WO2019204163A1 - Compositions d'engrais à base d'azote liquide et additifs associés - Google Patents

Compositions d'engrais à base d'azote liquide et additifs associés Download PDF

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Publication number
WO2019204163A1
WO2019204163A1 PCT/US2019/027346 US2019027346W WO2019204163A1 WO 2019204163 A1 WO2019204163 A1 WO 2019204163A1 US 2019027346 W US2019027346 W US 2019027346W WO 2019204163 A1 WO2019204163 A1 WO 2019204163A1
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Prior art keywords
fertilizer
urea
liquid
inhibitor
nitrification
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PCT/US2019/027346
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English (en)
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Michael Massoud Hojjatie
Thomas David Fairweather
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Tessenderlo Kerley, Inc.
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Publication of WO2019204163A1 publication Critical patent/WO2019204163A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • 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
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C05C9/02—Fertilisers containing urea or urea compounds containing urea-formaldehyde condensates
    • 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
    • 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 is related to liquid nitrogen fertilizer compositions, and a method for producing such fertilizer compositions.
  • the present invention furthermore relates to additive packages for liquid nitrogen fertilizer compositions, and to nitrogen fertilizer compositions with urease and/or nitrification inhibitors.
  • Urea is a white crystalline solid containing about 46% nitrogen that is widely used in the agricultural industry as a nitrogen fertilizer. World urea consumption is estimated to have exceeded 160 million tons in 2014-2016.
  • urea fertilizer can be purchased as prills or as a granulated material.
  • Urea can be applied to soil as a solid or as an aqueous solution.
  • Aqueous urea solutions also can be applied to certain crops as a foliar spray.
  • Urea's high nitrogen content (-46%) helps reduce handling, storage and transportation costs over other dry nitrogen forms. Urea, when properly applied, results in crop yield increases equal to other forms of nitrogen fertilizer.
  • Nitrogen from urea can be lost to the atmosphere if urea fertilizer remains on the soil surface for extended periods of time during warm weather. Urea breakdown can begin as soon as it is applied to the soil. Typically, urea does not break down if the soil is totally dry. However, in the presence of the enzyme urease and a small amount of soil moisture, urea normally hydrolyzes to ammonia and carbon dioxide. This can occur in 2 to 4 days; more quickly on high pH soils and at higher temperatures.
  • Urease is a nickel-dependent metallo-enzyme, which catalyzes the hydrolysis of urea to ammonia and carbamate. The carbamate then spontaneously hydrolyzes to form carbonic acid and a second molecule of ammonia. At physiological pH, the carbonic acid proton dissociates and the ammonia molecules equilibrate with water, becoming protonated and resulting in a net increase in pH.
  • the rate of catalyzed hydrolysis is 10 14 times the rate of the uncatalyzed reaction.
  • Nickel-dependent ureases are found in a wide array of different organisms; many have been isolated from various bacteria, fungi, and higher plants.
  • nitrate rather than ammonium. Once an ammonium ion is formed, volatilization losses are not a factor and the nitrogen can be utilized for crop growth directly or be converted to nitrate-nitrogen by soil microorganisms. This conversion occurs rapidly in the presence of bacteria and may lead to an excess of nitrate-nitrogen in the soil environment. In order to prevent this rapid conversion, nitrification inhibitors have been developed to inhibit bacterial activity. For example, Nitrosomonas bacteria in the soil transform ammonia into nitrite anion (N0 2 ) that in turn is oxidized to form a nitrate (N0 3 ) anion by Nitrobacter and
  • Nitrosolobus bacteria as follows:
  • the nitrification rate is most rapid in soils with pH values between 7 and 8, and decreases with decreasing pH values.
  • Nitrification of ammonia to nitrate introduces nitrate into the soil, from which the nitrate then leaches into vicinal groundwater.
  • urea containing liquid fertilizers like for example UAN, triazone-urea mixtures (like N-sure) and urea-aldehyde adducts.
  • Liquid fertilizer solutions and fluid fertilizers are popular in many areas because they are safe to handle, convenient to mix with other nutrients and chemicals and are easily applied.
  • a solution of urea [CO(NH 2 ) 2 ] and ammonium nitrate [NH 4 NO 3 ] (UAN) containing between 28 and 32 percent nitrogen (N) is one of the most popular liquid N fertilizers. It is frequently used with other fertilizers, including ammonium thiosulfate.
  • UAN ammonium thiosulfate.
  • Such solutions of UAN are widely used as a source of N for plant nutrition.
  • the NO 3 portion (25 percent of the total N) is immediately available for plant uptake.
  • the NH 4 + fraction (25 percent of the total N) can also be assimilated directly by most plants, but is rapidly oxidized by soil bacteria to form NO 3 (nitrate). Soil enzymes hydrolyze the remaining urea portion
  • SCU sulfur coated urea
  • PCU polymer coated urea
  • PSCU sulfur/polymer coated urea
  • a device for a slow-release fertilizers based on ammonium for low nitrate plant feeding comprising a hollow body with an opening is described in EP356755.
  • the hollow body is filled with the ammonium fertilizer.
  • EP476550 describes a soil additive ball for the nitrate-free supply of nitrogen to plants consisting of gypsum to slow down volatilization of urea.
  • urease inhibitor prevent or depress the transformation of amide nitrogen in urea to ammonia. They slow down the rate of hydrolysis of urea and reduce the volatilization of ammonia.
  • Nitrification inhibitors delay the oxidation of ammonium by depressing the activity of the soil bacteria responsible for nitrification.
  • nitrification inhibitors and urease inhibitors.
  • agents for improving the nitrogen utilization of mineral and/or organic fertilizers that contain urea are described in EP1183220. These agents comprised alkyl, aryl, and aralkylamino compounds.
  • Urea fertilizers containing urease inhibitors comprising metal nitrate are described in GB2285803.
  • urease inhibition in urea based fertilizers by phosphorus compounds is described in EP119494, EP119495, EP119487, WO02/083697, WO00/058317, WO97/022568, US569800, US4824783, US5883297, US5883297, US5698003, US4618691, US4540428, US4539037, US4537614, US4530714, US4518413, US4517007, US4517004, US4517003, US45l7,002, US4932992, US4932992 and US4242325.
  • Urease and nitrification inhibition of nitrogenous fertilizers with castor oil and oil derived from plants is described in US6315807 and US4932991.
  • Use of heterocyclic compounds as urease inhibitors is described in US4932991 and US4954156.
  • Organo Boranes or their derivatives are used as an antagonistic inhibitor to urease with urea fertilizers in US4462819.
