US20060115586A1 - Process and apparatus for coating a controlled release product in a rotating drum - Google Patents
Process and apparatus for coating a controlled release product in a rotating drum Download PDFInfo
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- US20060115586A1 US20060115586A1 US11/292,048 US29204805A US2006115586A1 US 20060115586 A1 US20060115586 A1 US 20060115586A1 US 29204805 A US29204805 A US 29204805A US 2006115586 A1 US2006115586 A1 US 2006115586A1
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- Prior art keywords
- coating
- drum
- plow
- coating materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/006—Coating of the granules without description of the process or the device by which the granules are obtained
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/12—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic in rotating drums
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
- B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
- B05B13/0221—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work characterised by the means for moving or conveying the objects or other work, e.g. conveyor belts
- B05B13/025—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work characterised by the means for moving or conveying the objects or other work, e.g. conveyor belts the objects or work being present in bulk
- B05B13/0257—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work characterised by the means for moving or conveying the objects or other work, e.g. conveyor belts the objects or work being present in bulk in a moving container, e.g. a rotatable foraminous drum
Definitions
- This invention relates to an improved process and apparatus for coating a substrate in a rotating drum.
- fertilizer granules are coated in a rotating drum by spraying and/or dribbling coating components onto the top surface of the bed of fertilizer granules.
- the coating materials such as castor oil and isocyanate, do not easily penetrate into the granule bed.
- One of the reasons for this is their high viscosity and surface tension, which inhibits penetration into the granule bed. Because these coating materials do not readily penetrate into the bed, they first coat the drum surface, and are subsequently transferred onto the surface of the fertilizer granules.
- the coating materials cannot spread effectively on the surface of the fertilizer granules within the time it takes for the castor oil and isocyanate to react to form polyurethane (approximately four minutes at 75° C.).
- fouling is severe, especially on the drum surface around the coating material nozzles. In many cases, the coating drum must be cleaned every two weeks. Not only is the cleaning process expensive, but the production interruptions and higher raw material consumption negatively affects net profits. Moreover, fouling adversely affects the quality of the controlled release product.
- Coating quality (and therefore product performance) is reduced in prior art processes since there is limited opportunity for coating materials to mix in the stoichiometric ratios necessary to form the desired optimum coat on substrate granules.
- isocyanate is typically dribbled onto the surface of the granules in a narrow line, while castor oil is either dribbled or sprayed.
- the opportunity for mixing of these two components with each other and on the surface of the granules is limited, even if the isocyanate and castor oil are delivered substantially simultaneously.
- One reason for this is that granules moving in a rotating drum exhibit a linear layer flow, with slow lateral mixing between layers.
- a process for coating a substrate in a rotating drum wherein a pocket is created in a substrate bed into which pocket coating materials are delivered.
- the present invention is also directed to a controlled release product produced according to the process of the invention.
- a rotatable drum for coating a substrate comprising a mixing zone and a drying zone, wherein the mixing zone comprises (a) one or more means for creating a pocket in a substrate bed, and (b) one or more means for delivering coating materials into the drum.
- FIG. 1 illustrates linear layer flow of substrate granules in a rotating drum.
- FIG. 2 shows the simultaneous delivery of polymer coating, premix and/or monomers into a hole or pocket in a granule bed created by a plow in a rotating drum according to an embodiment of the invention.
- FIG. 3 shows a number of possible shapes for a plow for use in a process of the invention.
- FIG. 4 shows the simultaneous dribbling of polymer coating, premix and/or monomers along the back of a plow to multiple locations onto and/or into a substrate granule bed according to an embodiment of the invention.
- FIG. 5 shows the use of the plow of FIG. 4 to simultaneously delivery polymer coating, premix and/or monomers into a hole or pocket in a granule bed created by the plow.
- FIG. 6 shows the use of burying devices to bury coating materials in a hole or pocket in a granule bed created by a plow according to an embodiment of the invention.
- FIG. 7 shows the placement of a plow in the wet zone of a rotating drum and the effect on the dry zone when injection nozzles are placed in front of and behind the plow according to different embodiments of the invention.
- FIG. 8 shows a baffle structure and orientation in the dry zone of FIG. 7 according to an embodiment of the present invention.
