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    • 专利摘要:
    METHODS AND SYSTEMS FOR COATING GRANULAR SUBSTRATES The present invention relates to methods and systems for coating substrates. More specifically, the invention relates to methods and systems in which the coating and curing steps are carried out in separate containers. These methods and systems provide a more efficient and more effectively controlled coating process.
    公开号:BR112013020384B1
    申请号:R112013020384-6
    申请日:2012-02-09
    公开日:2021-03-16
    发明作者:Marcus Anthony Bertin；Laurence G. Dammann；Robert M.A. Radabauch；Arthur Ray Shirley Jr.；Willem Van Pol
    申请人:Everris International B.V；
    IPC主号:
    专利说明:

    Fundamentals of the invention Field of the Invention
    [001] The present invention relates to methods and systems for coating granular substrates such as fertilizers. Description of the Correlated Technique
    [002] The idea of a controlled release fertilizer is well known in the art. These fertilizers are typically manufactured by applying a coating on the fertilizer to form a coated mixture and to cure the coated mixture, that is, to form a coated fertilizer with a coating layer, in a single reaction vessel such as a drum or pot of rotation. Additional layers of coating can be applied, using the same process, that is, coating and curing in a single reaction vessel.
    [003] U.S. Patent No. 3,223,518, for example, which is incorporated herein by reference in its entirety for reference, discloses granular, particulate or pelletized fertilizers encapsulated by a non-hydroscopic, non-hydroscopic organic resin encapsulation coating. To obtain the characteristics of controlled release, the patent discloses a fertilizer encapsulated by a multiplicity of coatings obtained by a process of coating and curing fertilizers in a single rotating drum.
    [004] US patent No. 3,285,223, which is incorporated in its entirety into this document for reference, describes the coating and encapsulation of granular materials with a multiplicity of coatings with a specially designed apparatus that provides means of heating, insufflation and rotating in a single container. The patent describes the device as a "curing chamber for oxidation or polymerization of liquid coating" of materials.
    [005] Patents Nos. 4,772,490 and 7,722,696, which are incorporated into this document as a reference in their entirety, have developed resins that can be cured at room temperature. More specifically, the resin is a combination of polyol, cardol, cardanol, derivatives or oligomers thereof and polyisocyanate or isocyanate. The resin is cured or encapsulated in the fertilizer by activation with an amine catalyst. This process, however, was implemented in a single reaction chamber or reactor.
    [006] Although methods of producing controlled release fertilizers that use a single drum or reactor (ie batch processing) are functional and are commonly used, there are several problems associated with these methods. In single drum processing, for example, there is a greater tendency for the generation of lumps or balls of coated materials. For this reason, product quality is lower and more variable and the operation of the drum or machinery may become unstable during operations. In addition, single drum operations cannot handle extremely viscous coating materials. This limits single drum processes to liquid-based coating systems and limits the opportunity to use coating systems free of solvents, solids or containing a high solids content.
    [007] The operation of a single drum involves (1) mixing the substrate and the coating material; and (2) curing the coating in the same reactor. Mixing and curing are two different unit operations that require different conditions. For this reason, the use of a single drum for both operations involves consensus.
    [008] This is of particular relevance when working with fast curing systems, high viscosity mixtures and / or high production systems. If the coating of fast curing systems, for example, is conducted in a single drum, it is unlikely that a satisfactory mixture will be obtained before curing. This reduces the uniformity of the coating. In addition, high viscosity mixtures have more drastic requirements to obtain a satisfactory mix. These requirements are not typically met in a single drum. Finally, large production systems involve large equipment to allow sufficient residence time to ensure proper mixing and curing. Therefore, the use of a single drum is not suitable for such methods.
    [009] In curing systems where a gaseous catalyst is used, normal operation requires that it is generally operated with a discontinuous addition of catalyst or pulse creation cycles. See CA 2,115,998. This involves complex process control and possible sub-optimal use of the catalyst itself.
    [010] Therefore, there is a need in the art to develop efficient and effective methods and systems for coating substrates such as fertilizers. Summary of preferred embodiments of the invention
    [011] The present invention addresses these needs by proposing several methods and systems for coating substrates.
    [012] In one embodiment, the invention proposes a method of coating a substrate that involves separating the mixing process from the curing process. In a specific embodiment, the method comprises (a) mixing a substrate and a coating material in a mixing device to form a coated mixture; and (b) transferring the coated mixture to a separate reactor and curing the coated mixture in the reactor and forming a coated substrate.
    [013] In another embodiment, this process is repeated to provide additional coating layers, for example, to the substrate. In a specific mode, the method comprises (a) mixing a substrate and a coating material in a first mixing device to form a first coated mixture; (b) transferring the first coated mixture to a first reactor and curing the first coated mixture in the first reactor to form a coated substrate with a first layer; (c) mixing the coated substrate of (b) with a coating material in a second mixing device to form a second coated mixture; and (d) transferring the second coated mixture to a second reactor and curing the second coated mixture in the second reactor to form a substrate coated with a second layer, the first reactor being separate and distinct from the first mixing device and optionally, the the second reactor is separate and distinct from the second mixing device.
