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WO2024099948A1 - Utilisation de phosphate de diméthylpyrazole dans des engrais de type can - Google Patents

Utilisation de phosphate de diméthylpyrazole dans des engrais de type can Download PDF

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Publication number
WO2024099948A1
WO2024099948A1 PCT/EP2023/080810 EP2023080810W WO2024099948A1 WO 2024099948 A1 WO2024099948 A1 WO 2024099948A1 EP 2023080810 W EP2023080810 W EP 2023080810W WO 2024099948 A1 WO2024099948 A1 WO 2024099948A1
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Prior art keywords
weight
component
calcium
magnesium carbonate
composition
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English (en)
Inventor
Maarten Staal
Uwe Thiel
Markus Schmid
Manuel KNAUER
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BASF SE
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BASF SE
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Priority to EP23801424.5A priority Critical patent/EP4615816A1/fr
Publication of WO2024099948A1 publication Critical patent/WO2024099948A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to use of dimethylpyrazole phosphate (DMPP) in solid fertilizer compositions A containing ammoniumnitrate and a salt selected form calcium carbonate, magnesium carbonate, calcium sulfate and combinations thereof.
  • DMPP dimethylpyrazole phosphate
  • the present invention also relates to a fertilizer composition comprising DMPP and the solid fertilizer composition A, and to a process for producing a fertilizer composition comprising the incorporation of DMPP into the fertilizer composition A.
  • Fertilizers are applied to soil or to plant tissues to supply the plant with nutrients including macro nutrients and micronutrients.
  • Nitrogen fertilizers are made from ammonia (NH 3 ) produced by the Haber-Bosch process, which is used as a feedstock for all other nitrogen fertilizers, such as anhydrous ammonium nitrate (NH4NO3) and urea (CO(NH2)2).
  • CAN fertilizers also known as nitro-limestone or nitrochalk, is one of the widely used nitrogen fertilizer providing ammonium compound.
  • CAN fertilizers can be considered as near-neutral in its effect on soil pH and therefore can be used on soils that have a low pH without lowering the pH further.
  • CAN are nitrogen fertilisers which contains equal parts of fast acting nitrate-nitrogen and longer lasting ammonium-nitrogen and an inorganic component containing calcium minerals, typically limestone. This ensures a more continuous nitrogen supply to the crop and thus better efficiency of use, and also makes it suitable for unseasonal application during summer or winter.
  • Ammonium compounds are converted microbially to nitrate (nitrification) in the soil within a relatively short time.
  • Nitrate however, can be leached from the soil.
  • the leached fraction is no longer available for plant nutrition, and so for this reason rapid nitrification is undesirable.
  • nitrification inhibitors are added to it, which inhibit nitrifying microbes in the soil responsible for the conversion of ammonium (NH4 + ) into nitrate ( NO3-), to increase the residence time of NH 4 + .
  • DMPP 3,4-dimethylpyrazole phosphate
  • DMPP 3,4-dimethylpyrazole phosphate
  • transition metal complexes such as zinc, copper or manganese complexes – see for example U.S. Pat. No.4,522,642.
  • the volatility of the pyrazole compounds can thus be reduced.
  • the widespread application of zinc, copper or manganese to the soil is, however, undesirable.
  • Complexes of alkali metals or alkaline earth metals which are environmentally tolerable, are not adequately stable, however, and hydrolyze in the aqueous environment. It has furthermore been attempted by neutralization of the pyrazole compounds with mineral acids, such as phosphoric acid or hydrochloric acid, to decrease their volatility.
  • DE 4128828A describes the use of nitrates and phosphates of 3-methylpyrazole for the coating of fertilizers.
  • U.S. Pat. No.3,635,690 also describes the stabilization of pyrazole derivatives by mineral acids, such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
  • mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
  • These acidic salts of the pyrazole compounds may partly or completely dissociate into the pyrazole compound and salts of phosphoric acid under the high pH conditions present in CAN fertilizers. Dissociation, however results in increased volatility and loss of the pyrazole compound.
  • DE 4128828A suggests the sealing of the coated fertilizer with wax or oil.
