellulose coating. The internal coating may include one or more layers. The internal coating may also even out or increase regularity of the prill surface. The internal coating may render the overall shape of the prill more round, regular, stable, or the like. The internal coating may render the surface of the prill smooth, having a relatively uniform texture free of deviations. The wax or wax mixture disclosed herein may be applied in various manners. For example, wax may be applied as a pre-wax or wax pre-coating, as described above. Alternatively, the wax may become part of the cellulose-based coating composition such that the wax is mixed with other components forming the coating composition. Alternatively, still or in addition, a wax may be included via an outer coating composition and form post-coating layer(s), added as top layer(s) after the cellulose-based coating composition is applied. In one or more embodiments, a prill may include alternating layers of outer coating composition and cellulose-based coating composition. In another embodiment, the wax may be eliminated altogether. The embodiment with no wax contemplates use of an oil as a dissolving solution for the modified cellulose. Unlike traditional solvents, the oil remains as part of the deposited cellulose-based composition, substituting a need for the addition of wax. The precoating or internal coating may be applied in one or more layers or coatings. For example, the number of individual coatings may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more. The weight, thickness, texture, configuration of each layer may be the same or different. The modified cellulose-based coating may be applied in one or more layers or coatings. For example, the number of individual coatings may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more. The coatings may be discrete or connected by at least some bonds, crosslinked. The individual coatings may be applied on top of one another, forming a multi-layer coating. Since one or more layers may feature one or more defects such as pinholes, cracks, the like, or a combination thereof, the multi-layer coating may secure continuous coverage of the prill with the cellulose-based coating, preventing premature release of the nutrients from the prill. Since coating integrity may vary, the application of multiple coats may thus ensure continuous coverage resulting in the desirable impermeability and/or release. Each coating may have the same or different properties such as composition, weight, degree of water impermeability, rheology, morphology, etc. An increased number of coatings may translate into an increased weight of the coating, based on the total weight of the fertilizer particle. The total coating weight may be about 1-20, 1.5-10, or 2-8.5 wt.%, based on the total weight of the fertilizer particle or the prill. The total coating weight may be about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 10.2, 10.5, 10.7, 11, 11.2, 11.5, 11.7, 12, 12.2, 12.5, 12.7, 13, 13.2, 13.5, 13.7, 14, 14.2, 14.5, 14.7, 15, 15.2, 15.5, 15.7, 16, 16.2, 16.5, 16.7, 17, 17.2, 17.5, 17.7, 18, 18.2, 18.5, 18.7, 19, 19.2, 19.5, 19.7, or 20 wt.%, based on the total weight of the fertilizer particle or the prill. Greater percentages than 20 wt.% such as 25, 30, 40, 50, or 60 wt.% are also contemplated. It was surprisingly observed that coating weight affects morphology of each coating. For example, a greater weight may cause formation of bridging effects which may negatively influence performance of the coating. Figs. 4A and 4B are scanning electron microscope (SEM) images showing morphology of example C8 modified cellulose coatings applied over an urea prill at 1 wt.% (Fig.4A) and 3 wt.% (Fig.4B), respectively, based on the total weight of a CRF particle (prill + coating). The coating weight of a single coating may be about 0.05 – 5, 0.5-3.5, 0.8- 2.8, or 1-3 wt.%, based on the total weight of the fertilizer particle or the prill. The coating weight of a single coating may be about, at least about, or at most about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5.0 wt.%, .%, based on the total weight of the fertilizer particle or the prill. In a non-limiting example, each coating may be about 1 wt.%, based on the total weight of the fertilizer particle or the prill. Crosslinking may occur between individual layers of the multi-layer coating as well as between a wax in the precoating, outer layer, or both, and an adjacent layer of the modified cellulose coating. The outer coating composition may be applied over the modified cellulose- based coatings. The outer coating may include a wax such as one or more waxes named above. The wax in the internal coating, cellulose-based coating, the outer coating, or their combination may be the same or different. The outer coating may include one or more layers such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more layers. The weight, thickness, texture, configuration of each layer may be the same or different. A non-limiting example of a particulate or granular fertilizer may thus include a core and the cellulose-based coating with the absence or addition of the internal wax layer, outer wax layer, or both. Non-limiting examples of the particulate or granular fertilizer is shown in Figs.7A-14. The entire particulate or granular fertilizer, or portions thereof, may be biodegradable as the one or more coatings, the nutrient core, or their combination may be biodegradable. EXAMPLES Example 1 – Esterification of cellulose with caprylic acid via heterogenous reaction. Microcrystalline cellulose (MCC) was reacted with caprylic acid. The formed modified cellulose powder was dissolved in a solvent, tetrahydrofuran (THF) to become flowable and formed into a layer on a Petri dish. No visible aging or loss of flexibility was observed after 3 weeks, as can be seen in Fig.5. Example 2 - Esterification of cellulose with caprylic acid via homogenous reaction MCC and lithium chloride (LiCl) were dried in vacuum for 1 h at 125°C. All commercial chemicals were of reagent grade or better. Octanoyl chloride (C₈H₁₅ClO) was used without further purification. Dimethylacetamide (DMAc) and pyridine were distilled prior to use. The reaction protocol included feeding MCC (2 g) into a three-neck flask. 50 ml DMAc was added and MCC was dispersed by stirring for about 30 min at about 160°C to give a slurry. About 4.5 g LiCl was added to the slurry after the temperature was reduced to about 80°C. The mixture was subsequently stirred at about 80°C until a transparent cellulose solution was obtained. 10 mL of pyridine was added to the solution and then about 6.31 ml C8H15ClO dissolved in about 50 ml DMAc was added dropwise. The reaction ran between about 3-8 h at about 80°C. Subsequently, the product was precipitated by adding methanol and separated by centrifugation. Finally, the product was vacuum dried at about 50°C for about 24 h. Nuclear magnetic resonance (NMR) spectroscopy was used to assess degree of substitution of cellulose with caprylic acid. NMR revealed the substitution at about 76%. The formed modified cellulose was made into a layer on a Petri dish. No visible aging or loss of flexibility was observed after 3 weeks, as can be seen in Fig.6. Example 3 Urea prills were coated with about 1 wt.% cellulose in THF solution. The cellulose was 8C modified cellulose and 16C modified cellulose. Both types of the coating showed no measurable release over the span of 3 weeks. The coated prills are shown in Figs.7A and 7B, respectively. Example 4 Urea prills were coated with 2 wt.% 16C modified cellulose ester in THF solution. Each individual coating was deposited uniformly in a predictable manner with build-up of weight with each subsequent coating application. Each coating left behind small indentations at the surface. The stages of the progressive coating process are shown in SEM images of Figs.8A and 8B, in which (a) corresponds to 1 coat, 2.5 wt.% CE, (b) corresponds to 2 coats, 6 wt.% CE, (c) corresponds to 3 coats, 12 wt.% CE, and (d) corresponds to 4 coats, 18 wt.% CE. Examples 5-8 Different urea prills were coated with a weight of C16 modified cellulose according to the Table 2 below. The solution included 0.1 g 16C + 5 ml THF. Table 2 – Examples 5-8 Example 5 6 7 8