- the means for creating the hole or pocket is not particularly limited, and includes a mechanical device, such as a plow, or high pressure air.
- a mechanical device such as a plow
- substantially improved results are obtained when the coating materials are introduced behind the plow in the applications of coating materials to fertilizer.
- the improved method of the invention not only reduces fouling, but there is also improved mixing of the fertilizer granules with coating materials.
- An improved controlled release profile is observed, suggesting that coating materials are more uniformly distributed onto the granules because of improved mixing.
- Improved mixing also reduces the time required to coat the fertilizer granules, resulting in shorter residence drum times and improved efficiency.
- substrates are fertilizer and plant nutrients
- the process of the invention could be applied to a variety of other substrates.
- substrates include drugs, vitamins, etc.—any substrate for which controlled release delivery would be beneficial, and which can be coated in a rotating drum.
- the fertilizer or plant nutrient material preferably comprises a water soluble compound.
- the plant nutrient comprises a compound containing nitrogen, phosphorus, potassium, sulphur, micronutrients, or a mixture thereof.
- a preferred plant nutrient comprises urea.
- useful plant nutrients are ammonium sulphate, ammonium phosphate, diammonium phosphate and mixtures thereof.
- useful micronutrients include copper, zinc, boron, manganese, iron and mixtures thereof.
- Useful plant nutrient materials are also described in U.S. Pat. No. 5,538,531 and U.S. Pat. No. 6,358,296.
- thermoset polymers include those derived from phenolic, aminoplastic or epoxy resins, some polyesters, polysulphides, and polyurethanes.
- the thermoset polymer is preferably derived from an epoxy resin.
- the thermoset polymer is a polyurethane or a substituted polyurethane.
- the thermoset polymer is formed by reacting a polyol or a mixture of polyols and an isocyanate or a mixture of isocyanates.
- the polyol may be any hydroxy-terminated polyol, such as a polyether, polyester, polycarbonate, polydiene, polycaprolactone, or a mixture thereof.
- polyols such as hydroxy-terminated polyhydrocarbons, hydroxy-terminated polyformals, fatty acid triglycerides, hydroxy-terminated polyesters, hydroxymethyl-terminated polyesters, hydroxymethyl-terminated perfluoromethylenes, polyalkylene-ether glycols, polyalkylene-arylene-ether glycols and polyalkylene-ether triols.
- Preferred polyols include polyethelene glycols, adipic acid-ethylene glycol polyesters, poly(butylene glycol), poly(propylene glycol) and hydroxy-terminated polybutadiene (see, for example, British patent No. 1,482,213). More preferred are polyether polyols and most preferred are polyether polyols having a molecular weight in the range of from about 60 to about 20,000, more preferably from about 60 to about 10,000 and most preferably from about 60 to about 8,000.
- polyols are also described in U.S. Pat. No. 5,538,531.
- polyols having from about 2 to about 6 hydroxy groups, and preferably having at least one C 10 -C 22 aliphatic moiety are described.
- the polyol is castor oil or a mixture of castor oil with other polyols.
- the polyol may also be derived from natural sources, such as soybean, corn, canola, and the like. Polyols derived from natural sources can be used as they are or can be used to derive a synthetic polyol, such as a synthetic polyol based on soybean oil, which is commercially available from Urethane Soy Systems Corp. (Princeton, Ill.).
- polystyrene resin Another useful class of polyols are oleo polyols, such as described in U.S. Pat. No. 6,358,296.
- a mixture of polyols may also be used, for instance, castor oil with ethylene glycol, castor oil with oleo polyol, castor oil with polyethylene glycol, castor oil with polypropylene glycol, or a polypropylene (or polyethylene) glycol mixture of different end groups and molecular weight.
- any suitable isocyanate may also be used.
- the isocyanate compound suitable for use may be represented by the general formula: Q(NCO) i wherein i is an integer of two or more and Q is an organic radical having a valence of i.
- Q may be a substituted or unsubstituted hydrocarbon group (e.g., an alkylene or arylene group).
- Q may be represented by the formula: Q 1 -Z-Q 1 wherein Q 1 is an alkylene or arylene group and Z is chosen from the group comprising —O—, —O-Q 1 —, CO—, —S—, —S-Q 1 -S— and —SO 2 —.