  • CAN fertilizers In the case of hygroscopic active compound salts, however, this process does not lead to a satisfactory resistance to hydrolysis. What is more, nitrification inhibitors based on the pyrazole compounds and at the same time suitable for CAN fertilizers have rarely been disclosed.
  • WO 2015/086823A2 describes fertilizer mixtures comprising 2-(N-3,4-dimethylpyrazole)- succinic acid (DMPSA), which are based on calcium ammonium nitrate (CAN) mineral fertilizers, and also to a process for preparing DMPSA.
  • the CAN fertilizers described therein generally contain 6 to 15% by weight, especially 10% of calcium, which equals concentrations of calcium carbonate of 15 to 37.5% by weight, especially 25% by weight.
  • EP 4015489 discloses solid, particulate, ammonium based fertilizers containing an ammonium salt, a nitrification inhibitor, e. g. a 3,4-dimethylpyrazole derivative, such as DMPP or DMPSA, and an acidic compound in an amount of up to 5% by weight, and an anticaking and/or moisture repellent coating comprising a wax, a phosphate ester and an amine.
  • a nitrification inhibitor e. g. a 3,4-dimethylpyrazole derivative, such as DMPP or DMPSA
  • an acidic compound in an amount of up to 5% by weight
  • an anticaking and/or moisture repellent coating comprising a wax, a phosphate ester and an amine.
  • DMPP degradation should be less than 20% after 6 months storage at 20°C.
  • CAN type fertilizers which contain DMPP whose content does not significantly change during prolonged storage of the fertilizer.
  • the fertilizers should be less susceptible to loss of ammonia caused by nitrification.
  • DMPP in a solid fertilizer composition, especially a CAN-type fertilizer composition, in which at least a portion of calcium carbonate (CaCO3) of the inorganic component is replaced by calcium sulfate (CaSO4) and/or magnesium carbonate (MgCO3), such that the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition in anhydrous form.
  • such fertilizers show an increased stability of DMPP and reduced loss thereof, in particular during storage.
  • DMPP would not be stable in CAN and CAN type fertilizers due to the high pH value of CAN fertilizers and CAN type fertilizers, which is typically above pH 6.
  • CAN fertilizer compositions and CAN type fertilizer compositions as described herein which typically have a pH value of above pH 6, e. g. a pH ⁇ 7.
  • the pH of the fertilizer composition remains nearly unchanged when at least certain amount of CaCO 3 is replaced with CaSO 4 and/or MgCO 3 in accordance with the present invention.
  • the fertilizer composition according to the invention still has a pH value of ca. 7.
  • a first aspect of the present invention relates to the use of a composition (b) containing at least one of the following compounds: (b.1) magnesium carbonate, (b.2) calcium sulfate, (b.3) calcium magnesium carbonate (b.4) magnesium oxide, or a mixture of calcium carbonate with at least one of magnesium carbonate, calcium sulfate, calcium magnesium carbonate and magnesium oxide, where the total amount of calcium carbonate, magnesium carbonate, calcium sulfate, calcium magnesium carbonate and magnesium oxide is at least 95%, based on the total weight of the component (b); in a solid fertilizer composition A containing (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4
  • the present invention relates to use of dimethylpyrazole phosphate (DMPP) as a nitrification inhibitor in a solid fertilizer composition A comprising (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b) containing at least one of the following compounds: (b.1) magnesium carbonate, (b.2) calcium sulfate, (b.3) calcium magnesium carbonate, (b.4) and magnesium oxide, or a mixture of calcium carbonate with at least one of magnesium carbonate, calcium sulfate, calcium magnesium carbonate and magnesium oxide, where the total amount
  • DMPP dimethylpyrazole phosphate
  • the present invention is beneficial for application of DMPP in CAN and CAN type fertilizers.
  • CAN and CAN type fertilizers are widely used fertilizers, but the conversion of ammonium to nitrate, when applied to the soil, results in N2O emissions and the formed nitrate can leach into ground water.
  • the present invention enables DMPP, which is one of the most efficient nitrification inhibitors, to be applied to CAN and CAN type fertilizers and to reduce the N losses from CAN and CAN type fertilizers.
