US20140235438A1 - Multi-purpose lignin-carbohydrate binding system - Google Patents

Multi-purpose lignin-carbohydrate binding system Download PDF

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Publication number
US20140235438A1
US20140235438A1 US14/110,350 US201214110350A US2014235438A1 US 20140235438 A1 US20140235438 A1 US 20140235438A1 US 201214110350 A US201214110350 A US 201214110350A US 2014235438 A1 US2014235438 A1 US 2014235438A1
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polyols
lignosulfonate
granule
mixture
lignin
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Harold E. Thompson
Toula Xenikis
Domini Upton
Keith Cochran
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OMS Investments Inc
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OMS Investments Inc
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Assigned to OMS INVESTMENTS, INC. reassignment OMS INVESTMENTS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UPTON, DOMINI, THOMPSON, HAROLD E., XENIKIS, Toula, COCHRAN, Keith
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    • C05G3/0058
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00Fertilisers characterised by their form
    • C05G5/10Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12Granules or flakes
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00Calcareous fertilisers
    • C05D3/02Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05FORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F11/00Other organic fertilisers
    • C05F11/02Other organic fertilisers from peat, brown coal, and similar vegetable deposits
    • C05G3/02
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00Fertilisers characterised by their form
    • C05G5/30Layered or coated, e.g. dust-preventing coatings
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00Fertilisers characterised by their form
    • C05G5/45Form not covered by groups C05G5/10 - C05G5/18, C05G5/20 - C05G5/27, C05G5/30 - C05G5/38 or C05G5/40, e.g. soluble or permeable packaging

Definitions

  • Binders are used to adhere fertilizers and other components together into a single particle.
  • Conventional binders do not contribute either economical or practical value to the fertilizer formulations. Thus, it is a cost ineffective component.
  • the use of a binder in a fertilizer composition also results in a granular fertilizer that is insufficiently hard and/or round. These granular fertilizers make encapsulation with polymers or resins difficult, resulting in inconsistent slow release fertilizers.
  • binders only contribute to the agglomeration of dispersed fertilizer fines and particles. Additionally, these binders constitute a significant portion of the fertilizer composition, resulting in a fertilizer with reduced nutrient value. Due to these shortcomings, fertilizers using conventional binders result in products with low commercial viability.
  • the objective of this invention is to provide a new binding formulation and a processing methodology for manufacture of fertilizer particles that overcome these limitations.
  • the present invention relates to a novel, dual purpose binder formulation or system. More particularly, the invention provides a binding formulation that agglomerates or binds dispersed particles or fines into a granular composition having desired properties such as increased granule hardness or crush resistance, increased roundness or sphericity, and increased durability and uniformity.
  • the binding formulation also serves as an in situ chelating agent for micronutrients and also allows for single-stage granulation processing.
  • dispersed particles or fines is comprised of an active agent, such as a fertilizer, are agglomerated or bound together with a binder formulation comprising a lignin-based binder and a carbohydrate based binder.
  • a binder formulation comprising a lignin-based binder and a carbohydrate based binder.
  • This combination of binders results in granules having increased hardness or crush resistance, increased sphericity or roundness, and increased durability. These enhance properties are due, in part, to the synergistic effects of combining binders made of lignin based materials and carbohydrates.
  • the lignin-based material is a lignosulfonate
  • the carbohydrate is a mixture of polyols, such as a blend of monosaccharides and disaccharides.
  • the mixture of polyols may comprise sorbitol, maltiol, hydrogenated starch hydrolysates (“HSH”), or combinations thereof
  • the invention provides a process of agglomerating dispersed particles or fines into substantially spherical and crush resistant granules.
  • the agglomeration process may be achieved by a single-stage process comprising atomizing and spraying a specific ratio of lignin-based materials and carbohydrate binder, such as a polyol mixture, into an agitating bed containing particles or fines.
  • This single-stage process allows intimate mixing of the particles or fines with the novel binder to achieve an improved granule.
  • the process may additionally comprise a recycling step, where undersized granules are reintroduced into the agitating bed until the desired granule size is achieved.
  • the ratio of lignin to carbohydrate, such as a polyol, may vary depending on the solubility of the particles to be agglomerated.
  • the resulting product achieves the desired properties of increased hardness or crush resistance, increased sphericity or roundness, and increased durability. These enhanced properties are due to the synergistic effects of combining the novel binder formulation and the single-stage processing method.
