Method of making a fertilizer seed core

Information

  • Patent Grant
  • 11806689
  • Patent Number
    11,806,689
  • Date Filed
    Wednesday, February 8, 2017
    7 years ago
  • Date Issued
    Tuesday, November 7, 2023
    a year ago
Abstract
Described herein is a method of making a fertilizer granule. The method includes supplying a fertilizer component, an liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones; mixing the fertilizer component, liquid component, binder and filler to yield a thixotropic mixture; and passing the thixotropic mixture through the die head.
Description
BACKGROUND

Granular fertilizers are widely used to increase plant growth. Granular fertilizers can comprise a seed core. The production of the fertilizer seed core by extrusion can be problematic. Issues arrive with seed core integrity, material flow and pelletization, particularly when the extrusion composition is thixotropic. Accordingly, there is a need in the art for a method of making fertilizer seed cores by extrusion.


SUMMARY

Disclosed herein is a method of making a fertilizer seed core, the method comprising: supplying a fertilizer component, a liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones; mixing the fertilizer component, liquid component, binder and filler to yield a thixotropic mixture; and passing the thixotropic mixture through the die head, wherein the die head comprises openings 0.5 to 4 millimeter in diameter and wherein the end of the screw is 1 to 15 millimeters from the die head.


Also disclosed herein is a method of making a fertilizer seed core, the method comprising: supplying a fertilizer component, a liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones; mixing the fertilizer component, liquid component, binder and filler to yield a thixotropic mixture; and passing the thixotropic mixture through the die head, wherein the die head comprises openings 0.5 to 4 millimeter in diameter and wherein the extrusion process has a residence time of 5 seconds to 15 minutes.


The above described and other features are further set forth in the following figures, detailed description and claims.





BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are exemplary embodiments wherein the like elements are numbered alike.



FIG. 1 is a representation of the intake side of a die head having conical openings.



FIG. 2 is a transverse view along line A-A of FIG. 1.



FIG. 3 is a representation of the intake side of a die head having cylindrical openings.





DETAILED DESCRIPTION

According to the method of making a fertilizer seed core, a fertilizer component, a liquid component, e.g., an aqueous component, binder, filler, and optional additives are supplied to an extruder having at least three zones. The method can include supplying a viscoelastic agent to the agent. The binder, when mixed with the liquid component, forms a mixture which decreases viscosity when subjected to shear stress. The decrease in viscosity results in issues of seed core integrity, material flow and pelletization. It has been found that extrusion can be effectively achieved by supplying the liquid component to the extruder simultaneously with the binder or after the binder. When the liquid component is supplied to the extruder before the binder issues arise with the unequal distribution of components of the composition and uneven density, sometimes even resulting in lumps in the composition.


The dry ingredients, namely the fertilizer component, the binder, the filler and any dry additives, may be added to the extruder sequentially or simultaneously. In some embodiments the fertilizer component and the binder are dry mixed prior to being supplied to the extruder. Any dry additives can be included in the dry mix. Alternatively any dry additives can be supplied to the extruder simultaneously or sequentially with the dry mix.


The liquid ingredients, namely the liquid component and any liquid additives, can be added with some or all of the dry ingredients as long as the binder is added before the liquid component or simultaneously with the liquid component.


In some embodiments, the fertilizer component, the binder and any dry additives are supplied to the first zone of the extruder to form a first composition which is mixed as it is moved to a second zone of the extruder where the liquid component is supplied to the extruder to form a second composition. The second composition is mixed as it is moved to the die head. The first and second zones may be operated at a temperature of 0 to 70 degrees Celsius, for example, 0 to 40 degrees Celsius. In some embodiments the temperature of the first and second zones is substantially the same. The die head may be operated at a temperature of 0 to 70 degrees Celsius.


The term “first zone” and “second zone” as used in this context does not exclude extruder designs where the first zone or second zone consists of two or more separate zones of the extruder with the proviso that the second zone is downstream of the first zone. Additionally, it is expressly contemplated that an additional zone or zones may intervene between the first zone and second zone.


In some embodiments the die head has a dead space of 1 to 6 millimeters (mm), or 7 to 10 mm, or 1 to 15 mm. The dead space is the distance between the end of the extruder screw and the die head. Additionally, the die head can comprise eccentric openings. When the openings are eccentric the diameter of the openings refers to the longest linear dimension. This is shown in FIG. 1 as “D”. The die head openings can have a diameter of 0.5 to 4.0 millimeters on the outflow side. The land length of the die head openings (the distance from the inside of the extruder to the outside of the extruder) can be 3 to 10 mm, or 10 to 16 mm, or 3 to 16 mm. The die head openings can be conical or cylindrical. Conical openings have a broader opening at the intake and narrow to a smaller opening at the outflow. The outflow openings can have a diameter that is 30 to 100% of the intake openings. Within this range the outflow openings can have a diameter that is 30 to 70%, or, 50 to 100% of the intake openings. The conical openings can have an angle, 40, of 40 to 45 degrees. Cylindrical openings have substantially the same size opening at the intake and outflow locations.


Turning now to FIG. 1, an exemplary die head 10 is shown with circular openings 20. The die head is shown from the intake side. A cross section of the die head taken along line A-A is shown in FIG. 2. FIG. 2 shows the die head 10 having conical openings 20. The conical openings have an angle 40 and a length 30. The arrow shows the direction of flow for the thixotropic composition. FIG. 3 shows a die head 10 having cylindrical openings 20.