  • a commercially successful urease inhibitor preferably is (1) environmentally and toxicologically safe under a reasonable set of handling conditions, (2) non-phytotoxic, (3) highly active and specific for the urease enzyme, (4) cost effective, (5) nonvolatile and compatible with a wide range of fertilizer materials, and (6) has mobility similar to that of urea.
  • N-(n-butyl)-thiophosphoric triamide is a well-known example of urease inhibitors.
  • NBPT is commercially available under the trademark Agrotain® available from Agrotain International, St. Louis, MO (Koch).
  • Dicyandiamide DCD
  • 2-chloro-6-(trichloromethyl)-pyridine nitrapyrin
  • DCD diicyandiamide
  • nitrapyrin 2-chloro-6-(trichloromethyl)-pyridine
  • DMPP 3, 4- dimethylpyrazolphosphate
  • NBPT and DCD are organic compounds and not freely soluble in aqueous inorganic fertilizers.
  • Several references describe the dissolution of NBPT and/or DCD and its incorporation into urea based liquid fertilizers. Usually organic solvents are used to dissolve these compounds, which either are not compatible with aqueous (water) based fertilizers and/or environmentally hazardous (WO2017/083714, US4517003, W02017/081183, US4530714, US2007/157689, US8048189, US2015/0174140, US2014/40090432).
  • Such solutions advantageously can then be added as additive to N- and/or S-containing fertilizers, wherein especially a mixed N-S fertilizer (III) can be advantageous to the end user.
  • Additives are easy to use and give less dosage problems. The use of concentrates further reduces transport costs.
  • the art does not yet provide a water based solution of such urease and/or nitrification inhibitors, wherein the inhibitors are present in high concentration.
  • the art does not yet provide either solutions with reduced amount of organic solvents.
  • sulfur containing fertilizers are in use for liquid fertilizer applications, for example (bi)sulfite based liquid fertilizers (like potassium sulfite), polysulfide based liquid fertilizers, and/or thiosulfate based liquid fertilizers.
  • Preferred in the present invention are thiosulfate based liquid fertilizers.
  • Thiosulfate based liquid fertilizers are well known, and comprise for example:
  • Thio-Sul® Ammonium thiosulfate (Thio-Sul®), which is a 50-60% aqueous solution, (grade is 12-0- 0-26S).
  • KTS® Potassium thiosulfate
  • CaTs® Calcium thiosulfate
  • Magnesium thiosulfate which is a 24-25% solution, (grade is 0-0-0- 10S- 4Mg)
  • Thiosulfate is an important intermediate in microbial sulfur cycling in soils and sediments. It has been suggested that tetrathionate might be an inhibitor of soil urease by reacting with -SH groups in jackbean urease to form an S-sulpho derivative, as follows:
  • Ammonium thiosulfate has been used in conjunction with urea and urea-containing fertilizer products for the purpose of reducing nitrogen loss.
  • urea ammonium nitrate fertilizer solution UAN
  • addition of ammonium thiosulfate to an urea ammonium nitrate fertilizer solution (UAN) can slow the urea hydrolysis rates after application to soil (Sullivan, D.M., and Havlin, J. L., Soil Sci. Soc. Am. J., 56, 957-960, 1992).
  • UAN urea ammonium nitrate fertilizer solution
  • the urease inhibition activity of ammonium thiosulfate is not observed in all circumstances, and the effect is considered insufficient.
  • thiosulfate may be the effective nitrification inhibitor.
  • Liquid sulfur based fertilizers like thiosulfate fertilizers are often combined by a distributor or farmer with other liquid fertilizers, like for example dissolved urea or UAN.
  • liquid fertilizer compositions comprising a sulfur based fertilizer, urea and an urease and/or nitrification inhibitor.
  • US 5024689 describes liquid fertilizers comprising urea, ammonium thiosulfate, and dicyandi amide.
  • Gautney et al. (Ind. Eng. Chem. Prod. Res. Dev. (1985) 24: 155-181) describe the solubility of DCD and some other inhibitors in liquid fertilizers.
  • US 5364438 describes a UAN with added NBPT and DCD. The amounts are described as up to 0.4wt% NBPT and up to 2 wt% DCD.
  • US 5364438 further describes a UAN with 1.4 wt% of DCD and 2 wt% of ammonium thiosulfate.
  • the amount of S in this liquid fertilizer is below 1 wt%.
  • the invention relates to an additive solution (I) of at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2), said solution comprising: urea (al) and/or an urea-aldehyde adduct (a2) and/or an urea-triazone fertilizer (a3), water (b), at least one organic co-solvent (c), and further
  • At least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) wherein compounds (a) are present in an amount of at least about 20 wt%, preferably at least about 25 wt%, relative to the total weight of compounds (a)+(b)+(c), and
  • compounds (d) are generally present in an amount of from about 0.04 to about 75 wt%, from about 0.04 to about 60 wt%, usually from about 0.04 to about 40 wt%, preferably from about 0.1 to about 30 wt%, relative to the total weight of the additive solution (I).
  • compounds (al) and/or (a3) are preferred over compounds (a2) in view of their capacity to dissolve high amounts of the inhibitors (dl and/or d2).
  • Compounds (al), (a2) and (a3) may be referred to herein individually or collectively as“(a)” or“compound (a)” or“compounds (a)”.
  • the additive solution hence comprises: urea (al) and/or an urea-triazone fertilizer (a3), water (b), at least one organic co-solvent (c), and further
  • the amount of urease inhibitors (dl) is at least about 1 wt%, preferably at least about 2 wt%, at least about 2.5 wt%, at least about 3 wt%, at least about 4 wt%, more preferably at least about 5 wt%, relative to the total weight of the additive solution (I).
  • the additive solution comprises: urea (al) and/or an urea-triazone fertilizer (a3), water (b), at least one organic co-solvent (c), and further
  • nitrification inhibitor (d2) at least one nitrification inhibitor (d2), or a combination of at least one nitrification (d2) inhibitor and at least one urease inhibitor (dl),
  • the amount of nitrification inhibitors (d2) is at least about 0.1 wt%, preferably at least about 1 wt%, more preferably at least about 2 wt%, at least about 2.5 wt%, at least about 3 wt%, at least about 4 wt%, even at least about 5 wt%, relative to the total weight of the additive solution (I).
  • the amount of compounds (d) is at most about 80, 75, 70, 65, 60, 55, 50, 49,
  • the amount of compounds (d) is at least about 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 wt% or more.
  • the amount of compounds (d) is from about 0.04 to about 50 wt%, preferably from about 0.04 to about 40 wt%, and more preferably from about 0.1 to about 30 wt%.
  • the minimal amount of compounds (d) in the additive solution (I) of the invention is at least about 1, 2, 3, 4 or 5wt%.