  • the invention provides a method of covering a seed and binding the seed with a material mixture beneficial for seed germination.
  • This method may be used to produce an “all-in-one” seed product that is capable of germination upon appropriate hydration and exposure to sufficient sunlight.
  • the material mixture comprises a soil conditioner that allows sufficient air transport to the seed, a fertilizer, and a general purpose soil enhancer.
  • the seed and material mixture are bound together using the binding formulation of the invention, which comprises a specific ratio of lignin-based material and a carbohydrate binder.
  • the carbohydrate binder is a mixture of polyols. The combination of the lignin and polyol produces an agglomerated particle which is substantially spherical and resistant to crushing.
  • the agglomerated particle is a self-contained granule capable of germinating, when properly hydrated and exposed to sufficient sunlight, without the need for additional fertilizers or micronutrients.
  • the resultant granule may additionally comprise micronutrients, such as but not limited to calcium, magnesium, sulfur, boron, copper, iron, chloride, molybdenum, zinc, or combinations thereof.
  • the seed may be grass, vegetable, or flower seed.
  • the self-contained grass seed or “all-in-one” grass seed is capable of germinating grass, when properly hydrated and exposed to sufficient sunlight, without the need for additional mulching or fertilizers.
  • the active agent included in the granules may be a fertilizer, such as urea. It has been unexpectedly discovered that the novel binder formulation of the instant invention, when used in conjunction with urea produces an anti-caking effect.
  • the invention provides a method of cultivating a seed comprising the distribution of the covered seed with a material mixture beneficial for seed germination.
  • FIG. 1 depicts a schematic of a process flow diagram of the invention.
  • FIG. 2 depicts a graph showing the comparable release rates between the controlled release fertilizer granules manufactured using the dual binder system of the invention versus reference controlled release fertilizer granules.
  • FIG. 3 shows the effects of in situ chelation of micronutrients.
  • FIG. 4 shows the all-in-one seed using the novel binder and rice hull.
  • FIG. 5 shows the all-in-one seed using the novel binder and perlite.
  • FIG. 6 shows a graph depicting preferred particle size distributions for heavy bulk density materials.
  • FIG. 7 shows a graph depicting preferred particle size distributions for heavy bulk density materials.
  • FIG. 8 shows a graph depicting non-preferred particle size distributions for heavy bulk density materials.
  • the present invention provides a composition, a method of making a composition and a method of using a composition comprising an agglomerated particle using a novel dual binder formulation or system.
  • the binder formulation produces granules achieving desired properties such as increased particle hardness, increased crush resistance, increased roundness (i.e., sphericity), and increased durability and uniformity. These granules are produced utilizing a single-stage granulation process. The granules produced by this method may also be water soluble.
  • the binder system of the invention includes a lignin or lignin-derived material and a mixture of polyols, each present at a ratio sufficient to generate granules with the desired properties.
  • the ratio of the lignin to polyols used in the binder system is dictated by the solubility of the particles or fines to be agglomerated. “Solubility” of a particle or fine used in the formulation is directly related to a formula's tendency to form agglomerated particles or granules. The more soluble the particle or fine, the lower the ratio of lignin to polyols. The less soluble the particle or fine, the higher the ratio of lignin to polyols.
  • the binding formulation does not use hazardous chemicals such as formaldehyde and other petroleum-based products.
  • the dual binder formulation or system of the invention uses natural and renewable by-products.
  • the binder formulation does not include hazardous chemicals such as, but not limited to, formaldehyde, petroleum-based chemicals, carbonate, sulfate, silicate strengthener, dextrin, maltodextrin, cyclodextrin, pectin, soy lecithin, agar, corn starch, plantain starch, pre-gelantinized starch, or sodium starch glycolate, nor does it include other polymer-based binders such as, but not limited to, polyethylene (PE), polypropylene (PP), or polyethyl glycol (PEG).
  • PE polyethylene
  • PP polypropylene
  • PEG polyethyl glycol
  • the binder formulation of the invention also does not include pharmaceutical binders such as, but not limited to, hydroxyl methyl cellulose, hydroxypropyl methyl cellulose, ethoxylated stearyl alcohols, latose, polyvinylpyrrolidone, methyl cellulose, polyethylene glycol, microcrystalline cellulose, soybean oil, cottonseed oil, gelatin, or sucrose.