- isocyanate compounds which fall within the scope of this definition include hexamethylene diisocyanate, 1,8-diisocyanato-p-naphthalene, xylyl diisocyanate, (OCNCH 2 CH 2 CH 2 OCH 2 O) 2,1-methyl-2,4-diisocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, chlorophenylene diisocyanates, diphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4′4′′-triisocyanate and isopropylbenzene-alpha-4-diisocyanate.
- Q may also represent a polyurethane radical having a valence of i.
- Q(NCO) i is a compound which is commonly referred to in the art as a prepolymer.
- a prepolymer may be prepared by reacting a stoichiometric excess of an isocyanate compound (as described above) with an active hydrogen-containing compound, preferably the polyols described above.
- the polyisocyanate may be, for example, used in proportions of from about 30 percent to about 200 percent stoichiometric excess with respect to the proportion of hydroxyl in the polyol.
- the isocyanate compound suitable for use in the process of the present invention may be selected from dimers and trimers of isocyanates and diisocyanates, and from polymeric diisocyanates having the general formula: [Q′′(NCO) i ] j wherein both i and j are integers having a value of 2 or more, and Q′′ is a polyfunctional organic radical.
- Such isocyanates may be used together with compounds having the general formula: L(NCO) k wherein k is an integer having a value of 1 or more and L is a monofunctional or polyfunctional atom or radical.
- isocyanate compounds which fall within the scope of this definition include ethylphosphonic diisocyanate, phenylphosphonic diisocyanate, compounds which contain a ⁇ Si—NCO group, isocyanate compounds derived from sulphonamides (QSO 2 NCO), cyanic acid and thiocyanic acid.
- Non-limiting examples of suitable isocyanates include: 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, furfurylidene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylpropane diisocyanate, 4,4′-diphenyl-3,3′-dimethyl methane diisocyanate, 1,5-naphthalene diisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene, 2,4-diisocyanato-s-triazine, 1-methyl-2,4-diisocyanato cyclohexane, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,4-n
- Particularly preferred isocyanates are those described in U.S. Pat. No. 5,538,531 and U.S. Pat. No. 6,358,296.
- An isocyanate mixture may be preferred for some coatings.
- the polyol and isocyanate are used in amounts such that the ratio of NCO groups in the isocyanate to hydroxy groups in the polyol is in the range from about 0.5 to about 3.0, more preferably from about 0.8 to about 2.0, and most preferably from about 0.9 to about 1.1.
- thermoset polymer may be formed by using amine group-terminated or mercaptan-terminated monomers.
- a urea-formaldehyde resin may be used.
- Additives may be included in the coating materials. For instance, if the coating materials are hydrophilic, then they will be compatible with hydrophilic substrate surfaces and they will be easy to spread on the surface. If the coating materials are hydrophobic however, there will be difficulty in spreading the coating materials on the substrate surface. Under these circumstances, additives like wetting agents, flow agents, levelling agents and coupling agents may be used to improve spreadability. If the viscosity of the coating is high, an additive may be also be used to improve spreadability.
- additives Another function of additives is to increase the hydrophobicity of the coating. Hydrophobic additives reduce the release rate of coated substrate.
- Preferred additives are organic additives, such as petroleum products, coal products, natural products and synthetic products. Lubricants derived from these may also be used. Exemplary organic additives include commercially available coating additives and paint additives (such as wetting agents, flow agents, levelling agents and coupling agents), wax, paraffin oil, bitumen, asphalt, oil derived from coal, canola oil, soybean oil, coconut oil, linseed oil, tung oil, vegetable wax, animal fat, animal wax, and forest products such as tall oil, modified tall oil, tall oil pitch, and pine tar. Mixtures of these materials may also be used. Particularly preferred organic additives are hydrophobic materials.
- the organic additive is wax
- preferred waxes are those described in U.S. Pat. No. 5,538,531 or a silicone wax, such as is available from Dow Corning.
- Preferred waxes have a drop melting point of at least 10° C., preferably between about 20° C. to about 120° C., and more preferably between about 30° C. to about 120° C.
- the wax is substantially non-tacky below about 40° C.