    [014] In another embodiment, the invention proposes a system for coating substrates with a curable coating material. In a specific embodiment, the system comprises (a) at least one mixing device; and (b) at least one reactor which is separate and distinct from the mixing device, the mixing device being able to mix the coating material with a substrate and the reactor being capable of curing the coating material. In an alternative embodiment, the system comprises (a) at least one mixing device capable of mixing a substrate and coating a substrate; and (b) at least one separate medium for curing a coated material.
    [015] In other embodiments, the invention proposes that (a) the mixing device is a kneading mill; (b) the reactor is a drum or rotating pan. Brief description of the drawings
    [016] Figure 1 shows a schematic diagram of an exemplary substrate coating method of the present invention.
    [017] Figure 2 shows the results of a quick release test (65 ° C) for coated 220SGN urea processed at 230 kg per hour.
    [018] Figure 3 shows the results of a quick release test (65 ° C) for coated 220SGN urea processed at 450 kg per hour.
    [019] Figure 4 shows the results of a quick release test (65 ° C) for 250SGN urea processed at 230 kg per hour.
    [020] Figure 5 shows the release of coated fertilizers over time in quartz sand. The coating weights (from top to bottom in the graph) were 3.0%, 4.0%, 5.0% and 6.0%.
    [021] Figure 6 shows the release of coated fertilizers over time on the ground. The coating weights (from top to bottom in the graph) were 3.0%, 4.0%, 5.0% and 6.0%.
    [022] Figure 7 shows the release of coated fertilizers over time in a tree bark mixture. The coating weights (from top to bottom in the graph) were 3.0%, 4.0%, 5.0% and 6.0%. Detailed description of the preferred embodiments of the invention
    [023] The present invention proposes improved methods for coating substrates. The invention proposes, for example, methods of preparing coated substrates by separating the step of mixing a substrate with coating material from the curing step. These methods involve mixing a substrate with a coating material in a mixing device, then transferring the mixture to a separate reactor and curing the coated mixture. Optionally, the cured product is transferred to a second mixing device where an additional coating material is added and mixed with the cured product. The second mixture can then be transferred to a separate second reactor for curing. This process can be repeated numerous times to achieve the desired coating levels or designs.
    [024] The present invention also proposes improved systems for coating substrates. These systems comprise at least one mixing device and at least one reactor that is separate and distinct from the mixing device. The mixing device is capable of mixing a coating material with a substrate and the reactor is capable of producing accuracy of the coating material.
    [025] The invention also proposes improved mixing devices for mixing substrates and coating materials. More specifically, the invention proposes mixing devices such as kneading mills.
    [026] The inventors have determined that the methods and systems for coating substrates described in this document offer advantages over the methods of a single reactor currently used to coat substrates. Separating the coating and curing processes, the inventors unexpectedly discovered that the coating process can be more easily controlled. Surprisingly, the separation of the coating step from the curing step unexpectedly resulted in increased coating efficiency as well as a reduction in the likelihood of premature curing of the coating materials. In addition, the resulting coated substrates demonstrated a consistent release profile independent of the environment (potting mix, sand, soil, for example) and thus can be used in a variety of controlled release applications.
    [027] Other advantages are obtained using the processes described in this document. The inventors have found, for example, that substrates can be coated with extremely viscous coating materials. This allows the use of coating systems with a high solids content or even without solvents. In addition, the use of a continuous process opens up the potential for large production of fast curing systems that results in the release of equipment for other types of coating applications. The inventors also found that by separating the coating and curing processes, contamination of the equipment is reduced.
    [028] Thus, using the methods of the present invention, the number, types, thickness of layers can be controlled by separating the steps. In addition, greater flexibility can be employed in the types of substrates, coating materials and reaction conditions. In addition, the methods and systems described in this document can also be used in a continuous or batch process mode.
    [029] As described here, various substrates, coating materials, curing methods, catalysts, mixing devices and reactors can be used in these methods and systems. (a) Substrates
    [030] The present invention proposes several methods and systems for coating substrates. Suitable substrates for use in these methods and systems include any substance on which the application of a coating is desired.
    [031] Typically the substrates are water-soluble or partially water-soluble substrates. Water-soluble substrates can be found in granular form, as opposed to non-granular form. The term "granular" or "granule (s)" refers to the compacting and / or agglomeration by physical or chemical means of smaller particles into a single particle. In addition, the word granules can also refer to a material produced by a process of compaction or granulation of non-granular or pulverized substrates. Non-granular or pulverized substrates can be homogeneous or heterogeneous mixtures. For this reason, the substrate can be a homogeneous granule consisting of a single mixture, or alternatively, a heterogeneous granule or composite comprising a mixture of substrates. The granular substrate can be in the form of a pellet, cake, prill, tablet, spherical granule or polyangular granule. The resulting granular substrate can vary in size from approximately 20 SGN size guide number (SGN) to approximately 1000 SGN, with more preferably from approximately 50 SGN to approximately 500 SGN and even more preferable from approximately 100 at 150 SGN to approximately 300 or 400 SGN, with even more preferable from approximately 100 SGN to 400 SGN.
    [032] The granular substrate may include agricultural, medicinal, chemical, agrochemical or confectionery products. Agricultural products can include fertilizers, acaricides, avicides, bactericides, biocides, germicides, rodenticides, vulpicides, nutrients, defoliants, pH adjusters, soil conditioners, crop protection agents, desiccants, antibiotics, pesticides, herbicides, fungicides, regulators growth agents, insecticides, animal or insect repellents, molluscicides, nematocides, and their mixtures or combinations.