  • pharmaceutical binders such as, but not limited to, hydroxyl methyl cellulose, hydroxypropyl methyl cellulose, ethoxylated stearyl alcohols, latose, polyvinylpyrrolidone, methyl cellulose, polyethylene glycol, microcrystalline cellulose, soybean oil, cottonseed oil, gelatin, or sucrose.
  • Lignins which are by-products of the wood pulping process, are converted into lignosulfonates or sulfonated lignins.
  • the lignosulfonates of the binder formulation contribute to granules hardness, roundness, and uniformity.
  • Polyols are derived from traditional corn syrups, and act as tackifying agents that contribute to the speed and efficiency of the particle or fine granulation process. This reduces the need for multi-stage processes.
  • the novel binder formulation of the invention allows for intimate mixing of dispersed particles or fines, such as fertilizers, micronutrients, soil conditioners, inert carriers, pesticides, plant growth hormones, plant growth regulators, soil moisture enhancers, seeds, and wetting agents.
  • dispersed particles or fines such as fertilizers, micronutrients, soil conditioners, inert carriers, pesticides, plant growth hormones, plant growth regulators, soil moisture enhancers, seeds, and wetting agents.
  • the fertilizer granules produced possess increased nutritional value while simultaneously increasing hardness, roundness, sphericity, and crush resistance.
  • the invention provides a binding formulation comprising less than about 15%, between 3% and 12%, or approximately 5-6% of the total weight of the agglomerated granule.
  • the invention further permits intimate mixing of dispersed particles or fines, such as fertilizer and micronutrients (e.g., iron) into an agglomerated granule.
  • agglomerated granule such as fertilizer and micronutrients (e.g., iron)
  • An added advantage of the invention is the in situ chelation of micronutrients (e.g., iron sulfate and other metal sulfates) when admixed with the novel binder. This advantage allows for single-step granulation without the need for an added chelation step. The chelation of micronutrients, prevents oxidation, thereby optimizing the absorption of the micronutrients by plants.
  • lignins or lignin-derived materials are defined as materials recovered from the wood pulping process.
  • Lignin or lignin-derived materials may include lignosulfonates and salts thereof.
  • the source of lignins is well known in the art and include any conventional cellulosic material such as hardwood and softwoods. Lignosulfonates are recovered from the sulfite preparation of wood pulp.
  • the lignosulfonates may include calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, aluminum lignosulfonate, potassium lignosulfonate, or zinc lignosulfonate.
  • the lignin or lignosulfonate content in the binder system is based on the solubility of the particles or fines. In another embodiment, the lignin or lignosulfonate will represent about 5-6% of the total weight of the binding formulation.
  • the carbohydrate portion of the binding formulation enhances the sphericity and results in fewer process losses.
  • the spherical nature of granules is measured by “sphericity,” which is defined as the degree a given particle shape approximates a perfect sphere. The closer the fractional number is to 1.00, the more spherical the particle shape. This value is measured using an optical particle size characterization instrument such as the Camsizer®, marketed in the US by Horiba Instruments.
  • Formulations that are difficult to granulate tend to adhere to equipment rather than agglomerate with the other particles or fines. This property can reduce overall granule roundness and hardness, while increasing the proportion of undersized granules or fines that require recycling back into the granulator.
  • the addition of carbohydrates such as polyols or ‘sugar alcohols’ to the binder solution mixture significantly resolves these granulation problems.
  • Polyols or “mixture of polyols” include traditional corn syrups that undergo a catalytic hydrogenation process or other related process.
  • the polyols may include a mixture of monosaccharides, disaccharides, long chain polymeric polyols, which are also known as polyglycitol syrups or HSH, or combinations thereof.
  • the monosaccharides may include mannitol, dulcitol, iditol, or sorbitol.
  • the disaccharides may include isomalt, lactitol, polyglycitol, or maltitol.
  • the polyol should be formulated in the binder solution at a rate of 5%to 75%, or 10% to 20% or 6% to 20% of the weight of the main binder solution solids weight, for formulations having solubilities greater than 10 g/100 at 20° C.
  • the composition of the polyol should contain less than or equal to 15%, or may contain less than or equal to 10% of monosaccharides, less than or equal to 20%, preferably less than or equal to 15% of disaccharides, and greater than 50%, preferably greater than 65% HSH.