  • the additive solution comprises urease inhibitors (dl) in an amount of at least about 3, 4, 5, 6, 7, 8, 9 wt%, at least about 10 wt%, preferably at least about 15 wt%, up to 30 about wt% and more, and/or a nitrification inhibitors (d2) in an amount of at least about 3, 4,
  • the co-solvent generally is a polar protic and/or a polar non-protic solvent that is miscible with water, though some non-polar solvents can be used too.
  • the invention furthermore relates to a process for preparing an additive solution (I) as described above, comprising the step of dissolving at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) in a solution comprising: (a) urea (al) and/or an urea- aldehyde adduct (a2) and/or an urea-triazone fertilizer (a3), (b) water and at (c) least one organic co-solvent that preferably is selected from polar protic and/or polar non-protic solvents that are miscible with water.
  • Preferred solvents (a) are urea (al), urea-triazone fertilizers or a mixture of both (al+a3).
  • the invention furthermore relates to a process for preparing a liquid fertilizer (II) having at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2), comprising the step of adding to a liquid fertilizer at least one additive solution (I) as described above.
  • the liquid fertilizer (II) comprises a sulfur containing fertilizer, the sulfur containing fertilizer preferably being chosen from polysulfides, (bi)sulfites and/or from thiosulfate fertilizers.
  • the sulfur containing fertilizer is selected from thiosulfate fertilizers.
  • the sulfur containing fertilizer is selected from (bi)sulfites fertilizers.
  • the sulfur containing fertilizer is selected from polysulfide fertilizer.
  • the liquid fertilizer (II) comprises a liquid nitrogen containing fertilizer (like UAN) that can be provided in the form of a stock solution that still has to be diluted with water.
  • the invention also relates to a liquid fertilizer (II) that is prepared from a process as described herein [any of the above]
  • the invention furthermore relates to a liquid mixed N-S fertilizer composition (III) comprising: water,
  • a sulfur containing fertilizer selected from polysulfides, (bi)sulfites and/or thiosulfate fertilizers,
  • a nitrogen containing fertilizer more in particular an urea based nitrogenous fertilizer
  • At least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) wherein the amount of S is more than about 2 wt%, preferably more than about 5 wt%, relative to the total weight of the fertilizer (III), and
  • N is more than about 5 wt%, preferably more than about 20 wt%, and more preferably more than about 25 wt%, relative to the total weight of the fertilizer (III).
  • the liquid mixed N-S fertilizer composition (III) further comprises at least one co-solvent selected from polar protic and/or from polar non-protic solvents that are miscible with water.
  • the liquid mixed N-S fertilizer composition (III) further comprises at least one of compounds (al) and/or (a2) and/or (a3) as defined above.
  • the at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) present in said composition (III), are dissolved in an aqueous solution containing at least one of compounds (al) and/or (a2) and/or (a3), and further at least one co-solvent that preferably is selected from polar protic and/or polar non-protic solvents that are miscible with water.
  • the composition (III) of the invention is prepared from an additive solution (I) as described above [any of the above]
  • the invention furthermore relates to a kit-in-parts containing:
  • At least one additive solution (I) as described optionally containing a dye
  • liquid sulfur containing fertilizer that preferably is a stock solution of a thiosulfate fertilizer, the liquid sulfur containing fertilizer optionally containing a different dye, and,
  • a sheet or a card with dosage recommendations optionally, a sheet or a card with dosage recommendations.
  • an urea solution in water in combination with an organic solvent provided a way to permit the dissolution of high concentrations of urease inhibitors like NBPT and/or nitrification inhibitors like DCD. Inhibitor concentrations of up to about 20 wt% and more, even up to about 30 wt% and more could be reached, with substantially lowered amount of organic solvents.
  • the urea solution in its most simple form is an aqueous solution of "free" urea in water.
  • Urea dissolves well in water.
  • the form of urea plays herein no role. Both prills and granules can be used.
  • "liquid" urea products available in the market such as the products from Rentech Energy that are provided under the form of a liquid (having ⁇ 52 wt% urea) or under the form of a paste (having ⁇ 69 wt% of urea).
  • N-Sure® which is an urea-triazone fertilizer.
  • Urea-aldehyde adducts can also be used.
  • urea (al) and/or of urea-aldehyde adducts (a2) and/or of urea-triazone fertilizers (a3) is present in the additive solution (I) of the invention, which in a preferred embodiment is an aqueous solution.
  • suitable urea-aldehyde adducts are urea-formaldehyde adducts.
  • Compounds (al), (a2) and (a3) advantageously are all different from each other.
  • the amount of urea (al) and/or urea-aldehyde adducts (a2) and/or of urea-triazone fertilizers (a3) is at least about 25 wt%, more preferably at least about 30 wt%. Weight percentages (wt%) are herein relative to the total weight of compounds (a)+(b)+(c). [0058] Preferred in the context of the invention are urea (al) and/or urea-triazone fertilizers (a3), as these permit dissolving of the highest amounts of NBPT and/or DCD.
  • An urea-water solution is one example of a preferred way according to the invention to dissolve the urease (dl) and/or nitrification inhibitors (d2).
  • the ratio of water to urea generally will be between about 40 wt% water to about 60 wt% urea and about 60 wt% water to about 40 wt% urea, relative to the total weight of water and urea.
  • the preferred ratio of urea to water is about 1 : 1.
  • an urea-triazone fertilizer (a3) is used as solvent.
  • Urea-triazone is a liquid composition that may contain an amount of water of as low as about 8 wt%.
  • an urea (al) solution in water (b) is used for dissolving the above inhibitors (like NBPT and/or DCD).
  • an urea-triazone fertilizer generally having from about 5 to about 10 wt% of water is used as solvent by itself or in combination with urea.
  • both urea (al) and urea-triazone fertilizers (a3) were used as solvent.
  • Compounds (al), (a2) and/or (a3) are preferred over UAN as the latter does not allow to dissolve the same high amounts of the above inhibitors (like NBPT and/or DCD).
  • the amount of UAN in the additive solution (I) of the invention is less than about 20 wt%, less than about 15 wt%, less than about 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 wt%, relative to the total weight of this solution (I). Even more preferably less than about 0.5, 0.4, 0.3, 0.2 or 0.1 wt% of UAN is present in the additive solution (I) of the invention.
  • the additive solution will contain about 3 wt% water or more, preferable about 4 wt% or more. If urea is used, the amount of water generally will be about 15 wt% or more, preferably about 20 wt% or more. In one embodiment, the amount of water is about 40 wt% or less, preferably about 35 wt% or less.
  • the additive solution further comprises one or more organic solvents (further referred to herein as "co-solvents").
  • co-solvents organic solvents
  • the combination of dissolved urea and organic solvent is unexpectedly effective to dissolve high amounts of the inhibitors (d) in solution.