    [033] In a specific aspect, the granular substrate is a fertilizer. The fertilizer can consist of a single nutrient or a composite of several nutrients. Nutrients that can be used in the present invention include, but are not limited to, ammonium nitrate, ammonium sulfate, ammonium superphosphate, ammonium chloride, mono-ammonium phosphate, diamonium phosphate, calcium cyanamide, calcium nitrate, urea guanidine , guanidine nitrate and nitro guanidine, superphosphate and triple superphosphate, potassium nitrate, potash, potassium chloride, potassium sulfate, potassium metaphosphate, urea, urea phosphate and mixtures or combinations thereof. Those skilled in the art will note that other fertilizers may be used in the methods and systems described in this document.
    [034] In another special aspect, the fertilizer comprises nitrogen ("N"), phosphorus ("P"), potassium ("K"), NPK, NP, NK and PK. These elements can be combined in different relationships. In one aspect, for example, the NPK ratios can be 13-13-13, 27-0-0, 12-50-0, 0-0-50, 21-7-14, 15-15-15, or 10-11-18. Other NPK relationships will be evident to those skilled in the art.
    [035] In another special aspect, the fertilizer may contain secondary nutrients, such as sulfur, magnesium and calcium and / or micronutrients such as iron, manganese, zinc, copper, molybdenum, boron and cobalt.
    [036] In another special aspect, the fertilizer is urea. Urea can comprise different sizes. The size of the urea is, for example, that of an SGN that is between the limits of approximately 20 and approximately 1000 SGN, with more preferably from approximately 50 SGN to approximately 500 SGN, being even more preferable from approximately 100 or 150 SGN to approximately 300 or 400 SGN, with even more preferable from approximately 100 SGN to 400 SGN.
    [037] Those skilled in the art will note that various substrates can be applied to the methods and systems described here. The inventors have determined, for example, that the methods and systems described here can be used to prepare controlled release fertilizers. Those skilled in the art, however, will note that these methods and systems are applicable to a variety of substrates that can be coated with various coating materials. Variations in the substrate and coating material combinations will become evident to those skilled in the art and can be optimized to achieve the desired final product.
    [038] Patent No. 4,602,440 and provisional application No. 61 / 441,168, entitled “Self-Cleaning Mixing Devices and Methods of using the Same” filed on February 9, 2011, which are hereby incorporated by way of references in full, describe various substrates that are suitable for use in the methods and systems described here. (b) Coating materials
    [039] The methods and systems of the invention involve coating substrates with various coating materials. Coating materials suitable for use in these methods and systems include, but are not limited to, water-based latex coatings, molten resins, solvent-based polymer coatings, water-based polymers, edible coatings such as starches, gelatines or hydrocolloids , resins or paint with a high solids content and solvent-free resins or paints.
    [040] The coating material can be a water-based latex coating. The latex coating, for example, can be a polymeric insoluble latex material that comprises copolymeric mixtures of polyvinylidene chloride or ethylenically unsaturated comonomers such as alkyl methacrylates, acrylonitriles and alkyl acrylates and mixtures thereof. Other water-based latex coatings are known in the prior art such as those described in U.S. Patent Nos. 3,223,518, 3,259,482, 3,264,088, and 3,264,089, which are incorporated in full into this document as a reference. The latex layer is able to control the rate of nutrient release based on the weight of the coating and the thickness of the polymeric coating.
    [041] The coating material can also be a fused methylene urea resin, fused sulfur, fused waxes, polyurethane resins, alkyd resins, as well as other polymeric systems.
    [042] The coating material can be a solvent-based polymer. Solvent-based polymers that can be used in the methods and systems of the present invention are known in the art. See, for example, U.S. Patent Nos. 3,223,518 and 4,019,890, which are incorporated in full into this document as a reference.
    [043] The coating material can be a water-based polymer. Water-based polymers that can be used in the methods and systems of the present invention are known in the art. U.S. Patent Nos. 4,549,897 and 5,186,732, which are incorporated herein by reference in their entirety, provide examples of water-based polymers coated in the absence of solvents.
    [044] In a special aspect, the coating material is a polyurethane-based resin permeable to water or synthetic steam or reaction products produced from it. In a special aspect, the resin is a reaction product of a two-component system comprising a polyol component and an isocyanate component. In one embodiment, the polyol is a cardol, cardanol or derivatives or oligomers of these compounds. In other embodiments, the isocyanate component is a polyisocyanate component. Cardol, cardanol or its derivatives or oligomers can be obtained from a natural product and are therefore considered as a renewable raw material. The raw material can consist, for example, of cashew nut oils. U.S. Patent Nos. 4,772,490 and 7,722,696, which are incorporated in their entirety by reference, describe various resins comprising the reaction product of polyols, such as cardol, cardanol or derivatives or oligomers thereof with polyisocyanates, such as isocyanates.
    [045] The coating materials incorporated by the present invention may also include resins in both thermosetting and thermoplastic resins. The choice of type will be easily evident to those skilled in the art based on the specific applications of the desired coating. In one embodiment of the invention, thermosetting resins can be selected, but not limited to, epoxy polyester, vinylester, polyurethane, phenolic-epoxy or mixtures thereof. In another embodiment of the invention, thermoplastic resins can be chosen from polyamide (PA or nylon), polyesters such as poly (butylene terephthalate) (PBT) and poly (ethylene terephthalate) (PET), polycarbonate (PC), polyethylene (PE), polypropylene (PP), poly (vinyl chloride) (PVC) or their combinations. (c) Healing Methods and Catalysts
    [046] The methods and systems of the present invention involve curing coated mixtures. Those skilled in the art will note that the curing step4 can be carried out using a variety of methods.