- the preferred wax is a C 10 + alpha-olefin, and more preferably a C 20-100 alpha-olefin.
- the wax is a C 30 + wax, such as is available commercially from Chevron Phillips Chemical Company.
- the amount of organic additive may vary, depending on its purpose in the mixture, as would be apparent to a person of skill in the art. For instance, for some commercially available additives, an amount as low as 0.001% by weight of the coating composition may be used.
- Preferred organic additives and amounts are those that improve the release profile and mechanical handling of the polymer coated substrate.
- substrate granules exhibit a linear layer flow as shown in FIG. 1 .
- the granules in contact with the drum wall and those proximate to the drum wall move in the direction of the drum due to friction forces between the granules and (a) the drum wall and (b) other proximate granules.
- the granules on the surface of the granule bed and distal to the drum wall move in an opposite linear direction to the linear direction of rotation of the drum. This effect results in a layered flow pattern, which inhibits penetration of coating components through the granule bed.
- a variety of means can be used to create the hole or pocket in the granule bed.
- the hole or pocket is created by a mechanical device, such as a plow, or high pressure air.
- a mechanical device such as a plow, or high pressure air.
- FIG. 2 An example of a plow ( 10 ) creating a hole or pocket ( 20 ) in a substrate granule bed ( 30 ) in a rotating drum ( 40 ) is shown in FIG. 2 .
- a plow a variety of different shapes can be used, such as shown in FIG. 3 .
- the plow has a linear arm, curved to create a scoop at the end (e.g., a bent angle iron), which will create the hole or pocket in the fertilizer bed.
- a sharply angled arm e.g., a straight angle iron is less preferred, although it too may be used.
- the approach angle of the plow with respect to the substrate bed surface may be 5-175°, preferably 30-150°, more preferably 40-140°, and more preferably still 45-145°.
- the optimum approach angle of the plow with respect to the substrate granule bed surface is related to the shape of the plow and can be determined by one of ordinary skill in the art through routine experimentation.
- the depth of the plow in the substrate bed may be 5-95% of the substrate bed depth, preferably 10-90%, more preferably 20-80%, and more preferably still 30-70%.
- the optimum depth is related to the plow shape, approach angle, and loading rate of the drum, and can be determined by one of ordinary skill in the art through routine experimentation.
- the coating materials may be delivered substantially simultaneously, as single or divided injections by spraying or dribbling, into the hole or pocket in the substrate granule bed.
- a polyurethane coated fertilizer (a) premix (comprising a polyol and other coating components) or a polyol, and (b) isocyanate may be delivered into the hole or pocket through the same or different injection nozzles.
- FIGS. 4 and 5 illustrate the delivery of polymer coating, premix and/or monomers ( 50 , 60 ) in two injection streams behind the plow ( 10 ) into the hole or pocket ( 20 ) in the granule bed ( 30 ) of the rotating drum ( 40 ).
- the castor oil or premix may be delivered into the hole or pocket by dribbling or spraying.
- isocyanate is used, the isocyanate is typically dribbled into the hole or pocket, although it too may be sprayed.
- the castor oil or premix and the isocyanate are dribbled, preferably substantially simultaneously behind the plow.
- the first application of coating materials are delivered substantially simultaneously behind the plow.
- the materials when coating materials are delivered behind the plow, the materials begin mixing in the hole or pocket created such that the higher temperature premix or polyol helps to reduce the viscosity and surface tension of the isocyanate. This in turn increases the penetration speed of the isocyanate into the granule bed. If the coating materials are delivered in front of the plow, the materials are not delivered directly into the hole or pocket and the opportunity for mixing the reactive monomers is reduced. Improved mixing of the coating materials allows for a more even coating to be produced. Improved mixing is particularly important for the first application of coating materials.
- the injection nozzles and pipes used to deliver coating materials may be inserted below the surface of the moving granule bed. Where the injection nozzles are below the surface of the granule bed, there is a greater opportunity for mixing of coating components in the hole or pocket. Where the injection nozzles are inserted below the surface of the granule bed, the coating materials are typically dribbled into the hole or pocket.
- Burying devices such as shown in FIG. 6 can also be used to cover the hole or pocket ( 20 ) produced by a device such as a plow ( 10 ) or high pressure air.