  • the polyols contain at least 15% monosaccharides, 20% disaccharides, and 65% HSH.
  • the polyols may include 15% sorbitol, 20% maltitol, and 65% HSH.
  • the ratio of lignin or lignosulfonate to polyol may be adjusted to accommodate a wide range particle agglomeration solubilities.
  • particles with higher solubility i.e., having a greater tendency to form granules
  • particles having lower solubility i.e., having a lower tendency to form granules
  • particles with solubility of less than about 0.3 grams per 100 ml of water at 20° C. may have a ratio in the range of approximately 1.5:1 to about 4:1 of lignin-derived material to a mixture of polyols.
  • particles with a solubility of greater than about 10 grams per 100 ml of water at 20° C. may have a ratio in the range of approximately 5:1 to about 16:1.
  • Table 1 shows the relative ratio of polyol required for a given formulation solubility.
  • the ratio of lignosulfonate to polyol is at least 1.5:1. In another embodiment, the ratio of lignosulfonate to polyol is within the range of approximately 1.5-10:1. In yet another embodiment the ratio of lignosulfonate to polyol may include 2:1, 3:1, 4:1, 5:1, 10:1, or 16:1.
  • the agglomerated particles have the physical property of being substantially spherical and retaining significant resistance to crushing. These physical characteristics are the direct result of the process of agglomerating the particles in combination with the specific ratio of lignin and polyols applied to small and fine sized particles.
  • the process allows for small under-size particles to be recycled back into a granulating apparatus at a rate of 2-3 times the rate of freshly added particles.
  • the recycling process aids in the granulation process by allowing under-sized particles to gradually accumulation in particle size, without sacrificing granule properties.
  • the combination of a preferred binder formula, the application techniques and processing steps, such as recycle rate ratios gives rise to the above-cited desirable properties of the granules of the present invention.
  • the initial particle sizes used in the agglomeration process may vary.
  • fine or powdered sized particles are the starting material. These particles can be in the size range of about 20-40 Size Guide Number (“SGN”). In another embodiment, the SGN may range from about 4-10 SGN, if smoother particle surfaces are desired.
  • Particles which have been agglomerated into a granule may have sphericity percentages greater of at least 85%, more preferably 87%, 88%, 89%, 90%, 91%, or 93%.
  • the aspect ratios are greater than 0.78, more preferably, 0.8, 0.83, 0.87.
  • the agglomerated particle will also have a resistance to crushing which is capable of exceeding approximately 2.0 Lbs. force.
  • the granules generated by the invention have greater sphericity, hardness and aspect ratios, the granules produced are more effective for polymer or resin coatings. This allows for the production of consistent controlled release water soluble granule.
  • the coating which encapsulates the granule may be a sulfur-based coating, a solvent-based polymer coating, or water-based latex coating.
  • the intermediate coating is a water-based latex coating.
  • the latex coating can be selected from polymeric insoluble latex materials, wherein the material comprises copolymer blends of polyvinylidene chloride or ethylenically unsaturated co-monomers such as methyl methacrylates, acrylonitriles, and methyl acrylates, and mixtures thereof.
  • the latex layer is capable of controlling the rate of inner core release, based of the weighting and thickness of the polymeric coating.
  • the granules may also be encapsulated with molten methylene urea resin, molten sulfur, molten waxes, polyurethane resins, alkyd resins, as well as other polymer systems.
  • Solvent-based polymers that may be used in the invention are described, for example, in U.S. Pat. Nos. 4,019,890 and 3,223,518, which are incorporated herein by reference.
  • U.S. Pat. Nos. 4,549,897 and 5,186,732 provide examples of various water-based polymers coated in the absence of solvents, and provide for a safe and cost effective alternative, both of which are incorporated herein by reference.
  • the particles, particulates, or particulate matter of the invention may include any material desired to be agglomerated into a pellet, cake, prill, spheroid tablet, pastille, or flake.
  • the particle generally refers to the active agents bound together, with other components, to form a granular composition.
  • These particles may include agriculturally active materials such as fertilizers, pesticides, soil conditioners or agents, seeds, rice hulls, acaricides, avicides, bactericides, biocides, germicides, rodenticides, vulpicides, nutrient, pesticides, herbicides, fungicides, growth regulators, insecticides, animal and insect repellants, antibiotic, defoliants, pH adjustors, soil conditioners, molluscicides, and mixtures or combinations thereof.