    [047] For the purposes of the present invention, the term "cure" "cure" or its grammatical variations are intended to include polymerization, chemical coalescence, dispersion coalescence, chemical crosslinking, small particle melting, solvent evaporation, physical drying by change in temperature, coalescence of colloidal dispersions, melting of colloidal dispersions, melting of colloidal microparticles, setting, physical hardening, drying or any finishing step that seals, solidifies or hardens a liquid, semi-liquid layer, or slimy.
    [048] Curing may involve, for example, heating (or cooling) the coating mixture to a desired temperature, thus forming a hard coating. In one aspect, curing is carried out by raising the temperature by means of conduction heat, convection or radiation. Thus, in one mode, the temperature can be within the range of 0 ° C to approximately 1110 ° C. In a preferred embodiment, the temperature limits are 50 ° C to approximately 110 ° C, 50 ° C to approximately 100 ° C, 50 ° C to approximately 90 ° C, 50 ° C to approximately 80 ° C, from 50 ° C to approximately 70 ° C, or from 50 ° C to approximately 60 ° C. In another embodiment, curing takes place at a temperature of approximately 65 ° C or 75 ° C. Curing can also be carried out at room temperature.
    [049] Alternatively, the cure can be accelerated by adding a catalyst. The catalysts that can be used in the curing step are described in this document. In another aspect, curing in the presence of a catalyst can also occur either at room temperature or in the presence of heat. It should be apparent to those skilled in the art that the reactor temperature can be modified to achieve optimal cure times.
    [050] According to the various modalities of the present invention, the coating material, when coated on the substrate, is cured in a segregated reactor. The segregation of the mixing process from the curing process allows a more uniformly coated substrate to be created. Optionally, a catalyst can be added to reduce the time required for curing.
    [051] The curing process can be accelerated by adding catalysts to the reactor containing the coated mixtures. In one aspect, catalysts can be added to the coated mixture in gaseous form, in the form of gas mixtures with air or in the form of a liquid. The catalyst can be either an amine and / or a metal catalyst in liquid or solid form which can be mixed with or in the coating material.
    [052] Suitable amine catalysts that can be used in the methods and systems of the present invention include, but are not limited to, tertiary amine catalysts. The amine catalysts that can be used include, for example, trimethyl amine, triethyl amine, dimethylethyl amine, dimethylisopropyl amine, dimethyl letanol amine, vinyl imidazole, dimethylbutyl amine or 1,4-diazabicyclo [2.2.2] octane or combinations thereof . Those skilled in the art will appreciate that other amine catalysts can also be used in the methods and systems of the invention.
    [053] Suitable metal catalysts that can be used include, but are not limited to, dibutyltin dilaurate, dibutyltin diacetate, iron acetylacetonate, manganese acetylacetonate, stannous carboxylates such as stannous octoate, potassium octate or combinations thereof. Those skilled in the art will appreciate that other metal catalysts can also be used in the methods and systems of the present invention. (d) Mixing Devices
    [054] The methods and systems of the present invention involve the use of mixing devices. Those skilled in the art will appreciate that a mixing device is any device capable of intimately mixing, stirring, or mixing a substrate and the coating material in a uniform mixture.
    [055] Suitable mixing devices that can be used include, but are not limited to, mixing devices such as kneading mills, rotating drums, paddle mixers, nauta mixers, dosing mixers, extruders, tape mixers or pin mixers . Regardless of the type of mixing device used, suitable mixing devices comprise a mixing area or bed in which mixing takes place. These can include pots, barrels, boxes, beds or any other container that contains substrates and coating materials. In a special embodiment, the mixing device must have a rotating part and a static part.
    [056] The mixing devices can contain rotating elements capable of mixing substrates and coating material. The rotating elements can move bi-directionally or unidirectionally. The rotating elements can include paddles, agitators, tapes, helical threads, pins or combinations thereof. In one aspect, the rotating elements are blades that can be oriented or tilted either in a single direction or alternatively in opposite directions. The orientation and / or inclination of the blades will be apparent to those skilled in the art based on the specific degree of mixing or agitation required and the type of operation (batch or continuous, for example).
    [057] In a specific aspect, the mixing device is a crushing mill. The inventors have determined that the use of a kneading mill is advantageous in the preparation of coating substrates. In fact, a kneading mill allows the manipulation and control of a variety of mixing conditions. A kneading mill can be modified, for example, to control the temperature, the atmospheric conditions of mixing, the point of entry / injection point of the coating materials, and the direction and orientation of the mixture. For this reason, premature curing of a coated mixture can be prevented by controlling the atmospheric conditions of the kneading mill, by conducting the mixing step, for example, in a kneading mill in the presence of an inert nitrogen gas. These and other advantages can be realized using a mixing device in the methods and systems of the invention.
