WO2021075984A1 - Améliorations apportées et associées à des compositions d'engrais - Google Patents

Améliorations apportées et associées à des compositions d'engrais Download PDF

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Publication number
WO2021075984A1
WO2021075984A1 PCT/NZ2020/050128 NZ2020050128W WO2021075984A1 WO 2021075984 A1 WO2021075984 A1 WO 2021075984A1 NZ 2020050128 W NZ2020050128 W NZ 2020050128W WO 2021075984 A1 WO2021075984 A1 WO 2021075984A1
Authority
WO
WIPO (PCT)
Prior art keywords
nbpt
zinc oxide
urea
suspension
urea granules
Prior art date
Application number
PCT/NZ2020/050128
Other languages
English (en)
Inventor
Murray Selwin Zander
Regan James Zander
Jordan Ross ZANDER
Original Assignee
Southstar Technologies Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southstar Technologies Limited filed Critical Southstar Technologies Limited
Publication of WO2021075984A1 publication Critical patent/WO2021075984A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C05C3/005—Post-treatment
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C05C9/005—Post-treatment
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • 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
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • 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
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes
    • 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
    • C05G5/38—Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins

Definitions

  • the present invention relates to improvements in and relating to fertiliser compositions.
  • the present invention relates to improvements in and relating to blended granular fertiliser compositions.
  • blended granular fertiliser compositions where a urease inhibitor and/or nitrification in inhibitor has/have been coated onto a quantity of one of the blended granules, and wherein the other quantity of fertiliser granules is an acidic fertiliser.
  • NBPT and DMPP are respectively a urease inhibitor and a nitrification inhibitor both useful in respectively combatting N0 2 emissions (volatilisation) and N0 3 losses mentioned above.
  • NBPT N-(n-propyl) thiophosphoric triamide
  • DPSA 2-(3,4-dimethyl-1H-pyrazol- 1-yl) succinic acid
  • N fertilisers One problem that currently exists is how to efficiently apply nitrification inhibitors and urease inhibitors to land in need thereof. Ideally applying to the land at the same time as N fertilisers would be useful.
  • urea granules or ‘urea granules associated with NBPT as used herein take into account the fact NBPT can either be: coated onto the outside of urea granules; or melt mixed with urea (i.e. added to molten urea), and thereby incorporated into subsequently formed urea granules.
  • NBPT therein refers to a urea granule which includes NBPT therein and which has been formed by melting urea and adding NBPT thereto.
  • rapidly deterioration refers to NBPT breaking down and releasing measurable amounts of ammonia within or less than substantially 10 to 15 hours after being exposed to soil and/or moisture.
  • aqueous suspension formulation refers to a primarily water-based liquid suspension medium into which other optional suspension agents are added, to help hold zinc oxide and/or powdered NBPT in suspension, including one or more of, but not limited to: high melting point emulsifying wax;
  • FC50 suspension formulation refers to a 1:1 mixture of: linear alcohol ethoxylate (LAE);
  • suspension medium or ‘suspension’ as used herein refer to a liquid used to hold particulate matter including zinc oxide and/or powdered NBPT in suspension together with the help of one or more additional suspension agents.
  • suspension agents refers to substances which can help increase the viscosity of a liquid (i.e. by thickening the suspension medium) to assist in holding particulate matter in suspension over a period of time.
  • high melting point emulsifying wax as used herein generally refers:
  • granule refers to a particle of substance.
  • the particle will generally be of a size in the order of substantially between 1 mm -10mm and most preferably between 2mm-5mm.
  • the granule may be naturally occurring or may be fashioned by human manipulation.
  • the inventors have surprisingly discovered in field trials that protection of NBPT on a urea granule, using magnesium oxide, rapidly deteriorates when the granule is exposed to soil and/or moisture. A cost-effective solution to this problem was required.
  • a method of coating urea granules which include NBPT therein or NBPT as a layer thereon comprising the single step of:
  • a suspension of zinc oxide powder to the urea granules so as to form a layer thereon; wherein the zinc oxide powder is present in the suspension at substantially 5wt% to 50wt% of the total weight of the suspension medium, without the zinc oxide powder; and wherein the layer of zinc oxide protects the NBPT from rapid deterioration when exposed to soil and/or moisture.
  • a second aspect of the present invention there is provided the use of suspended zinc oxide powder to form a single protective layer on urea granules which include NBPT thereon or therein.
  • a third aspect of the present invention there is provided the use of suspended zinc oxide powder substantially as described above wherein the granules are coated with the single protective layer prior to mixing with a granulated acidic fertiliser.
  • a suspension including zinc oxide and NBPT as a single outer layer to control, or prolong protection of:
  • urea granules including NBPT therein, or thereon, together with a layer formed from suspended zinc oxide wherein the amount of zinc oxide used is substantially 0.03% of the total weight of the urea granules including zinc oxide.
  • a fertilizer blend including a quantity of urea granules coated with suspended zinc oxide substantially as described above together with a quantity of a fertiliser selected from granular or chip forms of: - Single super phosphate;
  • a fertilizer blend as substantially as described above wherein the fertilizer composition substantially as described above is blended with granular ammonium sulphate.
  • a ninth aspect of the present invention there is provided a method of protecting NBPT coated/containing urea granules substantially as described above wherein the amount of zinc oxide powder held in suspension is in a 1:1 ratio with the suspension formulation.
  • a suspension formulation which holds in suspension 45 micron or less zinc oxide powder at substantially 5wt% to 50wt% of the total weight of the suspension formulation.
  • a suspension formulation substantially as described above which also includes NBPT therein.
  • a suspension formulation which contains a 1:1 ratio of suspension medium to zinc oxide powder.
  • Figure 1 Is a graph showing the results of a 72-hour soil test measuring the ammonia release from various NBPT coated urea granules, including one which has an outer coat of magnesium oxide thereon, and uncoated urea granules (control);
  • Figure 2 is a graph showing the results of a 160-hour test measuring the ammonia release from various different NBPT coated urea granules, including one which also includes an outer layer of zinc oxide thereon, and uncoated urea granules (control);
  • Figure 3 is a graph showing the results of a 160-hour test measuring ammonia release of N-Protect coated urea granules mixed with GAS, and NBPT Coat coated urea granules with an outer layer of zinc oxide, and uncoated urea granules (control).
  • one preferred suspension formulation includes: i) an aqueous wax dispersion forming the suspension medium comprising:
  • aqueous wax dispersion substantially 10-50% by weight high melting point emulsifying wax; - water to make up to 100%; ii) (optionally) contains NBPT; wherein the amount of NBPT present is substantially: 10wt% -30wt% of the aqueous wax dispersion; iii) powdered zinc oxide at substantially 5wt% - 50wt%, of the aqueous wax dispersion including any NBPT; iv) (optionally) a dispersing clay; wherein the amount of dispersing clay is 5wt% - 50wt% of the aqueous wax dispersion excluding any NBPT or zinc oxide therein; v) a xanthan or guar gum being substantially 0.03wt% - 0.05wt% of the aqueous wax dispersion excluding any NBPT or zinc oxide therein.
  • zinc oxide is only added to the aqueous wax dispersion of Example 6 if it is not otherwise going to be applied to the urea granule.
  • the zinc oxide used in the examples above has a particle size of 45 micron.
  • NBPT is only added to the aqueous wax dispersion of Example 6 when NBPT is not otherwise being supplied to the urea granule.
  • aqueous suspension formulation is further detailed in the applicant’s PCT/NZ2020/050087 and NZ 760305 both of which are hereby incorporated by reference.
  • Aqueous Suspension according to Example 6 comprising:
  • Pico-SurfTM surfactant manufactured and sold by Sphere Fluidics including LAE. 2kg Cold Pressed Canola or boiled linseed oil 4kg ZnO powder sub 45 micron 4kg NBPT powder sub 45 micron
  • Example 10 This formulation is similar to Example 8 but the NBPT is in suspension for single step application.
  • Example 10 This formulation is similar to Example 8 but the NBPT is in suspension for single step application.
  • Aqueous Suspension according to Example 6 comprising:
  • Aqueous Suspension according to Example 6 comprising: 70kg KST wax emulsion
  • NBPT coat urea were compared against: uncoated urea (control);
  • NPBT coat coated urea together with an outer layer of MgO thereon.
  • This testing was undertaken using 10g of the various urea samples to be tested which were each added onto 100g of soil located within a sealed container.
  • the respective urea samples are saturated with water once applied to the soil to ensure ammonia release.
  • the sealed containers each having a lid with an ammonia detecting tube thereon communicating with the inside of the container once sealed.
  • the containers were then placed in a temperature-controlled room of 22 degrees Celsius and ammonia exposure levels measured on the tubes were recorded.
  • NBPT Coat urea and N-Protect coated urea produce similar ammonia release profiles.
  • NBPT Coat and N-Protect coated urea take around three times as long to release ammonia, compared to the control.
  • the NBPT Coat urea with an outer layer of MgO thereon had a quicker release of ammonia (i.e. rapid deterioration of NBPT) in soil than the NBPT Coat and N-Protect urea granules.
  • This new coating is a liquid suspension formulation of zinc oxide and has been named FC50.
  • FC50 coating when used as an outer layer was tested substantially following the same methodology described in relation to Figure 1 between N-protect coated urea granule, an NBPT Coat urea granule, and an NBPT coated urea granule having an outer coating of FC50 (NBPT Coat-FC50): these were again assessed against an uncoated urea (control) the results being shown in Figure 2.
  • the treated NBPT Coat urea and N-Protect urea are closely matched with uncoated urea releasing significantly earlier than the urea coated with the aforementioned NBPT treatments.
  • the NBPT Coat-FC50 urea however when viewed after a 90 hour plus duration had a significantly superior result to both N-Protect and NBPT Coat urea.
  • the inventors assessed whether the FC50 coat could provide superior protection of both a urea granule and an NBPT layer when mixed with granular ammonium sulphate (GAS) compared to NBPT Coat, and N-Protect coated, urea granules.
  • GAS granular ammonium sulphate
  • Suitable NBPT pre-coated urea may include but should not be limited to:
  • N-ProtectTM urea as manufactured by Solvay and sold by Ravensdown.
  • an NBPT coating may be applied to urea granules.
  • Suitable NBPT coatings may include dry powder form such as AGROTAINTM DRI-MAX manufactured and sold by KOCH Agronomic Services or in a liquid formulation such as AGROTAINTM Advanced 1.0.
  • liquid formulation of NBPT may be in the form of a wax emulsion.
  • the suspended zinc oxide may be applied to NBPT coated/containing urea granules in any number of different ways.
  • the zinc oxide suspension formulation (which may optionally in some embodiments also include NBPT therein) may be added to a rotating drum, or other suitable mixing apparatus, in which the urea granules, NBPT coated/containing granules to be coated, have been placed.
  • the zinc oxide suspension formulation may be sprayed onto the NBPT coated/containing urea granules.
  • the zinc oxide suspension formulation may also include NBPT therein and be sprayed onto to urea granules, to apply both NBPT and zinc oxide in a single step.
  • the suspension formulation used to suspend the zinc oxide powder and optionally the NBPT may be an aqueous suspension formulation or a non-organic solvent formulation as defined herein.
  • suspension formulations used in the present invention remain on the urea granule and form a layer containing the zinc oxide therein.
  • the zinc oxide powder may preferably have a particle size of 45 microns or less.
  • the amount of zinc oxide powder to protect the NBPT on, or in, the urea granules may be substantially 0.02% of the total weight of the urea granules including zinc oxide.
  • the NBPT may coated onto the urea granules as aforementioned.
  • the NBPT may be melt mixed with the urea to form urea granules which contain the NBPT therein.
  • the NBPT used in the suspension may be in the form of a powder.
  • the NBPT used in a powder blend with zinc oxide may have a particle size of substantially 45 microns or less. That is the zinc oxide powder and NBPT powder should have substantially similar particle sizes.
  • suspension medium may be any liquid formulation which is a non-organic solvent and which:
  • Such suspension mediums may include one or more surfactants therein to assist with the drying process to create a layer on the urea granules.
  • Some surfactants may include LAE therein.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Fertilizers (AREA)