- a preferred burying device is one or more blades ( 70 ). By sealing the cut made by the plow or air with one or more burying devices, mixing may be further improved.
- the materials wet the granules.
- This wetting of granules creates a “wet zone” ( 80 ) in the drum, which is illustrated in FIG. 7 .
- the granules stick together in this zone and move almost as a solid.
- Coating components can also be delivered into the wet zone at multiple delivery points. If there is multiple delivery of coating components, multiple plows may also be used at each or some, but at least one, of these delivery points.
- the coated granules enter the “dry zone”, in which the granules flow freely in a different flow pattern than when wet.
- the coating e.g., thermoset polymer
- dry e.g., thermoplastic polymer
- coated particles come into contact resulting in granules caking together and defects (such as an uneven coating thickness, craters, tears, pinholes, etc.) forming on the coating surface.
- defects such as an uneven coating thickness, craters, tears, pinholes, etc.
- the average linear velocity of coated particles in the drum should be reduced. This may be done by reducing drum speed, decreasing drum size, introducing baffles, etc., and as described in co-pending U.S. patent application Ser. No. 10/868,646.
- drum speed alone is reduced, it is preferably slowed to about 10% to about 80% of the speed of the drum in the wet zone. The same percent reduction also applies to the size of the drum, if it is the size that is reduced.
- Baffles can also be used to reduce the velocity of coated particles, depending on their orientation, height, and number.
- a preferred baffle orientation is shown in FIG. 8 .
- the baffles are oriented in a different direction to the avalanche flow of the coated particles (i.e., a direction different than or opposite to the rotational direction of the drum), resulting in a substantial reduction in velocity.
- baffles and reduced drum speed/size can also be used.
- a coating unit may be used in which multiple coating layers are applied to substrate granules. For instance, a coating unit having multiple regions for sequential application of coating materials could be used, each region having a wet and dry zone. In the wet zone of the first region, a device to create a hole or pocket, such as a plow, is used. If a plow is used, preferably the coating nozzles and pipes are located behind the plow. In the second and subsequent coating region wet zones a device may also be used to make a hole or pocket, although it is less important than in the first region wet zone.
- a plow is used in the second and subsequent wet zones, it has been discovered that it is less important for the coating nozzles and pipes to be located behind the plow in order for there to be a substantial reduction in fouling, although it is preferred to have the nozzles and pipes behind the plow.
- a coating unit is used which has three or four coating regions.
- the wet and dry zones may comprise the same physical region of the coating drum.
- the distinction between “zones” in this embodiment is simply a way to describe the stage of the coating process between application of coating materials (wet zone) and stabilization of coating, i.e., curing or drying (dry zone).
- the wet and dry zones comprise two distinct physical regions of the drum.
- the drum may be angled, such that substrate granules enter the drum at one end, comprising the wet zone, and move into the dry zone by gravitational force.
- the wet and dry zones may also comprise two drums, connected in series.
- drums may be used or multiple drums may be used. Where multiple drums are used, a variety of drum combinations can be used, including using one or more of the drums or drum combinations described above.
- a device such as a plow to create a hole or pocket in a granule bed in a first application of coating material to the granules, especially where coating materials are delivered behind the plow if used, results in an improved controlled release product. It has been surprisingly discovered that the product so produced exhibits an improved front-end (i.e., under ten days) water release rate in controlled release profiling tests compared to product produced where (a) no plow is used, and (b) coating components are delivered in front of the plow, if a plow is used.
- a rotary coating unit was used, having three coating regions, with three groups of nozzles and pipes, one group in each coating region.
- a premix (comprising castor oil) and isocyanate were simultaneously delivered through a pipe (i.e., dribbling or spraying) behind a bent angle iron plow that was welded into the coating unit.
- a pipe i.e., dribbling or spraying
- a bent angle iron plow that was welded into the coating unit.
- second and third coating regions plows were also used.
- the plow helped to reduce the release rate of the product. It was also discovered that by introducing the premix and isocyanate behind the plow, the dry zone of the first coating region increased from about 1 to 11 ⁇ 2 feet to approximately 5 feet. This increase in the dry zone is comparable to that of the second and third coating regions, which was not achievable before adding a plow and delivering coating materials behind the plow. This indicates better spreading of the coating materials on the substrate.