    [058] In another aspect, the mixing device comprises specific rotating elements that allow the movement of substrates and coating materials in a bidirectional manner. Prolonged mixing of substrate and coating materials can cause contamination of the mixing device. The inventors therefore found unexpectedly that the intermittent movement of the rotating elements in the opposite direction for a specified period of time increases the efficiency of the coating process. Thus in one aspect, the mixing device is designed to rotate the rotating elements, such as the kneading mill blades, in the forward rotation direction followed by the rotation of the rotating elements in the reverse rotation direction for a shorter time interval than in the forward direction. This aspect, as well as mixing devices suitable for use in the methods and systems described in this document are described in provisional application No. 61 / 441.168, entitled “Self-Cleaning mixing Devices and Methods of using the Same” filed on February 9, 2011, which is incorporated in its entirety into this document as a reference.
    [059] In another aspect, the mixing device comprises rotating blades that can be fixed to a movable shaft.
    [060] In another aspect, the mixing device may comprise mechanisms for introducing coating materials. A mixing device such as a kneading mill can, for example, comprise injection tubes and / or mixers that are capable of introducing coating materials into the mixing device. The insertion point is defined as the injection point. These injection points may be free to move transversely along the length of the kneading mill in a continuous manner to ensure an equal mixing in the total mixing area. The injection point can be adjusted and optimized, depending on the choice of substrates for resin formulations. Alternatively, the coating material can be sprayed onto or into the mixing device.
    [061] In another aspect, the mixing device is part of a system configured in line with a series of other mixing devices and reactors. These in-line systems allow both continuous and batch processing of substrates to coat a desired substrate with multiple layers. (e) Reactors
    [062] The methods and systems of the present invention involve curing coated mixtures in a reactor. For the purposes of the present invention, a "reactor", "reaction chamber" or "reaction vessel" refers to a place where curing takes place. Those skilled in the art will note that the reactor can be any device that is capable of curing a coated mixture. reactors that can be used include, but are not limited to, rotating drums, rotating bowls, rotating pans, rotating tubes, fluidized beds, nozzle beds, Wurster apparatus, or any container, chamber, or the like that allows curing. The reactor can be configured for different types of curing as already described above. The reactor can be configured, for example, to be heated to a certain temperature range or to a temperature, or to discharge various curing aids such as catalysts into the reactor.
    [063] In one aspect the reactor is separate and distinct from the mixing device. The reactor incorporated by the present invention is specifically designed for curing the coated mixture to be conducted as described in the curing section above. Thus, the intimate mixing or mixing as described in the present invention is carried out in a device that is separate and does not include the reactor in which the curing takes place. Thus, in one embodiment, the method of coating a substrate is carried out by intimately mixing or mixing a substrate and a coating material in a mixing device and transferring the coated mixture to a separate reactor in which the cure will have place. Thus, in one embodiment, the mixing device can be a kneading mill, which then transfers the cured mixture to a reactor such as a rotating drum. Those skilled in the art will note that any mixing device and reactor can be selected, provided that the intimate mixture or mixture occurs separately from the cure.
    [064] In another embodiment of the invention, a coated mixture that has been intimately mixed is directly introduced and received in a first reactor that produces the curing of the mixture by generating a coated substrate. Optionally, the first reactor can subsequently transfer the coated substrate to a second kneading mill for further mixing with coating material, then transferring to a second reactor for a second curing event. (f) Methods and Systems for Coating Substrates
    [065] For the purposes of the present invention, a "coated substrate" according to the present invention refers to a substrate that has been encapsulated by a coating material that has been cured. The coated substrate may comprise a single cured layer, which is referred to herein as a "first coated substrate" or may comprise two cured layers, which is referred to here as a "double coated substrate", secondary coated substrate, "two-layer substrate" layers ”or some equivalent of yours that will easily become evident to those skilled in the art. Such coated substrates, which comprise more than at least two layers, will be called "multilayer substrates" or some equivalent that will be evident to those skilled in the art. A multilayer coated substrate can include between three and approximately ten additional layers of cured coating material. If the substrate is a fertilizer, for example, the term "coated fertilizer" will refer to a granular fertilizer that has been encapsulated within a cured coating material.
    [066] For the purposes of the present invention, a "coated mixture (s)" is defined as substrate (s) that have been (were) coated with a coating material as a result of mixing or intimately mixing within a mixing device.
    [067] As discussed here, methods of coating a substrate according to the modalities of the present invention involve at least two essential steps. The first step involves combining a substrate with a coating material. Both types of substrates and coating materials have already been described here. The combination mentioned above is mixed in a mixing device for a period of time sufficient to mix them intimately in a coated mixture. In general, the types of mixing devices suitable for intimately mixing substrates with coating materials are rotating drums, powder mixers, nauta mixers, kneading mills, pin mixers, tape mixers, extruders or dosing mixers. In one embodiment, the mixing device is a crushing mill. The kneading mill is equipped with shovels or pins that intimately mix the coated mixes.
    [068] When the coated mixture is properly mixed, it is transferred to a separate reactor that provides an environment in which the coated mixture is cured. The suitable environment for curing can be dictated by temperature or the presence of a catalyst. In one embodiment, the temperature at which the coated mixture is cured is within the range of approximately 50 ° C to approximately 100 ° C. It is preferable that the reactor is set to a temperature of approximately 65 ° C or 70 ° C. In another mode, the reactor is at room temperature, but curing is accelerated by the presence of a catalyst. The types of catalysts suitable for curing the coated mixtures are mentioned in this document and those skilled in the art will understand what types of catalysts can be used to accelerate the curing process. Mixing devices and reactors can be placed in ventilation hoods to collect gases released from the process. High concentration of gaseous amine catalysts that are released from the method, for example, is neutralized with a solution of sulfuric acid. The neutralized gas is then released into the atmosphere.