  • particle, particulate, or particulate matter may refer to materials used in pharmaceutical compositions such as drugs, vitamins, or other supplements.
  • particle, particulate, or particulate matter may refer to materials used in the preparation of food products such as but not limited to, granulated cereals, candies, spices, nuts, and meats.
  • the term particle, particulate, or particulate matter will generally not include other components of the granular composition such as the lignin-derived material and the mixture of polyols.
  • the particle may include a fertilizer, nutrient, pesticide, herbicide, fungicide, growth regulator, insecticide, animal and insect repellant, antibiotic, or combinations thereof.
  • the agricultural product is a fertilizer.
  • urea particles combined with the novel binder of the invention exhibit unique anti-caking effects.
  • the polyol component of the binder system provides the unexpected benefit of inhibiting caking or clumping in urea-containing fertilizers by reducing the aspect ratios of the crystals formed in the fertilizer, such that the levels effectively eliminate caking in a treated fertilizer. The details of this benefit are outlined in U.S. Pat. No. 7,776,125, which is hereby incorporated by reference.
  • the particle may also include various seeds, such as grass, vegetables, flowers, or grains.
  • the agglomerated product may also be envisioned as an “all-in-one” seed product, which comprises fertilizer, soil conditioning agents, micronutrients, seed, perlite (or materials having similar open pore space in their physical composition such as synthetic expanded materials, coir, and diatomaceous earth), and optionally a bulk density materials (e.g., limestone, calcium carbonate, calcium sulfate, dolomite, marble, powdered granite, or combinations thereof), and which may be subsequently encapsulated by a protective coating.
  • This all- in-one seed product requires only the addition of water and sufficient sunlight to initiate growth.
  • the all-in-one-seed product is a granular product that comprises (i) particles comprised of a viable seed, soil conditioning agents, fertilizers, micronutrients, soil moisture enhancers, oxygen enhancers, growth enhancers, hormones, and fungicides, and mixtures thereof; and(ii) a binding agent comprising a lignin and a mixture of polyols in a ratio sufficient to agglomerate the particle into a spherical and crush resistant granular product.
  • the ratio of lignin and polyol in the binding agent will be determined by the solubility of the various particles.
  • the ratio of the lignin and the polyols in the binding agent is about 1.5:1 to about 4:1 when the solubility is less than about 0.3 g/100 ml of water at 20° C.
  • the addition of a bulk density material to the all-in-one granule provides surprisingly more granule hardness, sphericity, and germination rates.
  • a “bulk density material” provides for a final granule with improved hardness and spreadability when used in a rotary spreader or other broadcasting devices that distributes materials over a larger area.
  • the bulk density material also improves the overall efficiency in the granulation product by providing an aide or a substrate onto which the agglomeration process may occur.
  • the bulk density material allows for faster agglomeration rate by helping to roll up the seed and binder into granules, thereby and enhancing the formation of a spherical shape.
  • the ability to improve the efficiency of agglomeration, hardness, and sphericity is achieved.
  • the bulk density material may be any heavy material in the range of about 55 to 75 Lbs/cu Ft. (e.g., 60 to 70 Lbs/cu Ft.)
  • the bulk density material is selected from limestone, calcium carbonate, calcium sulfate, dolomite, marble, powder granite or any combination thereof.
  • the agglomeration rate and the formula's overall binder utilization efficiency is a direct function of the heavy bulk density material's particle size distribution. If the particle size distribution of bulk density material is too large, significantly more binder solution is required to roll up spherical granules. This can increase cost of the formula, while potentially reducing product performance. Thus, in one embodiment, the particle size distribution should have to least 99% of the material weight with a size less than 44 microns, with 30-70% of that weight having a particle size less than 5 microns, while also being larger than 1 micron. Using materials having larger particle size distribution slows down the granulation process and requires the use of greater amounts of binder solution. Also the use of excess binder increases production costs.
  • Also contemplated in the invention is a process of manufacturing an agglomerated particle to generate granules with increased crush resistance and sphericity.
  • the process involves the atomization of a specific ratio of lignin to polyol such that the binder solution is intimately mixed with the particles.
  • the viscosity of the binder solution is in the range of 10-20 cps at 25° C.
  • the atomization provides an intimate mixing of components with the added benefit of minimizing the amount of binder applied to the particles.