  • the same is true for the combination of an urea-triazone fertilizer and organic solvents.
  • This provides significant benefits, such as the ability to produce a highly stable additive solution.
  • This provides significant economic benefits, because the additive solution may be stored in a stable condition for extended periods of time at room temperature, without the need to add stabilizers such as ammonium polyphosphates.
  • the co-solvent (c) is herein different from compounds (a) and also different from (b) water (which is an inorganic solvent).
  • Co-solvents (c) for use in the additive solution of the invention are preferably chosen from one or more polar protic and/or polar non-protic solvents. Most preferred in the context of the invention are solvents that are miscible with water.
  • Protic organic solvents that might be used include C1-C6 alcohols like methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol; glycols like ethylene glycol, propylene glycol, glycerol; amino-alcohols like ethanolamine, di- ethanol amine and triethanol amine.
  • Other suitable solvents are dimethylsulfonoxide,
  • Non-protic polar solvents include dimethylsulfoxide (DMSO), dimethyl formamide (DMF), triethyl phosphate, dioxane and the like.
  • Preferred organic co-solvents include ethanol, ethylene glycol, DMSO and/or dioxane. Most preferred are ethanol and/or DMSO for dissolving for increasing the solubility of the inhibitors. Ethanol can work for both NBPT and DCD. DMSO is preferred for DCD.
  • the amounts of inhibitors (in particular NBPT and/or DCD) throughout the invention are expressed as weight percentages (wt%) relative to the total weight of the additive solution (I).
  • the co-solvent (c) is preferably used in an amount from about 5 to about 60 wt%, preferably in an amount from about 10 to about 55 wt%, and more preferably from about 15 to about 50 wt%, relative to the total weight of the additive solution (I) of the invention. In preferred embodiments, their amount is below about 45 wt%, preferably below about 40 wt%.
  • NMP N-methyl-2-pyrrolidone
  • PVP polyvinylpyrrolidone
  • the amount of NMP and PVP is less than about 10, 9, 9, 7, 6, 5, 4, 3, 2 wt%, more preferably less than about 1 wt%, more preferably less than about 0.5, 0.4, 0.3, 0.2 or 0.1 wt%.
  • the additive solution of the invention is substantially free from NMP and PVP, as these can be health deleterious . NMP for instance is listed as teratogenic.
  • Solutions (I) of the invention comprise at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (dl). Compounds (dl) and (d2) herein are different from each other, otherwise they would not have been mentioned separately.
  • a solution (I) of at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) said solution comprising urea (al), an urea- aldehyde adduct (a2) and/or an urea-triazone fertilizer (a3), water (b) and, ideally, also at least one organic co- solvent (c).
  • At least one urease inhibitor (dl) and/or at least one nitrification inhibitor(d2) at least one urease inhibitor (dl) and/or at least one nitrification inhibitor(d2), with compounds (dl) and (d2) advantageously being different from each other.
  • compounds (a) are usually present in an amount of at least about 20 wt%, preferably at least about 25 wt%, relative to the total weight of compounds (a)+(b)+(c). For compounds (a3) this amount can even be higher.
  • the inhibitors (dl and/or d2) are present in an amount of from about 0.04 to about 70 wt%, from about 0.04 to about 60 wt%, from about 0.04 to about 50 wt%, from about 0.04 to about 40 wt%, relative to the total weight of the solution (I), preferably in an amount of from about 0.1 to about 30 wt%.
  • the amount of inhibitors (dl and/or d2) in said solution (I) is at least about 1 wt%, more preferably at least about 2 wt%, at least about 2.5 wt%, at least about 3 wt%, at least about 3.5 wt%, at least about 4 wt%, at least about 4.5 wt%, more preferably at least about 5 wt%. Even more preferably, their amount is at least about 6, 7, 8, 9 or 10 wt%, relative to the total weight of the solution (I). More information on preferred amounts for the different compounds infra.
  • additive solutions Such solutions with possibly relative high amounts of nitrification and/or urease inhibitors are named hereinafter "additive solutions”. They can also be referred to as “inhibitor compositions” or “inhibitor solutions”. Preferred in the context of the invention are “water based” solutions.
  • the additive solutions (I) of the invention are in the form of "concentrates” that can be added easily to liquid fertilizers (II).
  • the liquid fertilizer (II) is provided in the form of a stock solution, meaning that in general water or another aqueous medium is added to become a final liquid fertilizer.
  • the inhibitors in question usually are present in an amount of at least about 5, 6, 7, 8, 9 wt%, preferably at least about 10, 11, 12, 13, 14 wt%, or even more preferably at least about 15, 16, 17, 18, 19 wt%, relative to the total weight of the additive solution (I). Even amounts up to about 20 wt%, up to about 25 wt%, up to about 30 wt% and more, or even up to about 40 wt% and more are achievable.
  • the urease inhibitors (dl) like NBPT usually are present in an amount from about 0.04 to about 40 wt% in the additive solution, preferably this amount is from about 0.1 to about 30 wt%, and more preferably this amount is from about 0.25 to about 30 wt%. Suitable amounts include for example at least about 1 wt%, preferably at least about 2 wt%, more preferably at least about 3 wt%, and even more preferably at least about 5 wt%.
  • concentrates that comprise at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt% up to about 30 wt% or more of urease inhibitors such as NBPT.
  • the nitrification inhibitors (d2) like DCD preferably are present in amount from about 0.1 to about 40 wt% in the additive solution, more preferably the amount is from about 0.1 to about 30 wt%. Suitable amounts include for example at least about 0.1 wt%, at least about 2 wt%, at least about 3 wt%, or at least about 5 wt%. Preferred though are concentrates that comprise at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt% up to at least about 30 wt% or more of nitrification inhibitors such as DCD.
  • An embodiment of the invention relates to an additive solution (I) of at least one urease inhibitor (dl), or a combination of at least one urease inhibitor (dl) and at least one nitrification inhibitor (d2), wherein the solution comprises:
  • compounds (a) are present in an amount of at least about 20 wt%, relative to the total weight of compounds (a)+(b)+(c), and
  • compounds (dl) are present in amount of at least about 0.04 wt%, preferably at least about 1 wt%, more preferably at least about 2 wt%, at least about 3 wt%, relative to the total weight of the solution (I), and
  • Another embodiment of the invention relates to an additive solution (I) of at least one nitrification inhibitor (d2), or a combination of at least one nitrification inhibitor (d2) and at least one urease inhibitor (dl), wherein the solution comprises:
  • nitrification inhibitor (d2) at least one nitrification inhibitor (d2), and optionally also at least one urease inhibitor
  • compounds (a) are present in an amount of at least about 20 wt%, relative to the total weight of compounds (a)+(b)+(c), and
  • compounds (d2) are present in amount of at least about 0.1 wt%, preferably at least about 1 wt%, more preferably at least about 2 wt%, at least about 3 wt%, relative to the total weight of the solution (I), and
  • Urease inhibitors (dl) are generally chosen from the group of: hydroxyurea, a-hydroxyketone, triketone oximes, hydroquinone (HQ), nitrapyrin and/or phosphoric triamide type inhibitors. Preferred are phosphoric triamide type inhibitors. Preferred urease inhibitors includes phosphoric triamide type inhibitors, preferred are thiophosphoric triamides, more preferred aliphatic thiophosphoric triamides. Particularly preferred are N-alkyl and/or N-acyl thiophosphoric triamides.