In some embodiments the die head comprises a cooling jacket in which a coolant such as water is circulated around the die head openings at a temperature of 0 degrees Celsius to room temperature (typically 25 degrees Celsius).


After leaving the die head, the thixotropic mixture is cut into pellets. In some embodiments, the mixture is cut into pellets immediately upon leaving the die head (at the die face) using a knife. The knife can be of any shape or design required to obtain the desired pellet size. In some embodiments the knife comprises 2 or more blades.


The fertilizer component comprises an inhibitor, a micronutrient or a combination comprising at least one of the foregoing. The inhibitor can comprise a urease inhibitor, a nitrification inhibitor or a combination comprising at least one of the foregoing. Exemplary inhibitors include N-(n-butyl)thiophosphoric triamide (NBTPT), 3,4-dimethylpyrazole phosphate (DMPP), thio-urea (TU), dicyandiamide (DCD), phenyl phosphorodiamidate (PPDA), 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol (terrazole), 2-amino-4-chloro-6-methyl-pyrimidine (AM), 2-mercapto-benzothiazole (MBT), 2-sulfaminalamidothiazole (ST), and combinations comprising at least one of the foregoing.


A micronutrient is a botanically acceptable form of a compound comprising boron (B), copper (Cu), iron (Fe), chloride (Cl), manganese (Mn), molybdenum (Mo), nickel (Ni), zinc (Zn) or a combination comprising at least one of the foregoing. Exemplary inorganic compounds include sulfate, oxides and salt. Specific examples include borax, anyhydrous sodium tetraborate, sodium tetraborate pentahydrate, sodium tetraborate decahydrate, potassium metaborates, potassium tetraborates, potassium peroxyborates, calcium metaborates, ammonium pentaborates, ammonium tetraborates, CuSO4, and ZnSO4. Exemplary organic compounds include Fe EDTA, Fe EDDHA, Ca EDTA, Zn EDTA, and Mn EDTA. EDTA is an acronym for ethylenediaminetetraacetate and EDDHA is an acronym for ethylenediamine-N,N′-bis(2-hydroxyphenylacetate).


The fertilizer component is present in an amount of 0.25 to 55 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler.


In some embodiments the fertilizer component comprises NBTPT. The NBTPT can be present in an amount of 0.25 to 6.0 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler. Within this range, the amount of NBTPT can be 0.8 to 2.2 weight percent.


In some embodiments the fertilizer component comprises DCD. The DCD can be present in an amount of 10 to 45 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler. Within this range, the amount of DCD can be 15 to 25 weight percent.


In some embodiments the fertilizer component comprises a combination of NBTPT and DCD. In these embodiments the combination of NBTPT and DCD can be present in an amount of 11 to 47 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler. Within this range, the amount of NBTPT can be 0.8 to 2.2 weight percent and the amount of DCD can be 15 to 25 weight percent. The combined amount of NBTPT and DCD can be 24 to 27 weight percent.


The binder comprises Plaster of Paris, flour, starch, cellulose, gluten, colloidal silica, kaolin, bentonite, polyethylene glycol (PEG), polycaprolactone, low molecular weight polyvinyl acetate, or a combination comprising at least one of the foregoing. The binder is present in an amount of 25 to 90 weight percent based on the combined weight of the fertilizer component, liquid component, binder and filler.


The liquid component, e.g., aqueous component, comprises water and any optional liquid additives. It is also contemplated that optional solid additives may be at least partially dissolved in the liquid component with the proviso that the liquid component has a solids content of less than or equal to 10%. The liquid component is present in an amount of 7 to 25 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler. Within this range the liquid composition may be present in an amount of 7 to 11, 11 to 16, or 20 to 25 weight percent.


In some embodiments the weight ratio of liquid component to binder is 5 to 30. Within this range the weight ratio can be 5 to 15, 10 to 20, or 15 to 30.


The filler comprises chalk powder, silica, rice husk, dried distillers grains with solubles (DDGS), calcite, calcium oxide, dolomite, talc, calcium carbonate, sand, chalk powder, sodium carbonate (Na2CO3), potassium carbonate (K2CO3), magnesium oxide (MgO), monopotassium phosphate (KH2PO4), sodium bicarbonate (NaHCO3), or a combination comprising one or more of the foregoing. The filler is a material which can facilitate the release of inhibitors, micronutrients or both from the seed core. The filler can also help improve the properties of the core. The filler is a dry ingredient and hence may be supplied as described above with regard to dry ingredients. The filler is present in an amount of 5 to 50 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler. Within this range the filler may be present in an amount of 5 to 20, 15 to 30, or 30 to 50 weight percent.


Additives can include viscoelastic agents, e.g., a polymer thickener, such as hydroxyl propyl methyl cellulose, polyethylene glycol, or a combination comprising at least one of the foregoing.


Optional additives can include, for example, surfactants, nucleation agents, recycled fertilizer particles, nucleating soil conditioners such as activated carbon, elemental sulfur, biocides such as pesticides, herbicides, or fungicides, wicking agents, wetting agents, heat stabilizers, adhesives such as cellulose, polyvinyl alcohols, fats, oils, gum arabics, vinylidene ultraviolet stabilizers, antioxidants, reducing agents, colorants, alternative binders (i.e., organochlorides, zeins, gelatins, chitosan, polyethylene oxide polymers, and acrylamide polymers and copolymers), and the like, as well as combinations comprising at least one of the foregoing.