  • a third aspect of the present invention is a fertilizer composition
  • a fertilizer composition comprising - 99 to 99.99% by weight, in particular 99.5 to 99.9% by weight, especially 99.6 to 99.8% by weight, based on the total weight of the fertilizer composition in anhydrous form, of a fertilizer composition A, as defined herein and hereinafter; and - 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight, especially 0.2 to 0.4% by weight, based on the total weight of the fertilizer composition in anhydrous form, of DMPP.
  • Further aspects of the invention relate to a process for producing a fertilizer composition, as defined herein and hereinafter, which comprises the incorporation of DMPP into a fertilizer composition A, as defined as defined herein and hereinafter.
  • CAN and CAN type fertilizer refers to a solid fertilizer composition A.
  • CAN fertilizer refers to a ammonium nitrate fertilizer wherein the total amount of calcium carbonate and magnesium carbonate is at least 20% by weight, based on the total weight of the fertilizer
  • CAN type fertilizer refers to a fertilizer, where the proportion of the total amount of calcium carbonate and magnesium carbonate is lower than 20% by weight.
  • the solid fertilizer composition A comprises 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a).
  • Ammonium nitrate (NH 4 NO 3 ) may be prepared by any suitable methods known to skilled person in the art, for example by reacting ammonia gas with nitric acid in water. The water must be then removed from the ammonium nitrate aqueous solution to yield solid ammonium nitrate, most often by evaporation.
  • the pH of the solid fertilizer composition is the pH of a 10% by weight aqueous solution of the fertilizer.
  • the solid fertilizer composition A further comprises 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of the component (b).
  • the component (b) of the fertilizer composition contains at least one of compound selected from the group consisting of magnesium carbonate, calcium sulfate, calcium magnesium carbonate and magnesium oxide, or a mixture of two or more of said compounds.
  • the component (b) may contain calcium carbonate (CaCO 3 ).
  • the component (b) does not contain more than 80% by weight, in particular not more than 65% by weight, especially not more than 50% by weight of calcium carbonate, based on the total weight of the component (b).
  • the amount of calcium carbonate in component (b) may be as low as 0% by weight or not more than 10% by weight, based on the total weight of the component (b).
  • the composition A comprises 0 to 17.9% by weight or 1 to 17.9% by weight, in particular 0 to 15.9% by weight or 2 to 15.9% by weight, in particular 0 to 14.9% by weight or 2 to 14.9% by weight, especially 0 to 12% by weight or 1 to 12% by weight of calcium carbonate, based on the total weight of the fertilizer composition A in anhydrous form.
  • any amounts given for calcium carbonate, magnesium carbonate and calcium sulfate refer to the anhydrates of these salts and are based on the total weight of the component (b), if not stated otherwise.
  • the total theoretical amount of magnesium carbonate (MgCO 3 ) and calcium sulfate (CaSO 4 ) provided by the components/constituents of component (b) is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e. g. from 3 to 40% by weight, preferably from 4 to 35% by weight and especially from 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • the theoretical amount of magnesium carbonate is understood as the stoichiometric proportions of Mg and carbonate (CO 3 ) present in the component (b) which correspond to the formula MgCO3.
  • the theoretical amount of calcium sulfate is understood as the stoichiometric proportions of Ca and sulfate (SO4) present in the component (b) which correspond to the formula CaSO 4 .
  • the component (b) may be pure components or a mixture of its constituents, provided that the theoretical amount of magnesium carbonate and calcium sulfate in the fertilizer composition is fulfilled.
  • the component (b) may be selected from the following constituents or mixtures of constituents, hereinafter compositions (i) to (xii): (i) magnesium carbonate; (ii) calcium sulfate; (iii) mixtures of magnesium carbonate with calcium sulfate, (iv) mixtures of magnesium carbonate with calcium carbonate, where the amount of calcium carbonate is in particular not more than 80% by weight and especially not more than 50% by weight, e.g.1 to 80% by weight, especially 4 to 50% by weight, based on the total weight of component (b), (v) mixtures of magnesium oxide with calcium carbonate, where the amount of calcium carbonate is in particular not more than 80% by weight and especially not more than 50% by weight, e.g.1 to 80% by weight, especially 4 to 50% by weight, based on the total weight of component (b), (vi) mixtures of calcium carbonate with calcium sulfate, where the amount of calcium carbonate is in particular not more than 80% by weight and especially not more than 50%
  • the total amount of the mentioned compounds is in particular at least 90% by weight, especially at least 95% by weight or at least 99% by weight, based on the total weight of the respective compositions (i)-(xii).