  • NPPT N-( n-Propyl)-thiophosphoric triamid
  • NBPT N-(n-butyl)-thiophosphoric triamide
  • NPPT N-(n-Propyl)-thiophosphoric triamid
  • NBPT N-(n-butyl)-thiophosphoric triamide
  • the urease inhibitor present in the additive solution is NPBT, used alone or in combination with one or more other urease inhibitors.
  • compound (dl) advantageously are different from compounds (d2).
  • Nitrification inhibitors (d2) are generally chosen from the group of: dicyandiamide (DCD), 3,4-dimethylpyrazzole phosphate (DMPP), 2-chloro-6- (trichloromethyl)-pyridine (N-Serve), thiourea (TU), 2-sulfanilamidothiazole, 4-amino- 1,2,1, triazole, 3 -mercapto- 1,2, 4-triazole, ammonium dithiocarbamate (ADTC), ammonium thiosulfate (ATS) and/or 3-mercapto-benzothiazole (MBT).
  • DCD dicyandiamide
  • DMPP 3,4-dimethylpyrazzole phosphate
  • N-Serve 2-chloro-6- (trichloromethyl)-pyridine
  • TU thiourea
  • 2-sulfanilamidothiazole 4-amino- 1,2,1, triazole, 3 -mercapto- 1,2, 4-triazole, am
  • DCD DCD
  • ATS TU and/or DMPP
  • DCD DCD
  • ATS TU and/or DMPP
  • the nitrification inhibitor present in the additive solution is DCD, used alone or in combination with one or more other nitrification inhibitors.
  • compound (d2) is DCD, used alone or in combination with one or more other nitrification inhibitors.
  • the additive solution (I) comprises NBPT. In another or the same embodiment, the additive solution (I) comprises DCD.
  • the additive solution (I) comprises NBPT and no other urease and/or nitrification inhibitors.
  • the additive solution comprises DCD and no other nitrification and/or urease inhibitors.
  • the additive solution comprises both NBPT and DCD but no other nitrification and/or urease inhibitors.
  • the co-solvent (c) that is used in the invention can be any organic solvent that is able to dissolve the inhibitors in question (like NBPT and/or DCD) and that is miscible with water. Suitable candidates can for instance be found amongst polar protic solvents and/or polar non- protic solvents.
  • Protic organic solvents include C1-C6 alcohols like methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol; glycols like ethylene glycol, propylene glycol, glycerol; amino-alcohols like ethanolamine, di-ethanol amine and tri ethanol amine and the like.
  • Non-protic polar solvents include dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), triethyl phosphate, dioxane and the like.
  • Particularly suitable are: lower alcohols (especially C1-C6 alcohols, and in particular ethanol), glycols (like e.g., ethylene glycol), dimethylsufonoxide (DMSO), amino-alcohols, dimethylformamide (DMF), dioxanes and/or triethyl phosphate.
  • glycols like e.g., ethylene glycol
  • DMSO dimethylsufonoxide
  • amino-alcohols amino-alcohols
  • DMF dimethylformamide
  • dioxanes dioxanes and/or triethyl phosphate.
  • Preferred are ethanol, glycols like ethylene glycol, DMSO, DMF and/or dioxanes.
  • Most preferred are ethanol and/or DMSO.
  • C1-C6 alcohols and in particular ethanol were found suitable to dissolve high amounts of urease inhibitors like NBPT. They can be used to dissolve DCD too.
  • Organic solvents like DMSO, dioxanes and DMF were found most suitable to dissolve high amounts of nitrification inhibitors like DCD. Particularly preferred for that purpose was DMSO.
  • the urease and/or nitrification inhibitors are dissolved in an urea solution in water supplemented with at least one co-solvent to reach high enough concentrations of the inhibitors.
  • the urease and/or nitrification inhibitors are dissolved in an urea-triazone fertilizer (having e.g., about 5 to about 10 wt% of water) supplemented with at least one co-solvent to reach high enough concentrations of the inhibitors. In that case no extra addition of water is needed to prepare a solution, as there is enough water in the product.
  • a combination of (1) urea in water and of (2) an urea-triazone fertilizer are used to dissolve the inhibitors, and advantageously at least one co-solvent is then used to arrive at high enough concentrations.
  • the additive solutions of the invention may further comprise at least one of (e): dyes, colorants, odor masking agents, flow aids, surfactants, silicas, thickeners, viscosity modifiers, pH control agents, etc.
  • Preferred compounds (e) are dyes and/or colorants.
  • the sum of the weight percentages of compounds (a)+(b)+(c)+(d), when expressed relative to the total weight of the additive solution (I) equals at least about 70 wt%, preferably at least about 80 wt%, more preferably at least about 90 wt%, and most preferably this sum adds up to 100 wt%.
  • a process for preparing an additive solution of the invention comprising the step of dissolving at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) in a solution comprising: urea (al) and/or an urea-triazone fertilizer (a3), water(b) and at least one co-solvent (c).
  • a solution comprising: urea (al) and/or an urea-triazone fertilizer (a3), water(b) and at least one co-solvent (c).
  • urea (al) and/or an urea-triazone fertilizer (a3) water(b) and at least one co-solvent (c).
  • urea (al) and/or an urea-triazone fertilizer (a3) water(b) and at least one co-solvent (c).
  • urease inhibitors (dl) are there.
  • nitrification inhibitor (d2) are present.
  • one or more compounds (a3) are used as solvent. Possibly a mix of compounds (al) and (a2) is used in the process of the invention. With the process of the invention any of the earlier described additive solutions (I) of the invention can be prepared.
  • a solution of urea (al) in water (b), and at least one organic co-solvent (c) is used to dissolve the inhibitors (d).
  • a solution of urea-triazone fertilizer (a3), water (a3, b), and at least one organic co- solvent (c) is used to dissolve the inhibitors (d).
  • one or more of the following compounds may be included in the additive solution of the invention: dye, colorant, odor masking agent, flow aid, surfactant, silica, thickener, viscosity modifier, pH control agent, etc (compounds e).