The fertilizer seed core can have any shape or size desired for their intended use. The fertilizer seed cores have an average particle diameter of 0.5 to 4.0 millimeters (mm). Within this range the average particle diameter can be greater than or equal to 0.75, or greater than or equal to 1.0 mm. Also within this range the average particle diameter can be less than or equal to 3.5 mm, or less than or equal to 3.0 mm. In some embodiments at least 90% by weight of the fertilizer seed cores have a particle diameter of 0.6 to 1.4 mm, for example 0.7 to 1.2 mm. Particle diameter is determined according to “Size Analysis—Sieve Method” IFDC S-107 issued by International Fertilizer Development Center (IFDC) which is the most common and internationally approved method used to determine fertilizer particle size.


The fertilizer seed cores are subsequently fattened with additional components such as urea and/or excrement to produce a fertilizer granule. By incorporating the fertilizer components such as inhibitors and micronutrients into the seed core these components are protected from degradation resulting from conditions required for subsequent processing steps.


The method and extruders disclosed herein include at least the following embodiments:


Embodiment 1: A method of making a fertilizer seed core, the method comprising: supplying a fertilizer component, an liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones; mixing the fertilizer component, liquid component, binder and filler to yield a thixotropic mixture; and passing the thixotropic mixture through the die head, wherein the die head comprises openings 0.5 to 4 millimeter in diameter and wherein the end of the screw is 1-15 millimeters from the die head.


Embodiment 2: The method of embodiment 1, wherein the die head openings have a land length of 3 to 16 millimeters.


Embodiment 3: The method of embodiment 1 or 2, wherein the fertilizer component is supplied to the extruder and the liquid component and binder are supplied to the extruder following the fertilizer component.


Embodiment 4: The method of embodiment 1 or 2, wherein the fertilizer component and the binder are supplied to the extruder and the liquid component is supplied to the extruder following the fertilizer component and the binder.


Embodiment 5: The method of embodiment 4, wherein the fertilizer component and the binder are supplied to a first zone of the extruder and the liquid component is supplied to a second zone downstream of the first zone.


Embodiment 6: The method of any one of embodiments 1-5, wherein the binder is present in an amount of 25 to 90 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler.


Embodiment 7: The method of any one of embodiments 1-6, wherein the liquid component is present in an amount of 7 to 25 weight percent, based on the combined weight of the fertilizer component, liquid component, binder and filler.


Embodiment 8: The method of any of the preceding embodiments, wherein the filler comprises chalk powder, silica, rice husk, dried distillers grains with solubles (DDGS), calcite, calcium oxide, calcium carbonate, dolomite, talc, sand, chalk powder, sodium carbonate, potassium carbonate, magnesium oxide, monopotassium phosphate, sodium bicarbonate, or a combination comprising one or more of the foregoing.


Embodiment 9: The method of any of the preceding embodiments, wherein the filler is present in an amount of 5 to 50 weight percent, based on the combined weight of the fertilizer component, liquid component, binder, and filler.


Embodiment 10: The method of any of the preceding embodiments, wherein the fertilizer component comprises a micronutrient, an inhibitor, or a combination comprising at least one of the foregoing.


Embodiment 11: The method of any of the preceding embodiments, wherein the binder comprises Plaster of Paris, flour, starch, cellulose, gluten, colloidal silica, kaolin, bentonite, or a combination comprising at least one of the foregoing.


Embodiment 12: The method of any of the preceding embodiments, wherein the liquid component comprises an aqueous component.


Embodiment 13, The method of any of the preceding embodiments, further comprising supplying a viscoelastic agent to the zoned extruder.


Embodiment 14: A method of making a fertilizer seed core, the method comprising: supplying a fertilizer component, an liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones; mixing the fertilizer component, liquid component, binder and filler to yield a thixotropic mixture; and passing the thixotropic mixture through the die head, wherein the die head comprises openings 0.5 to 4 millimeter in diameter and wherein the extrusion process has a residence of 5 seconds to 15 minutes.


Embodiment 15: The method of embodiment 14, wherein the fertilizer component is supplied to the extruder and the liquid component and binder are supplied to the extruder following the fertilizer component.


Embodiment 16: The method of embodiment 14, wherein the fertilizer component and the binder are supplied to the extruder and the liquid component is supplied to the extruder following the fertilizer component and the binder.


Embodiment 17: The method of embodiment 16, wherein the fertilizer component and the binder are supplied to a first zone of the extruder and the liquid component is supplied to a second zone downstream of the first zone.


Embodiment 18: The method of any of Embodiments 14-17, wherein the liquid component comprises an aqueous component.


Embodiment 19: The method of any of Embodiments 14-18, further comprising supplying a viscoelastic agent to the zoned extrude.


Embodiment 20: An extruder for performing the method of any of the preceding embodiments, wherein the extruder comprises a die head having openings with a land length of 3 to 16 millimeters.


Embodiment 21: The extruder of embodiment 20, wherein the die head comprises eccentric openings.


Embodiment 22: The extruder of embodiments 20 or 21, wherein the die head openings are conical.


Embodiment 23: The extruder of embodiment 22, wherein the die head has out flow openings having a diameter that is 30 to 70% of the intake opening diameter.


Embodiment 24: The extruder of any of embodiments 20-23, wherein the die head comprises a cooling jacket.