  • the weight ratio of calcium carbonate, including the calcium carbonate contained in dolomite, to the total weight of the other compounds, i. e. magnesium carbonate, including the magnesium carbonate contained in dolomite, magnesium oxide and calcium sulfate is in particular in the range of 1:20 to 1:1.
  • compositions (i)-(xii) preference is given to components (b), which are selected from compositions (i), (ii), (iii) and (iv), where in the composition (iv) the weight ratio of calcium carbonate to magnesium carbonate is in particular in the range of 1:1 to 1:20.
  • the amount of magnesium carbonate is preferably at least 90% by weight, in particular at least 95% by weight.
  • the amount of calcium sulfate is preferably at least 90% by weight, in particular at least 95% by weight.
  • the total amount of calcium sulfate and magnesium carbonate is preferably at least 90% by weight, in particular at least 95% by weight.
  • the total amount of calcium carbonate and magnesium carbonate is preferably at least 90% by weight, in particular at least 95% by weight.
  • the composition (b), in particular the compositions (i) to (xii), especially the preferred compositions (i) to (iv) may additionally contain further constituents, which are different from magnesium carbonate, calcium sulfate, calcium carbonate and calcium magnesium carbonate, in amounts of up to 10% by weight, in particular up to 5% by weight, based on the total amount of the respective composition (b) or (i) to (xii), respectively.
  • These further constituents are typically minerals which are suitable as inert inorganic components of fertilizer compositions which may be contained in minerals used as constituents of the composition in CAN type fertilizers.
  • such further constituents include silicates, alumosilicates, alumina, calcium oxide, calcium hydroxide, magnesium oxide, alkalimetal phosphate and alkalimetal hydrogen phosphates, or mixtures thereof.
  • the component (b) may contain up to 10% by weight, in particular up to 5% by weight of magnesium oxide, based on the total weight of the component (b).
  • any magnesium carbonate can be used in the component (b) of the fertilizer composition.
  • any magnesium carbonate can be used in the component (b) of the fertilizer composition.
  • magnesium carbonate occurs in nature in large quantities as magnesite (bitter spar) (MgCO 3 ) with a hardness of 4-41 ⁇ 2.
  • MgCO3 ⁇ 2H2O nesquehonite
  • MgCO3 ⁇ 5H2O lansfordite
  • Any of these minerals can be used as a magnesium carbonate for the purpose of the invention.
  • a combination of MgO with calcium carbonate can be used as a source of magnesium carbonate, optionally in combination with further magnesium carbonate, as long as the amount of Ca and Mg is such that the theoretical amounts of magnesium carbonate and calcium carbonate is as defined herein.
  • Magnesium carbonate can also be used in the form of dolomite, as long as the theoretical amount of MgCO3 contributed by dolomit and any other source of magnesium carbonate is as defined herein.
  • a combination of MgO with one of magnesium carbonate, calcium magnesium carbonate and calcium sulfate may also be used.
  • the amount of MgO is preferably in the range of 0.1 to 5 % by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • any calcium sulfate can be used in the fertilizer composition. Usually, naturally occurring calcium sulfate will be used.
  • calcium sulfate occurs naturally in the form of the minerals anhydrite CaSO4, gypsum Ca[SO4] ⁇ 2H2O (dihydrate) and bassanite Ca[SO4] ⁇ 1 ⁇ 2H2O (hemihydrate) in evaporites. Any of these minerals can be used as a magnesium carbonate for the purpose of the invention. Principally, any calcium carbonate can be used in the fertilizer composition. Usually, naturally occurring calcium carbonate will be used. Typically, calcium carbonate is found frequently in geologic settings and constitutes an enormous carbon reservoir. Calcium carbonate occurs as aragonite, calcite and dolomite as significant constituents of the calcium cycle.