    [069] It will be apparent to those skilled in the art that the method and process described in this document can be repeated over and over again. Those skilled in the art will observe that variables such as thickness, weight of the coating, or different layers and purpose of the coating will dictate the number of times and types of coating materials added in each subsequent repetition of the process. Thus, in one embodiment, the method can be repeated exactly (that is, using the same coating materials and curing times, heat and / or the presence of a catalyst) to obtain a multi-layered coated substrate. In another embodiment, the method may be repeated, but the types of coating materials added in each successive repetition of the method may be different. In addition, the weight of the coating material added at each successive stage can be the same or different. If a final coating weight of 4% is desired, for example, successive steps can be used for the application of the coating material, either in the same proportion or in different proportions (first a 3% coating, for example, followed by a 1%).
    [070] Those skilled in the art will note that the method of coating a substrate can be carried out in batches or can consist of a continuous process. The choice of batch or continuous processing can depend on a variety of factors. The variation in substrate and coating materials, for example, used in the production of the coated substrate, the cycle times between the generation of a mixture and the required curing times, and the economic factors of establishing a continuous production line. Those skilled in the art will appreciate that the method of the present invention can be adapted to either of the two production schemes.
    [071] In another embodiment of the invention, the process of coating a substrate can be implemented through a system. A system suitable for coating a substrate comprises a mixing device and a reactor. In an alternative embodiment, the system can comprise at least two mixing devices and at least two reactors. Mixing devices and reactors suitable for use in the system may include any of those described in this document.
    [072] The methods and systems of the invention can be used to produce coated substrates such as fertilizers. The coated substrates of the invention are useful in a variety of controlled release applications. The coated substrate can, for example, be released for 1, 2, 3, 4, 5, 6 or more months in different environments such as potting mix, soil or sand. EXAMPLES
    [073] The examples below describe several methods and systems contemplated by the invention. These examples are not intended to limit the methods, systems, mixing devices, reactors, substrates, coating materials, or curing methods claimed by the invention. On the contrary, these examples are intended to describe specific embodiments of the present invention in more detail. General Methods (g) Coating a Fertilizer with a Controlled Release polymer
    [074] A series of kneading mills and rotating drums have been set up to establish a continuous processing scheme as shown in Figure 1.
    [075] In this specific scheme, the process has been optimized for coating granules at a rate of approximately 250 kg per hour. The polyurethane-based resin used in the examples was prepared by reacting a liquid polyol (Askocoat EP 7717) with a liquid diisocyanate (Askocoat EP 05547 Comp B). See, for example, U.S. Patent No. 7,722,696 which is incorporated herein by reference in its entirety. The target substrates for the coating in the examples include the following soluble fertilizers: urea of 220 SGN or 150 SGN or NPK. It should be understood that other resins / coatings and substrates may be used, as described in this document.
    [076] The fertilizer granules were placed in a hopper that feeds the granules into a fluidized bed. The fluidized bed was previously heated by air flow to approximately 45 ° C. The previously heated granules were then transferred to a first kneading mill for mixing with the polyol resin. The two components of the resin (ie polyol and diisocyanate) were pumped separately into a static mixer before being injected into the kneading mill through two stainless steel tubes. The flow of the two resin components in the static mixer was controlled by mass flow controllers. Mixing the resin components immediately before injection prevented any undesirable curing within the steel tubes.
    [077] The fertilizer and resin were added to a kneading mill configured to mix and intimately mix the components in a coated mixture. Each kneading mill comprised two axes with fifteen blades each with a capacity of approximately 25 liters. The kneading mill was equipped with a 3.7 kW and 60 Hz motor. The kneading mill was also insulated for the purpose of temperature control and equipped with a removable top cover to control the atmospheric conditions in which the intimate mixing will occur. An inert nitrogen gas was pumped into the kneading mill to prevent unwanted and premature curing of the resin.
    [078] When the granules were enveloped by the resin to form a coated mixture, it was poured into the first reactor - a rotary curing drum. The drum was heated to approximately 65 ° C with a rotation of approximately 8.5 rpm. A liquid catalyst (N, N-dimethylisopropylamine, Sigma Aldrich, for example) was washed with nitrogen to generate a gaseous catalyst. The gaseous catalyst was introduced into the rotating drum through a perforated pipe. The coated and cured fertilizers left the first rotating drum and entered the second kneading mill. In the second kneading mill, additional coating materials were added as described above, and the secondary coated mixtures were subsequently transferred to a second rotating drum for curing. The product typically left the second kneading mill at approximately 55 ° C and the second rotating drum at approximately 70 ° C.
    [079] The coated and cured fertilizers produced consisting of two cured layers of coating material were cooled within the fluidized bed to approximately 30 ° C., A screening process was conducted to remove any agglomerates or fine particles. (h) Testing of Coated Fertilizers Produced
    [080] The performance of the coated fertilizer was measured by the rate of nutrient release from the granule when placed in contact with water. Slower release rates indicate greater product longevity in terms of the release of its nutrients over time. 1. Water leaching test and quick release profile test
    [081] Industry standards for determining product release characteristics include the water leaching test and the rapid release profile test (used only for testing urea).