The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. “Or” means “and/or.” The endpoints of all ranges directed to the same component or property are inclusive and independently combinable. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including at least one of that term (e.g., “colorant(s)” includes at least one colorant). “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. Substantially as described herein generally refers to greater than or equal to 75%, for example, greater than or equal to 75%, for example, greater than or equal to 95%.


As used herein, a “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, —CHO is attached through carbon of the carbonyl group.


All references cited herein are incorporated by reference in their entirety. While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope herein. Accordingly, various modifications, adaptations and alternatives can occur to one skilled in the art without departing from the spirit and scope herein.

Claims
  • 1. A method of making a fertilizer seed core, the method comprising: supplying a fertilizer component, a liquid component, a binder and a filler to a zoned extruder comprising a die head, a screw, and at least three zones;supplying the fertilizer component and the binder to the extruder and supplying the liquid component to the extruder following the fertilizer component and the binder;mixing the fertilizer component, the liquid component, the binder and the filler to yield a thixotropic mixture comprising equal distribution of the fertilizer component, the liquid component, the binder and the filler; andpassing the thixotropic mixture through the die head, wherein the die head comprises openings 0.5 to 4 millimeter in diameter and wherein either one or both of the end of the screw is 1-15 millimeters from the die head and/or the extrusion process has a residence time of 5 to 15 minutes.
  • 2. The method of claim 1, wherein the die head openings have a land length of 3 to 16 millimeters.
  • 3. The method of claim 1, wherein the binder is supplied to the extruder following the fertilizer component.
  • 4. The method of claim 1, wherein the fertilizer component and the binder are supplied to a first zone of the extruder and the liquid component is supplied to a second zone downstream of the first zone.
  • 5. The method of claim 1, wherein the binder is present in an amount of 25 to 90 weight percent, based on a combined weight of the fertilizer component, the liquid component, the the binder and the filler.
  • 6. The method of claim 1, wherein the liquid component is present in an amount of 7 to 25 weight percent, based on a combined weight of the fertilizer component, the liquid component, the binder and the filler.
  • 7. The method of claim 1, wherein the filler comprises chalk powder, silica, rice husk, dried distillers grains with solubles (DDGS), calcite, calcium oxide, calcium carbonate, dolomite, talc, sand, chalk powder, sodium carbonate, potassium carbonate, magnesium oxide, monopotassium phosphate, sodium bicarbonate, or a combination comprising one or more of the foregoing.
  • 8. The method of claim 1, wherein the filler is present in an amount of 5 to 50 weight percent, based on the combined weight of the fertilizer component, the liquid component, the binder, and the filler.
  • 9. The method of claim 1, wherein the binder comprises Plaster of Paris, flour, starch, cellulose, gluten, colloidal silica, kaolin, bentonite, or a combination comprising at least one of the foregoing.
  • 10. The method of claim 1, wherein the liquid component comprises an aqueous component.
  • 11. The method of claim 1, further comprising supplying a viscoelastic agent to the zoned extruder.
  • 12. The method of claim 1, wherein the die head comprises eccentric openings.
  • 13. The method of claim 12, wherein the die head has out flow openings having a diameter that is 30 to 70% of an intake opening diameter of the die head.
  • 14. The method of claim 1, wherein the die head openings are conical.
  • 15. The method of claim 1, wherein the fertilizer component is present in an amount of 0.25 to 55 weight percent, based on a combined weight of the fertilizer component, liquid component, binder and filler.
  • 16. The method of claim 1, wherein the fertilizer component comprises a nitrification inhibitor, an urease inhibitor, and/or a micronutrient.
  • 17. The method of claim 16, wherein the fertilizer component comprises one or more of N-(n-butyl)thiophosphoric triamide, 3,4-dimethylpyrazole phosphate, thio-urea, dicyandiamide, phenyl phosphorodiamidate, 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazol, 2-amino-4-chloro-6-methyl-pyrimidine, 2-mercapto-benzothiazole, and/or 2-sulfaminalamidothiazole.
  • 18. The method of claim 16, wherein the fertilizer component comprises N-(n-butyl)thiophosphoric triamide and/or dicyandiamide.
  • 19. The method of claim 16, wherein the fertilizer component is present in an amount of 0.25 to 55 weight percent, based on a combined weight of the fertilizer component, the liquid component, the binder and the filler.
  • 20. The method of claim 1, wherein the binder is present at 25 to 87.75 weight percent, the liquid component is present at 7 to 25 weight percent, and the filler is present at 5 to 50 weight percent, based on a combined weight of the fertilizer component, the liquid component, the binder and the filler.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 371 of International Application No. PCT/IB2017/050683, filed Feb. 8, 2017, which claims priority to U.S. Application No. 62/292,393 filed Feb. 8, 2016, both of which are incorporated herein by reference in their entirety.