  • the carbonate minerals form the rock types are limestone, chalk, marble, travertine, tufa, and others. Any of these minerals can be used as a magnesium carbonate for the purpose of the invention. Principally, any magnesium oxide can be used in the fertilizer composition.
  • the magnesium oxide may be naturally occurring magnesium oxide, such as periklas, or industrially produced magnesium oxide, including calcined magnesit or calcined magnesium hydroxide.
  • calcium carbonate can also be used in the form of dolomite, as long as the amount of calcium carbonate contributed by dolomite and any further calcium carbonate is as defined herein.
  • the component (b) comprises magnesium carbonate.
  • the component (b) comprises at least 90%, particularly at least 95%, preferably at least 99% by weight, especially 100%, based on the total weight of the component (b), of magnesium carbonate.
  • the component (b) is a mixture comprising magnesium carbonate and calcium sulfate. In this mixture, the weight ratio of magnesium carbonate to calcium sulfate is generally in the range of 1:40 to 40:1, preferably in the range of 1:30 to 30:1, especially in the range of 1:21 to 21:1.
  • the mixture of subgroup (1-b) does not contain more than 10%, in particular not more than 5% by weight or not more than 1% by weight, based on the total weight of component (b), of calcium carbonate.
  • the component (b) is selected from mixtures comprising calcium carbonate and at least one of magnesium carbonate and calcium sulfate, in particular from mixtures comprising calcium carbonate and magnesium carbonate and optionally calcium sulfate.
  • the component (b) is selected from mixtures comprising calcium carbonate and at least one of magnesium carbonate and calcium sulfate, in particular from mixtures comprising calcium carbonate and magnesium carbonate and optionally calcium sulfate, such as mixtures of calcium carbonate and calcium sulfate and mixtures of calcium carbonate, magnesium carbonate and calcium sulfate.
  • the weight ratio of calcium carbonate to the total weight of calcium sulfate and magnesium carbonate is generally in the range of 1:20 to 10:1 and frequently in the range of 1:15 to 5:1. High contents of MgCO3 are preferred.
  • the weight ratio of calcium carbonate to the total weight of calcium sulfate and magnesium carbonate is in the range of 1:20 to 1:1, in particular in the range of 1:15 to 1:2, more preferably in the range of 1:12 to 1:5.
  • the relative amount of calcium carbonate is preferably chosen such that the fertilizer composition A comprises calcium carbonate in an amount of 1 to 17.9% by weight, in particular 1 to 15.9% by weight, more particularly 1 to 14.9% by weight and especially 1 to 12% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • the component (b) is a mixture of calcium carbonate and magnesium carbonate, where the total amount of is at least 99% of the mixture.
  • this group of embodiments is referred to as subgroup (2-b).
  • the weight ratio of calcium carbonate to magnesium carbonate is generally in the range of 1:20 to 10:1 and frequently in the range of 1:15 to 5:1. High contents of MgCO 3 are preferred. Therefore, in a preferred group of embodiments the weight ratio of calcium carbonate to magnesium carbonate is in the range of 1:20 to 1:1, in particular in the range of 1:15 to 1:2, more preferably in the range of 1:12 to 1:5.
  • the relative amount of calcium carbonate is preferably choses such that the fertilizer composition A comprises calcium carbonate in an amount of 1 to 17.9% by weight, in particular 2 to 15.9% by weight, more particularly 1 to 14.9% by weight and especially 1 to 12% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b) which is according to group (1) of embodiments, wherein the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e.
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b), which is according to subgroup (1-a) or (1-b) of embodiment (1), wherein the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e.
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b), which is according to subgroup (1-b) of embodiment (1), wherein the weight ratio of magnesium carbonate to calcium sulfate is generally in the range of 1:40 to 40:1, preferably in the range of 1:30 to 30:1, especially in the range of 1:21 to 21:1, wherein the total amount of magnesium carbonate and calcium sulfate is at least 3%
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b), which is according to group (2) of embodiments, wherein the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e.
  • the weight ratio of calcium carbonate to the total weight of calcium sulfate and magnesium carbonate is preferably in the range of 1:20 to 1:1, in particular in the range of 1:15 to 1:2, especially in the range of 1:12 to 1:5.