  • a binder such as calcium lignosulfonate
  • a fertilizer containing micronutrients such as iron sulfate or other metal sulfates (e.g., zinc, manganese, copper, and magnesium)
  • intimate mixing allows chelation of the lignosulfonate.
  • the most effective chelation occurs when the weight percentage of lignosulfate used in the binder solution exceeds the weight percentage of total iron or metal by approximately 70%.
  • Less effective chelation which may result in oxidation, begins if the weight percentage of lignosulfate exceeds the weight percentage of iron or other metals by approximately 25%.
  • the binder solution is approximately 5-6% of the total weight of the final granular product.
  • the invention provides a method of manufacturing a granular product composition of the invention comprising: (i) proving particles comprised of active agents; (ii) providing a binding agent comprising a lignin or lignin-derived material and a mixture of polyols in a ratio which is dictated by the solubility of the particles; (iii) agitating or mixing the particles for a sufficient period of time to generate a homogeneous blend; and (iv) introducing an atomized form of the binding agent through an atomized spray for at least a portion of the time the particles are agitating or mixing.
  • the ratio of the lignin and polyol in the binding agent will vary depending on the solubility of the particles.
  • the ratio of the lignin to polyols in the binding agent is about 5:1 to 16:1 when the solubility of the particles is greater than about 10 g/100 ml at 20° C. In another embodiment, the ratio of the lignin to polyols in the binding agent is about 1.5:1 to 4:1 when the solubility of the particles is less than about 0.3 g/100 ml at 20° C.
  • the method of manufacturing may also comprise a drying step.
  • the times and temperature required for drying are dictated by the particular particle used in the manufacturing process.
  • the solubility of the particle used also plays a role in the determination of the drying times and temperatures.
  • the drying times for a particle having a solubility range of 11-80 g/100 ml at 20° C. will vary from about 10 minutes to about 20 minutes.
  • the temperature of drying may also be dictated by the particular particle used in the manufacturing process. Drying temperatures ranging from 120° F. to about 185° F. will be desired with particles having a solubility range of 11-80 g/100 ml at 20° C.
  • Particles having solubility less than 1.0 g/100 ml at 20° C. may have drying times of about 5 minutes to about 10 minutes. Drying temperatures ranging from 95° C. to about 115° C. will be desired with particles having solubilities of less than 1.0 g/100 ml at 20° C.
  • a mixing device such as but not limited to a drum, fluid bed, or pan, must move at a consistent speed such that the particles are moving in a continuous rolling motion.
  • the continuous motion allows the particles to pass before the binder spray nozzle section of the mixing device, providing for even application of the binder formulation.
  • the speed at which the particles roll is less critical than maintaining overall consistent movement. If the materials undergo intermittent motion, the relative sphericity of the granules will be compromised.
  • Another embodiment of the invention involves a method of fertilizing vegetation comprising adding a granule manufactured by the instant invention.
  • Such methods may include applying to vegetation a fertilizer composition which is substantially spherical and crush resistant, comprising an agglomeration of nutrients, micronutrients, lignosulfonate, and polyols in a ratio sufficient to generate a fertilizer granule which is at least about 70%-95% spherical.
  • the fertilizer granule is about 80%-90% spherical or about 87% spherical.
  • the spherical granule is also capable of withstanding 2 lbs/force when the lignin and polyols ratio is about 1.5:1 to about 16:1.
  • the ratio of the lignin to polyols vary depending on the solubility of the particles used in the manufacture of the granule.
  • Another embodiment of the invention is a method of cultivating grass comprising applying to said grass a composition comprising an agglomerated particle comprising a grass seed, perlite, nutrients, and micronutrients, wherein the particle comprises lignosulfonate and polyols in a ratio sufficient to form a particle that is at least 87% spherical and resistant to 2.0 lbs/force.
  • the lignosulfonate and polyols are in a ratio of about 1.5:1 to about 16:1, but vary depending on the solubility of the particles used in the manufacture of the granule.
  • the lignosulfonate may include calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, aluminium lignosulfonate, or combinations thereof.
  • the polyols may include monosaccharides, disaccharides, and HSH, which may comprise approximately 15% monosaccharides, 20% disaccharides, and 65% HSH.