PCT Information
Filing Document Filing Date Country Kind
PCT/IB2017/050683 2/8/2017 WO
Publishing Document Publishing Date Country Kind
WO2017/137902 8/17/2017 WO A
US Referenced Citations (118)
Number Name Date Kind
3056723 Galloway Oct 1962 A
3232740 Sor et al. Feb 1966 A
3300294 Hollstein Jan 1967 A
3314778 Campbell et al. Apr 1967 A
3322528 Hamamoto May 1967 A
3326665 Schäfer et al. Jul 1967 A
3331677 Campbell et al. Jul 1967 A
3388989 Sor Jun 1968 A
3400011 Fox Sep 1968 A
3441539 Schafer et al. Apr 1969 A
3499748 Fraser Mar 1970 A
3825414 Lee et al. Jun 1974 A
3846529 Poteet, III Nov 1974 A
3870755 Kamo et al. Mar 1975 A
3954436 Vad et al. May 1976 A
3961329 Naidich Jul 1976 A
3962329 Schoenaich et al. Jul 1976 A
4003717 Cass Jan 1977 A
4062890 Shank Dec 1977 A
4082533 Wittenbrook et al. Apr 1978 A
4671914 Prochazka Jun 1987 A
4880455 Blank Nov 1989 A
4994100 Sutton et al. Feb 1991 A
5124451 Hackl et al. Jul 1992 A
5169954 Hackl et al. Dec 1992 A
5219465 Goertz et al. Jun 1993 A
5240400 Fujimoto Aug 1993 A
5264019 Gossett, Jr. et al. Nov 1993 A
5300135 Hudson et al. Apr 1994 A
5352265 Weston et al. Oct 1994 A
5399186 Derrah et al. Mar 1995 A
5405426 Timmons Apr 1995 A
5414083 Hackl et al. May 1995 A
5466274 Hudson et al. Nov 1995 A
5476528 Trimm Dec 1995 A
5597917 Hackl et al. Jan 1997 A
5645624 Naka et al. Jul 1997 A
5741521 Knight et al. Apr 1998 A
5803946 Petcavich et al. Sep 1998 A
5843347 Nguyen Dec 1998 A
5851261 Markusch et al. Dec 1998 A
5862610 Lipert Jan 1999 A
5917110 Kust Jun 1999 A
5976210 Sensibaugh Nov 1999 A
6048376 Miller Apr 2000 A
6048378 Moore Apr 2000 A
6099770 Akers Aug 2000 A
6231633 Hirano et al. May 2001 B1
6391454 Mao et al. May 2002 B1
6500223 Sakai et al. Dec 2002 B1
6576035 Hartmann et al. Jun 2003 B2
6749659 Yu et al. Jun 2004 B1
6900162 Wertz et al. May 2005 B2
6936573 Wertz et al. Aug 2005 B2
6936681 Wertz et al. Aug 2005 B1
7213367 Wertz et al. May 2007 B2
8163058 Whitehurst Apr 2012 B2
8419819 Sutton Apr 2013 B2
8603211 Rahn et al. Dec 2013 B2
9034072 Gabrielson et al. May 2015 B2
9376350 Pursell et al. Jun 2016 B2
9394210 Gabrielson et al. Jul 2016 B2
9422203 Waliwitiya Aug 2016 B2
9446993 Li et al. Sep 2016 B2
20030037485 Carnegie Feb 2003 A1
20030205072 Van Der Merwe et al. Nov 2003 A1
20030224031 Heier et al. Dec 2003 A1
20040001884 Moroni et al. Jan 2004 A1
20040016275 Hartmann et al. Jan 2004 A1
20040016276 Wynnyk et al. Jan 2004 A1
20040050127 Ambri Mar 2004 A1
20040163434 Quin Aug 2004 A1
20040182953 Knoer Sep 2004 A1
20060089259 Driessen et al. Apr 2006 A1
20060142157 Birthisel et al. Jun 2006 A1
20090270257 Pursell et al. Oct 2009 A1
20090317468 Letmathe et al. Dec 2009 A1
20100011825 Ogle et al. Jan 2010 A1
20100139348 Wan et al. Jun 2010 A1
20110036009 Bissonnette et al. Feb 2011 A1
20110154873 Burnham et al. Jun 2011 A1
20110275520 Frey et al. Nov 2011 A1
20120017659 Pursell et al. Jan 2012 A1
20120067094 Pursell et al. Mar 2012 A1
20120090366 Pursell et al. Apr 2012 A1
20130152649 Kweeder et al. Jun 2013 A1
20130231493 Shishkov Sep 2013 A1
20130259582 Birthisel et al. Oct 2013 A1
20130305796 Hudson et al. Nov 2013 A1
20140033779 Bertin et al. Feb 2014 A1
20140047884 Gabrielson et al. Feb 2014 A1
20140102156 Pursell et al. Apr 2014 A1
20140223978 Kuo et al. Aug 2014 A1
20140230322 Zhang et al. Aug 2014 A1
20140255605 Van Kaathoven et al. Sep 2014 A1
20150031786 Lambeth Jan 2015 A1
20150047402 Walker et al. Feb 2015 A1
20150052960 Makin et al. Feb 2015 A1
20150101379 Gabrielson et al. Apr 2015 A1
20150125639 Rosen May 2015 A1
20150152017 Schumski et al. Jun 2015 A1
20150197460 Gabrielson et al. Jul 2015 A1
20150239790 Iwig et al. Aug 2015 A1
20150291481 Neff et al. Oct 2015 A1
20150299062 McKnight et al. Oct 2015 A1
20160075609 Gabrielson et al. Mar 2016 A1
20160076062 Medoff et al. Mar 2016 A1
20160185682 Katz Jun 2016 A1
20160340265 Kanagalingam et al. Nov 2016 A1
20170088480 Kannan et al. Mar 2017 A1
20170362139 Zhang et al. Dec 2017 A1
20180022661 Achille et al. Jan 2018 A1
20180208513 Kanagalingam et al. Jul 2018 A1
20180208519 Kanagalingam et al. Jul 2018 A1
20180297903 Ledoux et al. Oct 2018 A1
20200039893 Koripelly et al. Feb 2020 A1
20200131098 Hegde et al. Apr 2020 A1
20200140353 Hegde et al. May 2020 A1
Foreign Referenced Citations (120)
Number Date Country
667645 Feb 1995 AU
2015212412 Sep 2016 AU
2441175 Mar 2004 CA
2701995 Oct 2011 CA
1044450 Aug 1990 CN
1126465 Jul 1996 CN
1145059 Mar 1997 CN
1417172 May 2003 CN
1666972 Sep 2005 CN