Example 9 A urea prill was first coated with a precoating or internal coating including about 1.5 wt.% paraffin wax, based on the total weight of the fertilizer particle, and subsequently about 1.5 wt.% modified cellulose coating was applied on top of the precoating. The precoating thickness was about 10-50 µm and the cellulose coating about 25 µm. A SEM cross section of the fertilizer particle is shown in Fig.13. In Fig. 13, the fertilizer particle 50 includes the nutrient core/prill 52, the precoating or internal coating 54, and the modified cellulose coating 56. Example 10 A urea prill 52 was coated with wax precoating or internal coating 54, modified cellulose coating 56, and an outer coating 58. The fertilizer particle 50 is shown in Fig.14. Example 11 Example 11, a 16C cellulose ester, was prepared by the following procedure in a batch reactor.40g of base cellulose powder and a dehydration component, specifically lithium chloride, were added to a vacuum oven at about 125⁰C and low pressure for about 30 minutes. The cellulose powder was then added to a reactor. The reactor was a 5L batch reactor with temperature control oil jacket. About 1000 ml of a solvent, specifically DMAC, was added to the reactor. The reactor temperature was set to about 160⁰C. Mixing was initiated and continued for about 30 min once the temperature reached 160⁰C. A fatty acid was then added to modify the cellulose. The temperatures of the reactor was reduced to and kept at about 80⁰C. About 250 ml of a fatty acid, specifically 16 C palmitoyl chloride, was added with a peristaltic pump to the reactor. The addition was done slowly, over a period of about 30-40 minutes; a steady stream of about 1-2 drops/second. As the fatty acid was added, about 100 ml of an acid scavenger, specifically anhydrous pyridine was added periodically. This was accomplished in about 25 ml additions starting when the fatty acid was first added. Subsequent 25 ml additions were made when the fatty acid step was about 25%, 50%, and 75%, respectively, complete. About 1000 ml of a cellulose precipitant, specifically methanol, was added to the reactor. The cellulose ester precipitated out. The solution was collected from the reactor and separated using a vacuum pump and filter paper. Examples 12, 13 Cellulose-based coating compositions were prepared in a reactor of Example 11 based on the following components and their quantities. The resulting modified cellulose was a relatively lightweight solid, which was precipitated, dried, and stored for an extended period of time. Table 3 – Components and their quantities for synthesis of modified cellulose of Example 12 Component Quantity