  • compositions according to one or more embodiments of the present invention will be further described, and advantages thereof, will be made apparent with reference to the following examples, which are provided to illustrate the practice of the invention and not to limit its scope of the invention as defined by the appended claims.
  • the granulation process is conducted at ambient temperatures and therefore can be used for fertilizer and pesticide combinations, as well as biological materials such as seed.
  • Granules of the invention initially require all materials in the formulation to be sized in powder form with an approximate size of 20-40 SGN. All particle components, such as fertilizers, micronutrients, seeds, and perlite are mixed together to form a relatively uniform particle blend. This blending process ensures that the mixture is thoroughly mixed. The particle blend is then feed into a granulator apparatus at ambient temperature and normal humidity.
  • the binder solution i.e., lignosulfonate and polyols
  • the binder solution is applied at a temperature range of 110-130° F. and solution viscosity of 10-20 cps.
  • the viscosity of the binder solution allows for atomization of the binder, thereby allowing intimate mixing with powder blend.
  • the atomization is achieved by using air-assist spray nozzles that will deliver 10-25 SCFH of air per GPH of binder solution.
  • the wet granules are then conveyed to a pre-dryer, which may also be a rotating drum.
  • the pre-dryer removes approximately 30-50% of the moisture added from the binder solution in the granulator and operates in a temperature range of ambient to 135° F.
  • the pre-dryer removes enough moisture to allow increased granules strength for screening.
  • Undersized granules i.e., fines
  • the moisture level in the granulator apparatus is sufficient to allow effective adherence of the next layer of binder solution and powder blend.
  • Granules of the appropriate size are then dried in the fluid bed drier at a temperature range of ambient to 180° F. until a final moisture concentration 0.5-1.0% is achieved. (See FIG. 1 ).
  • the finished granules can be heated in-situ and transferred to other mechanical devices for resin coating to add controlled release coatings if desired.
  • Tables 2-7 show the material ratios loaded as powder mixes into the granulator on a continuous basis at 50 lbs/hr. Each trial was then completed in the same manner as described in the previous section.
  • This example shows the resulting physical data from materials produced using the inventive methods described herein.
  • the SGN is the average size diameter in mm times 100
  • the UI is the uniformity index
  • B/L is the aspect ratio
  • SPH is the sphericity divided by 100
  • the Load at Rupture is the crush strength in Lbs. force.
  • the Table below shows a heavy bulk density material (e.g., calcium carbonate) in the preferred size range included in a formula compared to a similar formula not containing the heavy bulk density material.
  • the results show on-size yield, which is an indication of agglomeration efficiency, increases, along with particle sphericity and granule crush strength.
  • This example shows the non-staining effect of the fertilizer with FeSO4 produced using the methods described herein.
  • These samples were compared to experimental products, designated “MC09-084-A,” which was produced using the inventive methods described herein.
  • MC09-084-A was formulated with iron sulfate (FeSO4) and irrigated in the same manner. The results show that the samples that did not have chelated iron oxidized and stained the concrete block. Samples MC09-084-A and the Kemira 17-10-13 did not stain the concrete.
  • FIGS. 6 , 7 and 8 show the particle size distributions of a heavy bulk density material.
  • the X-axis indicates the ASTM Mesh size measured in each sample, while the Y-axis indicates the weight % found in each ASTM Mesh size fraction.
  • Each sizing test was replicated four times, as displayed with four ‘bars’ in each size fraction.
  • FIGS. 6 and 7 provide example particle size distributions for heavy bulk density materials in the preferred size range of 99% of the material less than 44 microns and 30-70% also less than 5 microns.
  • FIG. 8 provides a heavy bulk density material with a particle size distribution with only 40% by weight of particle with a size less than 44 microns and about 9% less than 5 microns. This particles result in the granulation process requiring two times the amount of binder, compared to using the preferred particle size of heavy bulk density material.
  • the Table below shows the effect of 5 micron wt % versus binder solution utilization. This table shows that when the particle size distribution of the heavy bulk density material is similar to that displayed in FIG. 8 , binder requirements increase by nearly 2 ⁇ .
  • a single granule comprising a seed, fertilizer, soil conditioning agents, micronutrients, growth enhancer, hormones, fungicides, and perlite may be used to form an all inclusive or all-in-one seed particle.
  • an all-in-one system comprising the novel binding system of the invention was used.
  • the all-in-one system tested the effects of the novel binder to grow grass in either rice hulls or perlite.