101108781 Jul 2006 CN
1298679 Feb 2007 CN
101037371 Sep 2007 CN
101134695 Mar 2008 CN
101134697 Mar 2008 CN
101177365 May 2008 CN
101289350 Oct 2008 CN
101289353 Oct 2008 CN
101323545 Dec 2008 CN
101384523 Mar 2009 CN
101486614 Jul 2009 CN
101628838 Jan 2010 CN
101638348 Feb 2010 CN
101723752 Jun 2010 CN
102143927 Aug 2011 CN
102267842 Dec 2011 CN
102295491 Dec 2011 CN
102432388 May 2012 CN
102503686 Jun 2012 CN
102557838 Jul 2012 CN
102746073 Oct 2012 CN
102826917 Dec 2012 CN
102951968 Mar 2013 CN
103319120 Sep 2013 CN
103588576 Feb 2014 CN
103755450 Apr 2014 CN
103755498 Apr 2014 CN
103772074 May 2014 CN
103787798 May 2014 CN
103833490 Jun 2014 CN
103102216 Dec 2014 CN
104177201 Dec 2014 CN
104230529 Dec 2014 CN
104230575 Dec 2014 CN
104261723 Jan 2015 CN
104276877 Jan 2015 CN
104311366 Jan 2015 CN
104326847 Feb 2015 CN
102936169 Apr 2015 CN
104557278 Apr 2015 CN
105669332 Jun 2016 CN
1146080 Mar 1963 DE
1905834 Nov 1972 DE
142044 Jun 1980 DE
3042662 Jun 1982 DE
4128828 Mar 1993 DE
19631764 Feb 1998 DE
0047556 Mar 1982 EP
0174247 Mar 1986 EP
0255752 Feb 1988 EP
0491238 Jun 1992 EP
0877722 Nov 1998 EP
1043295 Oct 2000 EP
1067093 Dec 2004 EP
1724247 Nov 2006 EP
2431346 Mar 2012 EP
893153 Jun 1944 FR
893153 Jun 1944 FR
1356105 Mar 1964 FR
1212605 Nov 1970 GB
1435678 May 1976 GB
1535807 Dec 1978 GB
348780 Jul 1991 JP
H07-033576 Feb 1995 JP
H1116798 Apr 1999 JP
H11263689 Sep 1999 JP
H11278973 Oct 1999 JP
2001294792 Oct 2001 JP
100974639 Aug 2010 KR
101485578 Dec 2014 KR
596113 Aug 2012 NZ
429048 May 1974 SU
1549926 Sep 2016 TW
8900079 Jan 1989 WO
WO 1995026942 Oct 1995 WO
WO 1996018591 Jun 1996 WO
WO 2003006399 Jan 2003 WO
WO 2003045877 Jun 2003 WO
03066207 Aug 2003 WO
2004047974 Jun 2004 WO
2004098858 Nov 2004 WO
WO 2005075602 Aug 2005 WO
WO 2006044393 Apr 2006 WO
WO 2007022732 Mar 2007 WO
WO 2007041234 Apr 2007 WO
WO 2007086773 Aug 2007 WO
WO 2013017888 Feb 2013 WO
WO 2013019121 Feb 2013 WO
WO 2013121384 Aug 2013 WO
2013128402 Sep 2013 WO
WO 2014189183 Nov 2014 WO
WO 2015001457 Jan 2015 WO
WO 2015114542 Aug 2015 WO
WO 2015170217 Nov 2015 WO
WO 2016091205 Jun 2016 WO
WO 2016107548 Jul 2016 WO
WO 2016186526 Nov 2016 WO
WO 2017013573 Jan 2017 WO
WO 2017081183 May 2017 WO
WO 2017087265 May 2017 WO
WO 2017087264 May 2017 WO
WO 2017100507 Jun 2017 WO
WO 2017137902 Aug 2017 WO
WO 2017013572 Oct 2017 WO
WO 2017168288 Oct 2017 WO
WO 2018162533 Sep 2018 WO
WO 2018193344 Oct 2018 WO
WO 2018193345 Oct 2018 WO
WO 2018193358 Oct 2018 WO
WO 2019030671 Feb 2019 WO
201105819 Apr 2012 ZA
Non-Patent Literature Citations (79)
Entry
Al-Kanani et al., “Volatilization of ammonia from urea-ammonium nitrate solutions as influenced by organic and inorganic additives.” Fertilizer research 1990, 23, 113-119.
Allison, “The enigma of soil nitrogen balance sheets,” Adv. Agro. 1995, 7:213-250.
Al-Zahrani, S.M., “Utilization of Polyethylene and Paraffin Waxes as Controlled delivery Systems for Different Fertilizers” Ind. Eng. Chem. Res., 2000, 39(2):367-371.
Bolan et al., “Soil Acidification and Liming Interactions with Nutrient and Heavy Metal Transformation and Bioavailability,” Advances in Agronomy, 78:215-272, (2003).
Bose, et al., “New protocol for Biginelli reaction-a practical synthesis of Monastrol,” ARKIVOC, 2005, 3:228-236.
Chien, et al., “Recent developments of fertilizer production and use to improve nutrient efficiency and minimize environmental impacts,” Adv. Agro., 2009, 102:267-322.
Ciurli, et al. “Structural properties of the nickel ions in; urease: novel insights into the catalytic and inhibition mechanisms,” Coord. Chem. Rev. 1999, 331:190-192.
Gautney, et al., “Feasibility of cogranulating the nitrogen loss inhibitors dicyandiamide, thiourea, phenyl phosphorodiamidate, and potassium ethyl xanthate with urea,” Ind. Eng. Chem. Prod. Res. Dev., 1984, 23:483-489.
Gioacchini, et al., “Influence of urease and nitrification inhibitors on N losses from soils fertilized with urea,” Biology and Fertility of Soils, 2002, 36(2):129-135.
Hays, “Symposium on Controlled Release Fertilizer,” J. Agri. Food, 1971, 19:797.
International Preliminary Reporton Patentability issued in counterpart International Patent Application No. PCT/IB2015/050654, dated Aug. 2, 2016.
International Preliminary Reporton Patentability issued in International Patent Application No. PCT/IB2016/054271, dated Oct. 18, 2017.
International Search Report and Written Opinion issued in counterpart International Patent Application No. PCT/IB2015/050654, dated May 19, 2015.