- the controlled release urea (CRU) produced had a 15-20% N release at day 7 .
- This release rate is difficult to achieve both in the absence of a plow and, if a plow is used, with the coating components added in front of the plow in the first wet zone.
- the improved release rate demonstrates an improved mixing in the first application of coating to substrate.
- % N release of CRU produced according to the above process are shown in Table 1.
- TABLE 1 Day 7 Day 14 Day 21 (a) 42* 55 63 (b) 30 45 55 (c) 20 28 38 (d) 15 22 30 *% N release
- the water release data for the controlled release fertilizer material was also determined in accordance with the following procedure.
- a water release rate profile analysis was performed using a Technicon AutoAnalyzerTM, calibrated and used pursuant to the teachings of Automated Determination of Urea and Ammoniacal Nitrogen (University of Missouri, 1980).
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Application Number | Priority Date | Filing Date | Title |
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US11/292,048 US20060115586A1 (en) | 2004-11-30 | 2005-11-30 | Process and apparatus for coating a controlled release product in a rotating drum |
US12/756,835 US20100186470A1 (en) | 2004-11-30 | 2010-04-08 | Process and apparatus for coating a controlled release product in a rotating drum |
US14/850,666 US9878959B2 (en) | 2004-11-30 | 2015-09-10 | Process and apparatus for coating a controlled release product in a rotating drum |
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US63140904P | 2004-11-30 | 2004-11-30 | |
US11/292,048 US20060115586A1 (en) | 2004-11-30 | 2005-11-30 | Process and apparatus for coating a controlled release product in a rotating drum |
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US12/756,835 Continuation US20100186470A1 (en) | 2004-11-30 | 2010-04-08 | Process and apparatus for coating a controlled release product in a rotating drum |
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US11/292,048 Abandoned US20060115586A1 (en) | 2004-11-30 | 2005-11-30 | Process and apparatus for coating a controlled release product in a rotating drum |
US12/756,835 Abandoned US20100186470A1 (en) | 2004-11-30 | 2010-04-08 | Process and apparatus for coating a controlled release product in a rotating drum |
US14/850,666 Active 2026-07-16 US9878959B2 (en) | 2004-11-30 | 2015-09-10 | Process and apparatus for coating a controlled release product in a rotating drum |
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US14/850,666 Active 2026-07-16 US9878959B2 (en) | 2004-11-30 | 2015-09-10 | Process and apparatus for coating a controlled release product in a rotating drum |
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US (3) | US20060115586A1 (de) |
EP (1) | EP1827714B1 (de) |
CN (1) | CN101068628B (de) |
CA (1) | CA2588793C (de) |
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Cited By (26)
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US20090138313A1 (en) * | 2007-05-15 | 2009-05-28 | American Power Conversion Corporation | Methods and systems for managing facility power and cooling |
US20100186470A1 (en) * | 2004-11-30 | 2010-07-29 | Agrium, Inc. | Process and apparatus for coating a controlled release product in a rotating drum |
US20100233332A1 (en) * | 2004-06-14 | 2010-09-16 | Agrium Inc. | Process and apparatus for producing a coated product |
US20110307820A1 (en) * | 2005-05-02 | 2011-12-15 | American Power Conversion Corporation | Methods and systems for managing facility power and cooling |
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Also Published As
Publication number | Publication date |
---|---|
EP1827714B1 (de) | 2019-07-10 |
EP1827714A1 (de) | 2007-09-05 |
ES2745410T3 (es) | 2020-03-02 |
EP1827714A4 (de) | 2013-05-01 |
CN101068628A (zh) | 2007-11-07 |
US20150376078A1 (en) | 2015-12-31 |
US20100186470A1 (en) | 2010-07-29 |
CN101068628B (zh) | 2012-04-25 |
WO2006058422A1 (en) | 2006-06-08 |
EG24625A (en) | 2010-03-08 |
CA2588793A1 (en) | 2006-06-08 |
CA2588793C (en) | 2015-01-13 |
US9878959B2 (en) | 2018-01-30 |
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