  • the other components of the all-in one seed system were kept identical with the exception of either perlite or rice hull.
  • the all-in-one seeds comprising the novel binding system and perlite exhibited an increase in germination when compared to the all-in-one seed comprising the binding system and rice hulls. (see FIGS. 4 and 5 ).
  • the combination of perlite and novel binder allowed sufficient air flow transmission to allow germination of the grass seed.
  • the combination of rice hulls and novel binder did not allow sufficient air transmission to the seed and no germination could be achieved.
  • FIGS. 4 and 5 depict this difference when attempting to germinate the granulated seed particles in controlled greenhouse or growth chamber evaluation methods.
  • the perlite used in the all-in-one seed is a lighter material, typically having a bulk density ranging from 5-10 ls./cu. ft. It is a porous and open structure allowing for air transmission to the seed. However, this structure also helps the material achieve a relatively high liquid holding capacity in the range of about 200-300% of its own weight. The ability to retain high levels of liquid helps the particle provide more water for the new seedlings as they are growing and becoming established.
  • perlite may adsorb significant amounts of the binder solution, described herein, potentially causing a reduction in the granulation process.
  • the addition of more binder may seal off the open pores of the perlite, thus reducing its air transmission rate, resulting in a product with reduce seed germination rates.
  • bulk density materials such as limestone, calcium carbonate, calcium sulfate, dolomite, marble, powdered granite, or combinations thereof were added to the production of the all-in-one seed.

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  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
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  • Coloring Foods And Improving Nutritive Qualities (AREA)
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US9512046B2 (en) 2012-08-16 2016-12-06 The Mosaic Company Phosphatic clay products for use as soil wetting agents, and methods of delivery of phosphatic clays to soil
US20170022118A1 (en) * 2013-10-10 2017-01-26 E I Du Pont De Nemours And Company Soil conditioner compositions containing lignocellulosic biomass fermentation process syrup
US20150101378A1 (en) * 2013-10-10 2015-04-16 E I Du Pont De Nemours And Company Soil conditioner compositions containing lignocellulosic biomass fermentation process syrup
US9834483B2 (en) * 2013-10-10 2017-12-05 E I Du Pont Nemours And Company Soil conditioner compositions containing lignocellulosic biomass fermentation process syrup
US9499451B2 (en) * 2013-10-10 2016-11-22 E I Du Pont De Nemours And Company Soil conditioner compositions containing lignocellulosic biomass fermentation process syrup
WO2016032695A1 (en) * 2014-08-29 2016-03-03 The Mosaic Company Phosphatic clay products for use as soil wetting agents, and methods of delivery of phosphatic clays to soil
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US9988318B2 (en) * 2014-10-10 2018-06-05 Iowa State University Research Foundation, Inc. Biodegradable fertilizer
US20170144941A1 (en) * 2015-11-25 2017-05-25 Brian D. Gold Wool pellets for water retention with plants and related methods
US10131584B2 (en) 2015-11-25 2018-11-20 Brian D. Gold Fertilizer compositions including wool pellets and animal products, wool pellets including animal products, and related methods
US20190010093A1 (en) * 2016-02-29 2019-01-10 Genowefa Henryka LASKOWSKA Mineral fertilizer
WO2018045365A1 (en) * 2016-09-02 2018-03-08 Goertz Harvey M Particulate compositions and methods of use
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US20180237351A1 (en) * 2017-02-23 2018-08-23 Produquímica Indústria e Comaércio S.A. Granular fertilizers comprising macronutrients and micronutrients, and processes for manufacture thereof
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US11691928B2 (en) * 2018-05-18 2023-07-04 Lucent Biosciences, Inc. Compositions, systems and methods for delivery of an element in response to biological demand
US20210230082A1 (en) * 2018-06-26 2021-07-29 Nutrifield Pty Ltd Plant nutrient compositions
US11180424B1 (en) * 2018-12-07 2021-11-23 Fertile Peat Products, Llc Phosphate fertilizer with finely ground elemental sulfur, swelling agent and rock phosphate
US11370721B2 (en) * 2018-12-19 2022-06-28 Advanced Biological Marketing, Inc. Functional particles for delivery of beneficial agricultural components
WO2022232287A1 (en) * 2021-04-27 2022-11-03 Gmco Corporation Methods and compositions for dust and soil erosion control

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