Methanol 50-100 mL

Table 4 – Components and their quantities for synthesis of modified cellulose of Example 13 Component Quantity

Examples 14-20 Modified cellulose coatings were prepared by the process described in Example 11. The resulting modified cellulose was a relatively lightweight solid, which was precipitated, dried, and stored for a period of time prior to being mixed with a dissolving solution to liquify the cellulose to a flowable coating composition for an application over a prill. The dissolving solutions used in Examples 14-20 varied and are listed in Table 5 for each Example. The amount of the dissolving solution was about 50 ml / 1 g of modified cellulose. The resulting 16C cellulose ester was applied onto a fertilizer prill to form a coated prill. Some of the Examples also included beeswax blended with the modified cellulose. Nutrient release from the coated prill in time was studied. Coating weight was estimated to be about 2-5 wt.%, based on the total weight of the prill. Results are shown in Table 5. Table 5 – Nutrient release timeline from cellulose-based coatings of Examples 14-20 Example No. Dissolving solution Wax present in the blend Release

Examples 21-23 Cellulose-based coating compositions were prepared in a reactor of Example 11 based on the following components and their quantities. The resulting modified cellulose was a relatively lightweight solid, which was precipitated, dried, and stored for an extended period of time. Table 6 – Components and their quantities for synthesis of modified cellulose of Example 21 Component Quantity [wt.%]

Table 7 – Components and their quantities for synthesis of modified cellulose of Example 22 Component Quantity [wt.%]

Table 8 – Components and their quantities for synthesis of modified cellulose of Example 22 Component Quantity [wt.%]