Abstract

L'invention concerne un procédé d'enrobage de granulés d'urée dans lesquels se trouve du NBPT ou qui comprennent du NBPT sous forme d'enrobage, comprenant l'étape unique consistant à appliquer une suspension de poudre d'oxyde de zinc aux granulés d'urée de manière à former une couche sur ceux-ci ; la poudre d'oxyde de zinc étant présente dans la suspension à hauteur de pratiquement 5 % en poids à 50 % en poids par rapport au poids total du milieu de suspension, sans la poudre d'oxyde de zinc ; et la couche d'oxyde de zinc protégeant le NBPT d'une détérioration rapide lors de l'exposition à des engrais acides, de la terre et/ou de l'humidité.
PCT/NZ2020/050128 2019-10-17 2020-10-19 Améliorations apportées et associées à des compositions d'engrais WO2021075984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NZ75832919 2019-10-17
NZ758329 2019-10-17

Publications (1)

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WO2021075984A1 true WO2021075984A1 (fr) 2021-04-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023022611A1 (fr) * 2021-08-20 2023-02-23 Southstar Technologies Limited Améliorations apportées à des compositions de revêtement de fertilisant et se rapportant à celles-ci

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4395569B2 (ja) * 2001-12-21 2010-01-13 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ナノ微粒子分散物の製造のための表面を変性した酸化亜鉛
CN103800269A (zh) * 2014-02-27 2014-05-21 陆燕 一种纳米氧化锌防晒霜
WO2015034375A1 (fr) * 2013-09-04 2015-03-12 South Star Fertilizers Limited Améliorations apportées et associées à des compositions d'engrais
WO2017042194A1 (fr) * 2015-09-08 2017-03-16 Yara International Asa Composition à base d'urée-sulfate d'ammonium et son procédé de fabrication
WO2017081183A1 (fr) * 2015-11-12 2017-05-18 Yara International Asa Composition mixte améliorée à base d'urée et son procédé de fabrication
EP3309137A1 (fr) * 2016-10-13 2018-04-18 YARA International ASA Composition améliorée à base d'urée comprenant du soufre élémentaire et son procédé de fabrication
EP3372576A1 (fr) * 2017-03-07 2018-09-12 Yara International ASA Composition à base d'urée et son procédé de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4395569B2 (ja) * 2001-12-21 2010-01-13 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ナノ微粒子分散物の製造のための表面を変性した酸化亜鉛
WO2015034375A1 (fr) * 2013-09-04 2015-03-12 South Star Fertilizers Limited Améliorations apportées et associées à des compositions d'engrais
CN103800269A (zh) * 2014-02-27 2014-05-21 陆燕 一种纳米氧化锌防晒霜
WO2017042194A1 (fr) * 2015-09-08 2017-03-16 Yara International Asa Composition à base d'urée-sulfate d'ammonium et son procédé de fabrication
WO2017081183A1 (fr) * 2015-11-12 2017-05-18 Yara International Asa Composition mixte améliorée à base d'urée et son procédé de fabrication
EP3309137A1 (fr) * 2016-10-13 2018-04-18 YARA International ASA Composition améliorée à base d'urée comprenant du soufre élémentaire et son procédé de fabrication
EP3372576A1 (fr) * 2017-03-07 2018-09-12 Yara International ASA Composition à base d'urée et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023022611A1 (fr) * 2021-08-20 2023-02-23 Southstar Technologies Limited Améliorations apportées à des compositions de revêtement de fertilisant et se rapportant à celles-ci
AU2021218200A1 (en) * 2021-08-20 2023-03-09 Southstar Technologies Limited Improvements in and relating to fertiliser compositions

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