  • dye colorant
  • odor masking agent flow aid
  • surfactant silica
  • thickener thickener
  • viscosity modifier pH control agent
  • pH control agent etc
  • An advantage of additive solutions (I) of the invention is also that they are stable at room temperature (RT) for longer periods, without the need for stabilizers like ammonium polyphosphates.
  • RT room temperature
  • ammonium polyphosphates usually less than about 0.5 wt%, preferably less than about 0.4 wt% of ammonium polyphosphates are present in additive solutions of the invention.
  • no ammonium polyphosphates are present in additive solutions of the invention.
  • a process for preparing a liquid fertilizer (II) having at least urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) comprising the step of adding an additive solution (I) of the invention (any of the above) to a sulfur containing liquid fertilizer (II).
  • an additive solution (I) of the invention any of the above
  • DCD containing additive solutions of the invention were found compatible with thiosulfate fertilizers like ammonium thiosulfate.
  • a process for preparing a liquid fertilizer (II) having at least one nitrification inhibitor (dl) and/or at least one urease inhibitor (d2) comprising the step of adding an additive solution (I) of the invention (any of the above) to a nitrogen containing liquid fertilizer (II).
  • the nitrogen containing liquid fertilizer herein advantageously is different from compounds (d; dl and/or d2).
  • a preferred nitrogen fertilizer is one that comprises urea, more in particular urea and ammonium nitrate (like UAN, preferably UAN 28-32). Another example is liquid urea.
  • the nitrogen fertilizer can further comprise a sulfur containing fertilizer too.
  • the sulfur containing fertilizer in general is chosen from polysulfides, (bi)sulfite and/or thiosulfate fertilizers.
  • (bi)sulfite is meant sulfite, bisulfite or a mixture of both.
  • the sulfur containing liquid fertilizer herein advantageously is different from compounds (d; dl and/or d2).
  • the urease inhibitors (dl) are present in the liquid fertilizer in an amount of from about 0.04 to about 5 wt%, and preferably the nitrification inhibitors (d2) are present in the liquid fertilizer in an amount of from about 0.5 to about 10 wt%, this relative to the total weight of the liquid fertilizer.
  • the preferred concentration of NBPT in the liquid fertilizer (II) is from about 0.04 to about 2 wt%, preferably from about 0.04 to about 1.5 wt%.
  • the amount of NBPT herein is at least about 0.05 wt%, at least about 0.06 wt%.
  • the preferred end concentration for DCD in the liquid fertilizer (II) is from about 0.2 to about 5 wt%, preferably from about 1 to about 2 wt%.
  • both urease inhibitors and nitrification inhibitors are present then they are generally present in a ratio of between 1 : 10 to 6: 10, preferably 2: 10 to 3 : 10.
  • Provided in the invention are any liquid fertilizers that can be obtained via the process(es) here described.
  • the present invention furthermore provides for liquid "concentrated” nitrogen based fertilizers (II), preferably comprising urea, and more preferably comprising urea and ammonium nitrate, to which an additive solution of the present invention (any of the above) is added.
  • liquid "concentrated” nitrogen based fertilizers (II) preferably comprising urea, and more preferably comprising urea and ammonium nitrate, to which an additive solution of the present invention (any of the above) is added.
  • an additive solution having up to about 30 wt% NBPT and an additive solution having up to about 30 wt% DCD are both prepared, where after at least one of them, possibly both, are added to a stock solution of a liquid fertilizer (II), for example a stock solution comprising an UAN fertilizer, or a stock solution comprising an UAN fertilizer combined with a thiosulfate liquid fertilizer.
  • a liquid fertilizer for example a stock solution comprising an UAN fertilizer, or a stock solution comprising an UAN fertilizer combined with a thiosulfate liquid fertilizer.
  • an additive solution of urea in water and a co-solvent with up to about 30 wt% NBPT and another one with up to about 30 wt% DCD (possibly with an urea-triazone fertilizer (a3) as solvent instead of an urea solution in water), and combine the required amounts of NBPT and/or DCD solutions with a stock solution of a liquid fertilizer (II), for example one comprising an UAN fertilizer, or an UAN fertilizer combined with a thiosulfate liquid fertilizer (II).
  • a liquid fertilizer for example one comprising an UAN fertilizer, or an UAN fertilizer combined with a thiosulfate liquid fertilizer (II).
  • an additive solution of urea in water and optionally a co-solvent with up to about 30 wt% NBPT and another one with up to about 30 wt% DCD possibly with urea-triazone fertilizer as solvent instead of an urea solution in water
  • a stock solution of a liquid sulfur containing fertilizer for instance a thiosulfate liquid fertilizer to which, optionally, an UAN fertilizer is added.
  • This is suitable in particular for use with one or more DCD-based additive solutions of the invention, possibly one containing DCD and NBPT.
  • an additive solution of urea in water and optionally a co-solvent with up to about 30 wt% NBPT and another one with up to about 30 wt% DCD possibly with urea-triazone fertilizer as solvent instead of an urea solution in water
  • a stock solution of a mixed N-S fertilizer (III) comprising e.g., both an UAN fertilizer and a thiosulfate liquid fertilizer.
  • the invention further provides for additive solutions (I) obtainable according to any of the processes described herein and for liquid fertilizers (II) or (III) obtainable according to any of the processes described herein.
  • Additive solutions (I) of the invention are in particular suitable for the making of liquid mixed N-S fertilizers (III).
  • liquid mixed N-S fertilizer (III) composition comprising: water,
  • a sulfur containing fertilizer selected for instance from polysulfide, (bi)sulfite and/or thiosulfate fertilizers,
  • NF2 nitrogen containing fertilizer
  • At least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) (like NBPT and/or DCD)
  • the amount of S is more than about 2 wt%, preferably more than about 5 wt%, relative to the total weight of the fertilizer (III), and
  • the amount of N is more than about 5 wt%, preferably more than about 20 wt%, and more preferably more than about 25 wt% relative to the total weight of the fertilizer (III) .
  • Such liquid mixed fertilizer (III) can be prepared from one or more additive solutions (I) of the invention (any of those described heretofore).
  • Preferred sulfur containing fertilizers are thiosulfates, and more in particular Me- thiosulfates, wherein "Me” is (NH 4 ) 2 , K 2 , Ca, Mg, Mn, Zn, Cu and/or Fe. "Me” preferably is (NH 4 ) 2 , K 2 , Ca, Mg and/or Mn. Preferred are (NH 4 ) 2 , K 2 , Ca and/or Mg. Most preferred is (NH 4 ) 2.
  • the thiosulfates are provided in the form of an aqueous solution having > 4 wt% Me-thiosulfate (on solids); preferably more than about 5 wt%, more preferably more than about 10 wt%.