    [082] In the water release test, the coated NPK fertilizers were placed in water at 21 ° C and tested at two time intervals, after 24 hours and after 7 days. More specifically, twenty grams of coated fertilizer were placed in a flask containing 400 mL of demineralized water. The flask containing the sample was inverted three times to allow mixing and maintained at 21 ° C. After a period of 24 hours, the flask was inverted three times and a sample was taken to determine the amount of nitrogen, phosphorus and potassium in the water. The water was replaced and renewed with 400 mL of fresh demineralized water. The measurement was repeated again after 7 days. After the test, the remaining particles were ground, dissolved to a known volume and analyzed to verify the limit of the mass balance for each component. The results are given in% by weight of N, P2O5 and K2O released into the solution in one day and in seven days.
    [083] The quick release tests were conducted using coated fertilizers produced from urea. More specifically, twenty-five grams of coated fertilizer was placed in 900 mL of demineralized water and kept at a constant temperature of 65 ° C. Samples were taken every hour for 24 hours. The concentration of urea released in the water was measured by refractivity index. The results are given in% by weight of nitrogen released in the solution over time. two . Percentage of release using different coating weights under different conditions
    [084] The release of fertilizers coated with different weights (3%, 4%, 5% and 6%) was tested over three months in different environments: pot mix (also referred to as a mix of bark tree), quartz sand and soil. The bags used in each environment contained the same mass of fertilizer. The percentage of release was assessed after 2, 4, 8, and 12 weeks. Specific Examples
    [085] As a baseline for comparison, the behavior of uncoated materials in the water leaching test was tested, as described in this document, and is summarized in Table 1. The materials used in this control test were 220 granulated urea SGN, granulated urea of 150 SGN, and granulated NPK 13-13-13.Table 1. Leaching in water at 21 ° C for uncoated materials
    Example 1 - Urea of 220 SGN coated in the leach test in processed water at 230 kg per hour.
    [086] Urea of 220 SGN sieved was processed at a rate of 230 kg / H in the described system to obtain a coating weight of 4.3%. Two equivalent layers of polyurethane (ie, 2.15% in each layer) were added to the granules, one layer at each stage of the kneading / drum mill. Operating conditions and results can be seen in Table 2 and Figure 2.Table 2. Operating conditions resulting from water leaching


    [087] The product's performance was very satisfactory, providing a controlled release and a very low initial release for the declared coating weight. Example 2 - Urea of 220 SGN coated in the leaching test in water processed at 450 kg per hour.
    [088] In this example, the production rate has been increased to 450 kg / h. The speeds of the drums and kneading mills have been adapted to absorb the increased rates. The coating weight remained unchanged from the previous example, so a coating weight of 4.3% in two equivalent layers of polyurethane (i.e., 2.15% in each layer) was applied to each kneading mill. Operating conditions and results can be seen in Table 3 and Figure 3.Table 3. Operating conditions for water leaching results

    [089] The release rate of the product has increased compared to urea coated at 250 kg / h. This example demonstrated the flexibility of the rotary kneader-drum mill process / system to adapt to faster coating rates (almost twice the design capacity) without sacrificing quality. Example 3 - Urea of 150 SGN coated in the leach test in water processed at 230 kg per hour
    [090] Urea of 150 SGN sieved was processed at a rate of 230 kg / h. The coating weight was increased to 5.5% (that is, 2.75% in each layer) in two equivalent layers of polyurethane, applied in each kneading mill. The speeds of the kneading mills have been adapted to handle a substrate of smaller particle size. Operating conditions and results can be seen in Table 4 and Figure 4.Table 4. Operating conditions for water leaching results

    [091] It is a generally known fact that the coating of granules of smaller size presents problems and requires greater coating weights, due to its increased surface area. This example demonstrates that smaller granules can be successfully coated with this system. Example 4 - NPK 13-13-13 coated in a water leach test processed at 270 kg per hour.
    [092] A granulated 13-13-13 NPK substrate (13% N, 13% P2O5, and 13% K2O) was processed at a rate of 270 kg / h. Three different coating weights were used for this substrate: 4.3%, 5%, and 6%, each being applied in equivalent layers of polyurethane. The speeds were adapted to the different densities of the substrate. Operating conditions and results can be seen in tables 5, 6 and 7. Table 5. Operating conditions for water leaching results (coating weight 4.3%)
    Table 6. Operating conditions for leaching results in water (coating weight 5%)

    Table 7. Operating conditions for water leaching results (coating weight 6%)

    [093] These examples demonstrate that an NPK substrate can be successfully coated and that the coating weight can be adapted to achieve a desired release profile. Example 5 - Percentage of release using different coating weights in different environments.
    [094] The release of coated fertilizers (coating weights of 3%, 4%, 5% and 6%) was tested in a mixture of bark, quartz sand and soil. The operational conditions for each fertilizer were as follows:
    <<DRAW-CODE>
    [095] Figures 5-7 show the results of this experiment. The results demonstrate a consistent release profile of coated fertilizers for three months, regardless of the environment (pot mix, sand, soil). For this reason, the methods of the present invention are capable of producing coated substrates that are maintained over time in different environments.