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b), which is according to subgroups (2-a) or (2-b) of embodiment (2), wherein the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e.
  • the weight ratio of calcium carbonate to the total weight of calcium sulfate and magnesium carbonate is preferably in the range of 1:20 to 1:1, in particular in the range of 1:15 to 1:2, especially in the range of 1:12 to 1:5.
  • the solid fertilizer composition A comprises (a) 60 to 97% by weight, preferably 65 to 96% by weight, especially 66 to 95% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of ammonium nitrate as component (a); and (b) 3 to 40% by weight, preferably 4 to 35% by weight, especially 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of a component (b), which is according to subgroup (2-b) of embodiment (2), wherein the weight ratio of calcium carbonate to magnesium carbonate is generally in the range of 1:20 to 10:1, frequently in the range of 1:15 to 5:1, preferably in the range of 1:20 to 1:1, in particular in the range of 1:15 to 1:2, especially in the range of 1:12 to 1:5, wherein the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the
  • composition A may further contain up to 15% by weight, preferably up to 10% by weight, especially up to 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of further ingredients. Further ingredients are for example trace elements, further minerals, standardizers, binders, and the like.
  • the water fraction in the composition A is preferably not more than 1.0% by weight, more preferably not more than 0.5% by weight, more particularly not more than 0.3% by weight, based on the total weight of the fertilizer composition A in anhydrous form, and is therefore negligible in the balance of quantities.
  • the water fraction refers to free water, i. e. to water which is not bound in the crystalline materials of component (b), i.e. which is not hydrate water crystalline materials of component (b).
  • the nitrogen content of the composition A in anhydrous form is preferably 20% by weight, more preferably at least 22% by weight, very preferably in the range of 25 to 29% by weight, especially in the range of 26 to 28% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • the composition A comprises frequently in the range of 22 to 28% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of nitrogen, in which case, for example, there may be 13.5% by weight of fast-acting nitrate nitrogen and 13.5% by weight of slow-acting ammonium nitrogen, based on the total weight of the fertilizer composition A in anhydrous form.
  • the composition A may essentially consist of the aforementioned components (a) and (b) or may comprise further components. Frequently, the amount of the components (a) and (b) is at least 85% by weight, in particular at least 90% by weight and especially at least 95% by weight, based on the total weight of the composition A, except for water.
  • the term “essentially consists” means that the total amount of the aforementioned components (a) and (b) is at least 98% by weight, based on the total weight of the composition A, except for water.
  • Further constituents include, for example, trace elements, micronutrients, such as boron compounds, and salts of zinc, molybdenum, manganese, copper or iron, further minerals, standardizers and binders.
  • the composition A may comprise in the range of 0.1 to 1% by weight, preferably in the range of 0.1 to 0.5% by weight, more particularly in the range of 0.15 to 0.3% by weight, based on the total weight of the fertilizer composition A in anhydrous form, of boron as element and/or in the form of boron compounds.
  • the solid fertilizer composition A can be dissolved in water and may be in form of an aqueous solution.
  • pH value of the aqueous solution of the fertilizer composition A is greater than 6, preferably greater than 6.3, especially greater than or equal to 6.5.
  • the composition of A is calcium ammonium nitrate (CAN) mineral fertilizer, which contains at least one of magnesium carbonate and calcium sulfate, where the total amount of magnesium carbonate and calcium sulfate is at least 3% by weight, preferably at least 4% by weight, especially at least 5% by weight, based on the total weight of the fertilizer composition A in anhydrous form, e. g. from 3 to 40% by weight, preferably from 4 to 35% by weight and especially from 5 to 34% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • CAN calcium ammonium nitrate
  • the composition A of the invention customarily has a water content in the range of 0.1 to 0.5% by weight, preferably in the range of 0.1 to 0.2% by weight, more particularly in the range of 0.15% by weight, based on the total weight of the fertilizer composition A.
  • DMPP dimethylpyrazole phosphate is used as a nitrification inhibitor in a solid fertilizer composition A, as defined herein.
  • the abbreviation DMPP refers to dimethylpyrazole phosphate, in particular to 3,4-dimethylpyrazole phosphate (CAS 202842-98-6).