  • the thiosulfates are different from compounds (d).
  • the sulfur containing fertilizer (SF1) added is different from compounds (d).
  • Preferred nitrogen containing fertilizers are urea based fertilizers that can be urea, UAN, N-sure (urea-triazone), urea-methylene etc. Preferred are nitrogenous fertilizers that contain urea and ammonium nitrate, like UAN.
  • N-S fertilizer (III) at least one urease inhibitor and/or at least one nitrification inhibitor are present.
  • both the sulfur containing fertilizer (SF1) and the nitrogen containing fertilizer (NF2) are liquid fertilizers. They can be added as separate fertilizers, or can be provided under the form of a single liquid N-S fertilizer to which then at least one urease inhibitor (dl) and/or at least one nitrification inhibitor (d2) (like NBPT and/or DCD) are then added.
  • part of the fertilizers can be solid in nature.
  • a solid urea ammonium sulfate like e.g., a 33-0-0-12S fertilizer
  • a solid urea ammonium sulfate like e.g., a 33-0-0-12S fertilizer
  • a solid urea ammonium sulfate can be added to or be present in the liquid mixed N-S fertilizer (III) of the invention.
  • the urease inhibitor preferably is NBPT and the nitrification preferably is DCD. If NBPT is present, then often in a concentration of more than about 0.04 wt%, more preferably more than about 0.1 wt%, relative to the total weight of the mixed liquid fertilizer (III). If DCD is present, then often in a concentration more than about 0.04 wt%, preferably more than about 0.1 wt%, and more preferably more than about 0.2 wt%, relative to the total weight of the mixed liquid fertilizer (III).
  • NBPT is present, either alone or with DCD.
  • DCD is present, either alone or with NBPT.
  • both NBPT and DCD are present in the mixed N-S liquid fertilizer (III) as described herein.
  • the preferred ratio of NBPT to DCD is from 0.1 : 1 to 10: 1; preferred is a ratio of from 0.1 : 1 to 1 : 1, an example of a possible ratio is about 0.25: 1.
  • the claimed N-S fertilizers of the invention can be prepared avoiding the use of expensive or hazardous solvents such as DMF, NMP, etc. In fact they can be prepared using environmentally friendly solvents for delivery of the inhibitors (d), such as urea solutions or urea based compounds. Using materials of the invention it is possible to deliver these additives (compounds d) in aqueous N-S fertilizers.
  • NBPT for instance is not easy to dissolve in an aqueous solution any may present stability issues with some of the standard liquid fertilizers. Materials of the invention help reduce this incompatibility.
  • solutions (I) of the invention proved very stable and led to stable end fertilizers, in particular stable N-S fertilizers.
  • stock solutions (I) of the invention brings the necessary flexibility to the end user, they are easy to handle and friendly to man and the environment.
  • the mixing, adding of the required amounts of inhibitors from one or more additive solutions (I) of the invention can be done at the level of the liquid fertilizer producer or the distributor.
  • another aspect of the invention relates to a container tank holding one or more of the above described fertilizer compositions.
  • the container tank can be holding tank.
  • the liquid fertilizers (II) or (III) herein described can be pumped to tanker trucks for distribution.
  • kits-in-parts containing: at least one additive solution (I) of the invention, optionally containing a dye
  • At least one liquid sulfur containing fertilizer (any of those described), optionally containing a different dye, and,
  • a sheet or card with dosage recommendations optionally, a sheet or card with dosage recommendations.
  • the liquid sulfur containing fertilizer is a liquid thiosulfate fertilizer, most preferably is a stock solution of a liquid thiosulfate fertilizer.
  • Liquid fertilizers (II) or (III) as described herein preferably contain from about 28 to about 32 wt% of nitrogen. Preferred is an amount of about 28 wt% of total nitrogen. In another or the same embodiment, liquid fertilizers (II) or (III) as described herein preferably contain from about 1 to about 10 wt% of sulfur, preferably they contain about 5 wt% of total sulfur.
  • Yet another aspect of the invention relates to the use of one or more additive solutions (I) of the invention for the making of an 28-0-0-5 S fertilizer.
  • the most preferred urease inhibitor is NBPT and the most preferred nitrification inhibitor is DCD.
  • the ratio of water : urea : co-solvent is about 1 : 1 : 1. In another preferred embodiment the ratio of water : urea : co-solvent is about 1 : 1 :2.
  • the use of ethanol (used in relatively small amounts) further has the advantage that the additive solution obtained is not flammable.
  • urease and nitrification inhibitors are combined in one solution, it is preferred to use relative amounts according their required activity, but other relative amounts can be used. Suitable amounts are 10: 1 to 1 :20, preferably 1 : 1 to 1 : 10, like for example about 1 :2 for NBPT to DCD, preferably about 1 :4 for NBPT to DCD. More preferred ratios of the urease inhibitor to nitrification inhibitor given as ratio of NBPT to DCD is between 1 : 10 to 6: 10, more preferably between 2: 10 to 3: 10.
  • the additive solution may further comprise further components like for example odor masking agents, colorants, dyes, pH control agents, flow aids, surfactants, and combinations thereof (compounds e).
  • the odor of the compositions of the present invention is anyhow relatively low, in comparison to the whole-organic solvent solutions of the prior art. Nevertheless, it can be useful to add such a component, in particular if the additive has further useful properties, like for example also lowering the salt out temperature.
  • a preferred odor masking agent includes one of isoamyl butyrate, 4-allylanisole, limonene, terpineol, terpenes, 4-(2, 6, 6-trimethyl -2-cyclo-hex enyl)-3-buten-2-one, benzaldehyde, diethyl malonate, cyclohexyl acetate, anisole, a-ionone, mint oil, Japanese cherry and rose ketones.
  • the additive solution comprises an amount of less than about 5 wt% (by total weight of composition) of odor masking agent, preferably, less than about 3 wt%.
  • the additive solution comprises an amount of from about 1 wt% to about 3 wt% of the odor masking agent (for example, isoamyl butyrate).
  • the odor masking agent preferably lowers the salt-out temperature of the composition
  • a dye or colorant is present in the additive solution at an amount of about 0.05 wt% or higher, preferably about 0.1 wt%, or higher (wt% relative to the total composition).
  • Preferred are dyes and more in particular food grade dyes.
  • the dye - if present - generally is present in the composition in an amount of about 3 wt% or lower, preferably about 1 wt% or lower. Suitable examples include yellow, blue, red and/or green food grade dyes.
  • acid control agents acid, base or buffering compounds can be used.
  • an acidic compound can be included as a pH control agent to maintain or to adjust the pH of the additive solution.