Examples 24 and 25 Examples 24 and 25 were prepared by coating nutrient cores according to the methods described above and using the following materials: Example 24 included 1 wt.% beeswax pre-coat (single layer), 2.5 wt.% palmitoyl cellulose (3 layers, equal parts each), and 1 wt.% beeswax post coat or cap wax coating (single layer). Total coating weight was 4.5 wt.%, based on the total weight of the coated particle. Coated particles of Example 24 are shown in Fig. 15A after coating and cooling. Example 25 did not include any pre-coat. Example 25 included 2.5 wt.% palmitoyl cellulose (3 layers, equal parts each), and 1 wt.% beeswax post coat or cap wax coating (single layer). Total coating weight was 3.5 wt.%, based on the total weight of the coated particle. Coated particles of Example 25 are shown in Fig. 15B after coating and cooling. In both examples, the palmitoyl cellulose was mixed with the solvent as a premix for prill application. The solvent used was 505 methyl THF and 50% butyl acetate. The coating process resulted in fertilizer particles being fully, evenly coated. Both examples were subjected to a soak test in water with an uncoated urea as a control. While the uncoated urea dissolved in water in about 3 minutes, Example 24 and 25 dissolved in about an hour. While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the disclosure that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, to the extent any embodiments are described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics, these embodiments are not outside the scope of the disclosure and can be desirable for particular applications.

Claims

WHAT IS CLAIMED IS: 1. A solid particulate fertilizer comprising: a nutrient core; and a biodegradable coating, enclosing the nutrient core, the coating including a fatty acid-modified cellulose, the coating forming about 0.5-20 wt.%, based on the total weight of the solid particulate fertilizer or the nutrient core, the coating being semi-permeable, structured to gradually release one or more nutrients from the nutrient core in a predetermined manner.

2. The solid particulate fertilizer of claim 1, wherein the biodegradable coating is a multi-layer coating.

3. The solid particulate fertilizer of claim 1 further comprising a wax-based internal coating located between the nutrient core and the biodegradable coating.

4. The solid particulate fertilizer of claim 1, wherein the biodegradable coating is at least partially crosslinked.

5. The solid particulate fertilizer of claim 1, wherein the solid particulate fertilizer is a control release fertilizer.

6. The solid particulate fertilizer of claim 1, wherein the fatty acid-modified cellulose is a palmitoyl chloride-esterified cellulose.

7. The solid particulate fertilizer of claim 1, wherein the fatty acid-modified cellulose is a 16C modified cellulose.

8. A solid particulate fertilizer comprising: an internal nutrient core; and an external biodegradable coating surrounding the internal nutrient core, the coating including a fatty acid-modified cellulose and polymerized oil, the coating being semi- permeable, structured to gradually release one or more nutrients from the internal nutrient core through the coating.

9. The solid particulate fertilizer of claim 8, wherein the polymerized oil is a linseed oil.

10. The solid particulate fertilizer of claim 8, wherein the degree of esterification of the fatty acid-modified cellulose is about 40-70%.

11. The solid particulate fertilizer of claim 8, wherein the external biodegradable coating is hydrophobic.

12. The solid particulate fertilizer of claim 8, the nutrient core includes urea.

13. The solid particulate fertilizer of claim 8, wherein the external biodegradable coating has substantially uniform thickness.

14. A solid particulate fertilizer comprising: an internal nutrient core; and at least one external coating surrounding the internal nutrient core, the at least one external coating including a plurality of layers including a first layer having a wax, and a second layer including a fatty acid-modified cellulose, the coating being semi-permeable, structured to gradually release one or more nutrients from the internal nutrient core through the at least one external coating.

15. The solid particulate fertilizer of claim 14, wherein the wax is a beeswax.

16. The solid particulate fertilizer of claim 14, wherein the second layer further includes a polymerized oil.

17. The solid particulate fertilizer of claim 14, wherein the at least one external coating further comprises a third layer including a wax.

18. The solid particulate fertilizer of claim 14, wherein the at least one external coating is a substantially uninterrupted coating covering an entire surface of the internal nutrient core.

19. The solid particulate fertilizer of claim 14, wherein the fatty acid-modified cellulose is a palmitoyl chloride-esterified cellulose.

20. The solid particulate fertilizer of claim 14, wherein the first and second layers are crosslinked.