International Search Report and Written Opinion issued in counterpart International Patent Application No. PCT/IB2016/054271, dated Oct. 24, 2016.
International Search Report and Written Opinion issued in counterpart International Application No. PCT/IB2015/053056, dated Sep. 23, 2015.
International Search Report and Written opinion issued in International Application No. PCT/IB2018/052577, dated Aug. 1, 2018.
International Search Report and Written opinion issued in International Application No. PCT/IB2018/052578, dated Aug. 1, 2018.
International Search Report and Written opinion issued in International Application No. PCT/IB2018/052630, dated Aug. 9, 2018.
International Search Report and Written opinion issued in International Application No. PCT/IB2018/055946, dated Dec. 3, 2018.
International Search Report and Written Opinion issued in International Application No. PCT/IB2016/054270, dated Oct. 24, 2016.
International Search Report and Written opinion issued in International Application No. PCT/IB2017/050683, dated Jun. 20, 2017.
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2016/061486, dated Jan. 25, 2017.
International Search Report and Written Opinion issued in International Patent Application No. PCT/US2016/061487, dated Jan. 5, 2017.
Jarosiewicz & Tomaszewska, “Controlled-release NPK fertilizer encapsulated by polymeric membranes,” Journal of Agricultural and Food Chemistry, 2003, 51(2):413-417.
Kawakami, et al., “Physiological and yield responses of field-grown cotton to application of urea with the urease inhibitor NBPT and the nitrification inhibitor DCD,” European Journal of Agronomy, 2012, 43:147-154.
Lunt, et al., “Properties and Value of 1,1 -Diureido Isobutane (IBDU) as a Long-Lasting Nitrogen Fertilizer,” J. Agr. Food Chem., 1969, 17(6):1269-1271.
Mahmood et al., “Calcium Carbide-Based Formulations cause Slow Release of Acetylene and Ethylene in Soil and Nitrification Inhibition,” Communications in Soil Science and Plant Analysis, 2014, 45(17): 2277-2288.
Mahmood et al., “Effect of rate and application depth matrix-I calcium carbide based formulation on growth, yield and nitrogen uptake of wheat,” African Journal of Agricultural Research, 2011, 6(30): 6363-6398.
Mahmood et al., “Nutritional and physiological response of wheat to soil applied matrix-I formulated calcium carbide with and without nitro gen fertilizer,” Pakistan Journal of Nutrition 2012, 11(2): 154-159.
Office Action and Search Report issued in Corresponding Taiwanese Patent Application No. 104114189, dated May 9, 2019.
Office Action issued in corresponding Chinese Patent Application No. 201580008733.2, dated Jan. 11, 2019. (Machine Translation Provided).
Office Action issued in corresponding Chinese Patent Application No. 2015800087332, dated Jun. 13, 2019.
Office Action issued in corresponding Chinese Patent Application No. 201680051745.8, dated Jul. 23, 2019.
Office Action issued in corresponding Indian Patent Application No. 201617028561, dated Jun. 18, 2019.
Office Action issued in corresponding Taiwanese Patent Application No. 105122936, dated Sep. 5, 2019.
Office Action issued in corresponding Chinese Patent Application No. 201680051728.4, dated Aug. 11, 2020.
Office Action issued in European Patent Application No. 16741394.7, dated Dec. 7, 2018.
Patra, et al., “Use of urea coated with natural products to inhibit urea hydrolysis and nitrification in soil,” Biol. Fertil. Soils, 2009, 45:617-621.
Reddy, et al., New environmentally friendly solvent free syntehesis of dihydropyrimidinones catalysed by N-butyl-N, N-dimethyl-phenylethylammonium bromide, Tetrahedron Letters, 2003, 44:8173-8175.
Sanz-Cobena, et al., “Gaseous emissions of N2O and NO and NO3-leaching from urea applied with urease and nitrification inhibitors to a maize (Zea mays) crop,” Agriculture, Ecosystems & Environment, 2012, 149:64-73.
Search Report issued in corresponding Chinese Patent Application No. 201680051745.8, dated Jul. 2, 2019.
Search Report issued in corresponding Chinese Patent Application No. 201680051728.4, dated Aug. 5, 2020.
Sinclair et al., “Radiation Use Efficiency,” Advances in Agronomy 1999, 65: 215-265.
Soares, et al., “Ammonia volatilization losses from surface-applied urea with urease and nitrification inhibitors,” Soil Biology and Biochemistry, 2012, 52:82-89.
Subbarao, et al., “Scope and Strategies For Regulation of Nitrification in Agricultural Systems—Challenges and Opportunities,” Crit. Rev. Plant Sci., 2006, 25-303-335.