  • DMPP is typically the 1:1 adduct of dimethylpyrazole and phosphoric acid and has the molecular formula C5H8N2*H3PO4.
  • a liquid formulation of DMPP is commercially available as Vibelsol® of BASF SE)
  • DMPP comprises or is 3,4-dimethylpyrazole phosphate.
  • the content of 3,4-dimethylpyrazole phosphate in commercially available DMPP is at least 90%, based on the total weight of dimethylpyrazole phosphate present in the commercially available DMPP.
  • DMPP may be prepared by any suitable methods, which are known to a skilled person in the art.
  • DMPP may be used in solid or preferably in liquid form, i. e. dissolved in a suitable solvent, such as water. In most preferred group of embodiments, DMPP is used in the form of an aqueous solution.
  • the concentration of DMPP in the aqueous solution of DMPP is preferably in the range of 20 to 45% by weight, preferably in the range of 25 to 40% by weight, more preferably in the range of 27.5 to 36% by weight, based on the total weight of the solution of DMPP.
  • DMPP as an aqueous solution having a pH in the range of 1 to 5, especially in the range of 1 to 3.
  • phosphates contemplated are Na 2 HPO 4 , Na 3 PO 4 , K 2 HPO 4 , K 3 PO 4 , diammonium phosphate or calcium ammonium phosphate.
  • the amount of DMPP is in the range of 0.01 to 0.2% by weight, preferably in the range of 0.05 to 0.16% by weight, especially in the range of 0.1 to 0.14% by weight, based on the total weight of the fertilizer composition A in anhydrous form.
  • DMPP for example a liquid formulation of DMPP is sprayed onto composition A, in particular to granules thereof, and subsequently mixed to obtain a homogeneous distribution of DMPP on composition A.
  • Fertilizer composition and production process As mentioned above, the use of DMPP as a nitrification inhibitor in a solid fertilizer composition A, as defined herein, is associated with the unexpected benefits.
  • the fertilizer compositions according to the invention comprise - 99 to 99.99% by weight, in particular 99.5 to 99.9% by weight, especially 99.6 to 99.8% by weight, based on the total weight of the fertilizer composition in anhydrous form, of a fertilizer composition A, as defined herein; and - 0.01 to 0.2% by weight, preferably 0.05 to 0.16% by weight, especially 0.1 to 0.14% by weight, based on the total weight of the fertilizer composition in anhydrous form, of DMPP.
  • the solid fertilizer composition of the present invention can be produced by analogy to fertilizer compositions. Such processes comprise the incorporation of DMPP into the fertilizer composition A, as defined herein the required amounts.
  • the amount of DMPP used for producing the inventive fertilizer composition is in the range of 0.05 to 0.16% by weight, especially 0.1 to 0.14% by weight, based on the total weight of the fertilizer composition in anhydrous form.
  • the inventive fertilizer composition may also include small amounts of water, as for example in the range of 0.1 to 0.2% by weight, based on the total weight of the fertilizer composition including water. Large amounts of water in the fertilizer composition ought to be avoided.
  • the inventive fertilizer composition may be produced, for example, according to the following method:
  • the solid fertilizer composition A which is preferably calcium ammonium nitrate mineral fertilizer
  • DMPP calcium ammonium nitrate mineral fertilizer
  • the method is known, for example, from EP 0529473A1, hereby referenced in full.
  • Such application methods involve mechanical movement of the composition A to homogenize the application, for example by means of stirrers or by movement of the composition A for example in a drum.
  • the composition A is dried in order to remove the moisture introduced with the mixture.
  • the drying is preferably effected up to such a level of dryness that caking or dissolution of the composition A is reliably prevented.
  • it is advantageous to store coated or impregnated composition A for several days.
  • the coated or impregnated composition A may be further treated with e.g. anti-caking or anti-dust treatments.
  • the solid fertilizer composition A may be in form of granulates, powders, chips, tablets or extrudates. Particular preference is given to granulates. Thereby, the fertilizer compositions are obtained in the form of a granulate.
  • Typical particle sizes of these granules may be in the range of 1 to 8 mm, in particular in the range of 1.5 to 6 mm.
  • the particle size refers to the size of at least 90% by weight of the granules contained in the granulate. It can be determined by sieving.