    [096] In summary, the methods and systems of the present invention provide efficient and effective means for the production of coated substrates such as fertilizers. The experimental results demonstrate, among other things, that the production rate of the coating process can be increased without sacrificing the quality of the coating on the substrate. In addition, coated substrates have a consistent release profile and can therefore be used in a variety of controlled release applications.
    权利要求:
    Claims (17)
    [0001]
    1. Method of coating a fertilizing substrate, CHARACTERIZED as comprising the steps of: (a) mixing the fertilizing substrate and a coating material, in which said coating material is a thermosetting resin, in a mixing device to form a coated mixture, in which the mixing device is a kneading mill, paddle mixer, ribbon mixer, pin mixer, extruder, metering mixer, or nauta mixer; and (b) transferring said coated mixture to a separate reactor, and (c) curing said coated mixture in the reactor to form a coated substrate, wherein the mixing device is separate and distinct from the reactor.
    [0002]
    2. Method of coating a fertilizer substrate, CHARACTERIZED as comprising the steps of: (a) mixing the fertilizer substrate and a coating material in a first mixing device to form a first coated mixture, wherein said coating material is a thermosetting resin and in which the mixing device is a kneading mill, paddle mixer, ribbon mixer, pin mixer, extruder, metering mixer, or nauta mixer; (b) transfer said first coated mixture to a first reactor separated and curing said first coated mixture in the reactor to form a coated substrate with a first layer; (c) mixing the coated substrate of (b) with a second coating material in a second mixing device to form a second coated mixture; and (d) transferring said second coated mixture to a separate second reactor and curing said second coated mixture in the reactor to form a substrate coated with a second layer.
    [0003]
    Method according to claim 1 or 2, CHARACTERIZED by the fact that the fertilizing substrate is a granular particle.
    [0004]
    4. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the fertilizer is nitrogen, phosphorus, potassium or combinations thereof.
    [0005]
    5. Method, according to claim 4, CHARACTERIZED by the fact that the fertilizer is granular urea.
    [0006]
    6. Method, according to claim 5, CHARACTERIZED by the fact that granular urea is in the size range of about 100 SGN to about 400 SGN.
    [0007]
    Method according to any one of claims 1 to 6, CHARACTERIZED by the fact that the coating material comprises a polyol component and an isocyanate component.
    [0008]
    8. Method, according to claim 7, CHARACTERIZED by the fact that the polyol is cardol, cardanol, derivatives or oligomers thereof.
    [0009]
    9. Method according to any one of claims 1 to 8, CHARACTERIZED by the fact that said method further includes the addition of a catalyst to the reactor.
    [0010]
    10. Method, according to claim 9, CHARACTERIZED by the fact that the catalyst is in the gaseous form, of gaseous mixture with air, inert gas or liquid form.
    [0011]
    11. Method according to any one of claims 1 to 10, CHARACTERIZED by the fact that said method further includes the addition of a metal amine and / or catalyst to the reactor or resin formulation.
    [0012]
    12. Method according to claim 11, CHARACTERIZED by the fact that the amine catalyst is a tertiary amine of trimethyl amine, triethyl amine, dimethyl ethyl amine, dimethylisopropyl amine, dimethyl ethanol amine, vinyl imidazole, dimethyl butyl amine or 1, 4-diazabicycles [2.2.2] octane, or combinations thereof.
    [0013]
    13. Method according to claim 11, CHARACTERIZED by the fact that the metal catalyst is dibutyltin dilaurate, stannous octoate, iron acetyl lacetonate or potassium octoate.
    [0014]
    14. Method according to claim 11, CHARACTERIZED by the fact that said mixing device (s) is a kneading mill.
    [0015]
    15. Method according to any one of claims 1 to 14, CHARACTERIZED by the fact that said reactors are heated to a temperature range of 50 to 100 ° C.
    [0016]
    16. Method according to any one of claims 1 to 15, CHARACTERIZED by the fact that the reactor is a rotating drum.
    [0017]
    17. Method, according to any one of claims 2 to 16, CHARACTERIZED by the fact that it also comprises the repetition of steps (c) - (d).
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    同族专利:
    公开号 | 公开日
    CR20130437A|2013-11-22|
    BR112013020384A2|2016-07-12|
    IL227884D0|2013-09-30|
    EP2672813A1|2013-12-18|
    CO6801697A2|2013-11-29|
    EP2672813B1|2020-08-19|
    IL227884A|2017-02-28|
    AU2012214334A1|2013-09-12|
    CN103476249B|2016-04-20|
    CN103476249A|2013-12-25|
    US20140033779A1|2014-02-06|
    CA2826752A1|2012-08-16|
    MY163030A|2017-07-31|
    BR112013020384A8|2018-01-16|
    AU2012214334B2|2015-09-24|
    WO2012109432A1|2012-08-16|
    JP2014512938A|2014-05-29|
    CL2013002236A1|2014-04-11|
    EP2672813A4|2016-02-24|
    JP6245987B2|2017-12-13|
    US11142488B2|2021-10-12|
    CA2826752C|2018-11-06|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-02| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: A01N 25/00 Ipc: C05G 3/40 (2020.01), B01J 2/00 (2006.01) |
    2021-03-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161441180P| true| 2011-02-09|2011-02-09|
    US61/441,180|2011-02-09|
    PCT/US2012/024459|WO2012109432A1|2011-02-09|2012-02-09|Methods and systems for coating granular substrates|
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