Trenkel, “Controlled-release and stabilized fertilizers in agriculture.” International fertilizer industry association 1997, 11:1-156.
Upadhyay,“Urease inhibitors: A review.” Indian Journal of Biotechnology 2012, 11:381-388.
Watson, et al., “Rate and mode of application of the urease inhibitor N-(n-butyl) thiophosphoric triamide on ammonia volatilization from surface-applied urea,” Soil Use and Management, 2008, 24:246-253.
Wu, et al., “Guidelines For The Use of Fertilizers,” Chinese Agricultural Press, 2000, 122-123. (English Translation).
Yixing, et al. “Application Technology of Novel Slow and Controlled Release Fertilizer,” China Three Gorges Press, 2008, 1, pp. 90 and 92.
Yongkang, et al. “Modern Drying Technology,” Chemical Industry Press, 2007, 1:719-722.
Zaman, et al., “Effects of urease and nitrification inhibitors on the efficient use of urea for pastoral systems,” J. Soil Science and Plant Nutrition, 2013, 59(4):649-659.
Zaman, et al., “Improving pasture growth and urea efficiency using N inhibitor, molybdenum and elemental Sulphur,” Journal of Soil Science and Plant Nutrition, 2014, 14(1):245-257.
Dongpo et al., “Soil biological activities at maize seedling stage under application of slow/controlled release nitrogen fertilizers” Chinese Journal of Applied Ecology 2006, 17(6), 1055-1059 (English Translation of conclusion).
Office Action issued in Corresponding Chinese Application No. 201680051728.4, dated Jun. 3, 2021 (No English Translation provided).
Office Action issued in Corresponding Chinese Application No. 201911019580.8, dated Jul. 13, 2021 (English Translation provided).
Office Action issued in Corresponding Chinese Application No. 201880039588.8, dated Jul. 14, 2021 (English Translation provided).
Chinese Patent No. 103102216; Date of Publication: Dec. 10, 2014; Abstract Only, 1 page.
German Patent No. 3042662; Date of Publication: Jun. 3, 1982; Abstract Only, 1 page.
French Patent No. 1356105; Date of Publication: Mar. 20, 1964; Machine Translation, 7 pages.
French Patent No. 893153; Date of Publication: Jun. 1, 1944; Machine Translation, 3 pages.
International Search Report for International Application No. PCT/IB2017/050683; dated Jun. 20, 2017; 7 pages.
Japanese Patent No. 348780; Date of Publication: Jul. 25, 1991; Machine Translation, 7 pages.
Written Opinion of the International Search Report for International Application No. PCT/IB2017/050683; dated Jun. 20, 2017; 10 pages.
Office Action issued in corresponding Chinese Application No. 201880040046.2, dated Sep. 1, 2021.
Office Action issued in corresponding Chinese Application No. 202010394499.4, dated Oct. 9, 2021.
Office Action issued in corresponding Chinese Application No. 201680051728.4, dated Oct. 27, 2021.
Azeem, et al. “Review on materials & methods to produce controlled release coated urea fertilizer,” Journal of Controlled Release, 2014, 181:11-21.
Babu, et al. “Current Progress on bio-based polymers and their future trends,” Progress in Biomaterials, 2013, 2:8.
Extended European Search Report issued in counterpart European Patent Application No. 20166713.6, dated Nov. 11, 2020.
Extended European Search Report issued in European Application No. 1686688.7, dated Jun. 13, 2019.
Lookchem. “Hydroxypropyl methyl cellulose,” https://www.lookchem.com/Hydroxypropyl-methyl-cellulose/ pp. 1-2, 2015.
Lubkowski, “Coating Fertilizer Granules with Biodegradable Materials for Controlled Fertilizer Release,” Environmental Engineering and Management Journal, 2014, 13:2573-2581.
Office Action issued in counterpart Chinese Patent Application No. 201680051745.8, dated Dec. 2, 2020.
Office Action and Search Report issued in Corresponding Chinese Application No. 201880040397.3, dated Mar. 30, 2022.
Cantarella et al., “Agronomic efficiency of NBPT as a urease inhibitor: A review.” Journal of advanced research 2018, 13, 19-27.
Dillon et al., “Nitrogen sources and timing effects on nitrogen loss and uptake in delayed flood rice.” Agronomy Journal 2012, 104, 466-472.
Mahmood et al., “Dicyandiamide increases the fertilizer N loss from an alkaline calcareous soil treated with 15N-labelled urea under warm climate and under different crops.” Biol Fertil Soils 2011, 47:619-631.
Soliman et al., “Effect of method of N-application and modified urea on N-15 recovery by rice.” Fertilizer research 43.1 (1995): 143-148.
Related Publications (1)
Number Date Country
20210070671 A1 Mar 2021 US
Provisional Applications (1)
Number Date Country
62292393 Feb 2016 US