  • DMPP may also be added during the production of the granulate, e. g. by incorporating the DMPP in to the mass subjected to granulation.
  • the fertilizer compositions of the invention may be applied to the soil or to the plant tissue. The amount of the fertilizer composition applied will require on the demands of the plant.
  • the fertilizer composition of the invention is typically applied as solid fertilizer. EXAMPLES The invention is elucidated in more detail by the examples hereinafter. 1.
  • CAN and CAN type fertilizer used in the following examples are commercially available products. Prior to their treatment with DMPP they were analyzed with respect to their elemental composition as described below. All fertilizer samples were solid granules with an average particle size between 1 – 5 mm.
  • Nitrification inhibitor (DMPP) A DMPP containing nitrification inhibitor commercially available from BASF as Vibelsol®. 2. Fertilizer treatment 4 kg CAN fertilizer granules were added to a rotating disk mixer. While mixing, 15 g Vibelsol® formulation is sprayed onto the fertilizer granules using a syringe.
  • AN ammoniumnitrate
  • CaCO3 calcium carbonate
  • MgO magnesium oxide
  • CaSO 4 calcium sulfate
  • the following table summarizes the pH values, the analyzed mineral contents, calculated contents of AN, CaCO 3 , MgCO 3 , MgO and CaSO 4 of the fertilizer samples 1 to 5.
  • 4.2 Fertilizer treatment with the nitrification inhibitor and storage The untreated fertilizer samples 1 to 5 were treated with Vibelsol® and stored in closed bottles at 40 °C for 1 and 2 months, respectively. After the storage, the amount of active ingredient DMPP was analyzed using HPLC. Active ingredient recovery was calculated by dividing the measured DMPP concentration by the DMPP concentration measured before storage.
  • the results in table 2 show that, surprisingly, a good DMPP stability is achieved with CAN samples containing less than 15 wt.-% CaCO3.

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

Abstract

La présente invention concerne par conséquent l'utilisation de diméthylpyrazole phosphate (DMPP) en tant qu'inhibiteur de nitrification dans une composition d'engrais solide A comprenant (a) de 60 à 97 % en poids, de préférence de 65 à 96 % en poids, en particulier de 66 à 95 % en poids, sur la base du poids total de la composition d'engrais A sous forme anhydre, de nitrate d'ammonium en tant que composant (a) ; et (b) de 3 à 40 % en poids, de préférence de 4 à 35 % en poids, en particulier de 5 à 34 % en poids, par rapport au poids total de la composition d'engrais A sous forme anhydre, d'un composant (b) contenant au moins l'un des composés suivants : (b.1) du carbonate de magnésium, (b.2) du sulfate de calcium, (b.3) du carbonate de calcium-magnésium, (b.4) et de l'oxyde de magnésium, ou un mélange de carbonate de calcium avec au moins l'un parmi le carbonate de magnésium, le sulfate de calcium, le carbonate de calcium-magnésium et l'oxyde de magnésium, la quantité totale de carbonate de calcium, de carbonate de magnésium, de sulfate de calcium, de carbonate de calcium-magnésium et d'oxyde de magnésium étant d'au moins 90 % en poids, en particulier d'au moins 95 % en poids, sur la base du poids total du composant (b) ; la quantité théorique totale de carbonate de magnésium et de sulfate de calcium fournie par les composants contenus dans le composant (b) étant d'au moins 3 % en poids, de préférence d'au moins 4 % en poids, en particulier d'au moins 5 % en poids, sur la base du poids total de la composition d'engrais A sous forme anhydre, par exemple de 3 à 40 % en poids, de préférence de 4 à 35 % en poids et en particulier de 5 à 34 % en poids, sur la base du poids total de la composition d'engrais A sous forme anhydre. La présente invention concerne également une composition d'engrais comprenant du DMPP et la composition d'engrais solide A, et un procédé de production d'une composition d'engrais comprenant l'incorporation de DMPP dans la composition d'engrais A.
PCT/EP2023/080810 2022-11-07 2023-11-06 Utilisation de phosphate de diméthylpyrazole dans des engrais de type can Ceased WO2024099948A1 (fr)

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