  • Illustrative acids can include, but are not limited to, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, ammonium bisulfite (ABS) or any combination thereof.
  • a basic compound can be included as a pH control agent to maintain or to adjust the pH of the additive solution.
  • Illustrative base compounds for adjusting the pH can include, but are not limited to, ammonia, amines, e.g., primary, secondary, and tertiary amines and polyamines, sodium hydroxide (NaOH), potassium hydroxide (KOH), or a combination thereof.
  • Other Illustrative pH buffering compounds are for instance triethanolamine, sodium borate, potassium bicarbonate, sodium carbonate, potassium carbonate, or any combination thereof.
  • the additive solution (I) can be mixed with dissolved fertilizers.
  • Fertilizers are common water soluble inorganic fertilizers that provide nitrogen, and optionally further nutrients such as phosphorus, potassium, sulfur and other nutrients.
  • Examples of such fertilizers include: for nitrogen as the nutrient: urea, urea-aldehyde oligomers, nitrates and or ammonium salts such as ammonium nitrate, including in combination with urea e.g., as UAN type materials, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium phosphates, like mono-ammonium phosphate, di -ammonium phosphate and ammonium polyphosphate, ammonium sulfate, ammonium thiosulfate, and the like.
  • a fertilizer composition can comprise one or a combination of the fertilizers described herein.
  • Preferred nitrogenous fertilizers are those containing a nitrogenous compound such as urea, urea-aldehyde oligomers, nitrate salts, ammonium salt, or a mixture thereof, such as ammonium nitrate, ammonium sulfate, ammonium thiosulfate, ammonium polysulfide, ammonium phosphates, ammonium chloride, ammonium bicarbonate, ammonia, calcium nitrate, nitrate soda, calcium cyanamide.
  • a nitrogenous compound such as urea, urea-aldehyde oligomers, nitrate salts, ammonium salt, or a mixture thereof, such as ammonium nitrate, ammonium sulfate, ammonium thiosulfate, ammonium polysulfide, ammonium phosphates, ammonium chloride, ammonium bicarbonate, ammonia, calcium nitrate, nitrate soda
  • the nitrogenous fertilizer comprises urea (often about 1% to about 23% N solutions), or urea and ammonium nitrate (UAN).
  • urea and ammonium nitrate- containing fertilizers include, for example, UAN 18, UAN 28, UAN 30 and UAN 32, triazone, urea methylene, urea-aldehyde adducts and the like.
  • Preferred UAN concentrates include UAN 18, UAN 28, UAN 30, UAN 32, and more preferred UAN concentrates are UAN 28 or UAN 32, UAN 32 being most preferred.
  • Preferred urea (often about 2% to about 20% N solutions) and urea adducts include N-sure, an urea- triazone fertilizer and Trisert ® triazone fertilizers (often about 5% to about 25% N solutions).
  • the urea based fertilizer solution further comprises a sulfur containing fertilizer.
  • Suitable sulfur containing fertilizers include polysulfide, (bi)sulfite and/or thiosulfate salts.
  • Preferred polysulfide salts include calcium polysulfide (sold for instance under the name Solmenda ® (formerly Soil-MendTM), Sulforix ® or Rex Lime Sulfur) more preferred sulfur containing fertilizer salts include (bi)sulfite and thiosulfates.
  • Suitable (bi)sulfite based liquid fertilizer include K-ROW 23 ® (potassium sulfite) and ammonium bisulfite.
  • Sulfite components like sodium sulfite have been described as urease inhibitors.
  • the inhibitor is believed to bind to the di -nuclear Ni(II) center of some bacterial urease in a tridentate mode involving bonds between the two Ni(II) ions in the active site and all three oxygen atoms of the inhibitor.
  • thiosulfate salts include Me thiosulfate, wherein Me is ammonium, potassium, calcium, magnesium, manganese, zinc, copper and/or iron.
  • Preferred Me ions include ammonium, potassium, calcium and/or magnesium.
  • ammonium thiosulfate is used, because of its additional stabilizing effect on urea.
  • Thiosulfate based liquid fertilizers are well known, and comprise for example:
  • Thio-Sul® Ammonium thiosulfate (Thio-Sul®), which is a 50-60% aqueous solution, (grade is 12-
  • KTS® Potassium thiosulfate
  • CaTs® Calcium thiosulfate
  • Magnesium thiosulfate which is a 24-25% solution, (grade is 0-0-0- 10S-
  • a concentrated fertilizer composition is made by combining the inhibitor composition (additive solution) of the present invention with a concentrated
  • a diluted fertilizer composition is prepared by subsequently diluting the concentrated liquid nitrification-inhibited fertilizer composition with an aqueous medium, preferably water in a ratio of up to about 500 pbw, more preferably from about 10 to about 500 pbw and even more preferably from about 100 to about 300 pbw, of the aqueous medium per about 1 pbw concentrated liquid nitrogenous fertilizer composition.
  • an aqueous medium preferably water in a ratio of up to about 500 pbw, more preferably from about 10 to about 500 pbw and even more preferably from about 100 to about 300 pbw, of the aqueous medium per about 1 pbw concentrated liquid nitrogenous fertilizer composition.
  • the end use fertilizer composition of the present invention is made by combining the additive solution(s) (I) of the present invention, a concentrated liquid nitrogenous fertilizer, and an aqueous medium.
  • the end use fertilizer composition of the present invention comprises one or more urease inhibitors, preferably NBPT, alone or in combination with one or more nitrification inhibitors.
  • the end use fertilizer composition (II) of the present invention comprises from about 0.001 to about 5 pbw, preferably from about 0.01 to about 2 pbw urease inhibitor and/or nitrification inhibitor per about 100 pbw of the one or more nitrogenous fertilizer compounds.
  • the end use fertilizer composition is applied to target plants or to an environment for the target plants, i.e., to ground on or within which the target plants are growing or to be grown, at a rate of from about 0.01 pounds to about 5 pounds of the fertilizer composition, preferably from about 0.05 pounds to about 2 pounds of the fertilizer composition, per 1000 square feet of ground.
  • the end use fertilizer composition is applied to target plants or to an environment for the target plants at a rate effective to provide a dosage of fertilizer of from about 0.01 pounds to about 5 pounds of fertilizer, preferably from about 0.05 pounds to about 2 pounds of fertilizer, per 1000 square feet of ground.
  • composition of the present invention provides improved ease of handling of urease inhibitors and/or nitrification inhibitors, improved solubility characteristics, low toxicity of the water based solution with only a relatively low amount of organic solvents, good storage characteristics, and excellent miscibility with aqueous compositions, such as aqueous nitrogenous fertilizer formulations.
  • compositions are described as percent by weight on a ton basis.
  • Additive solutions (I) of the invention and liquid fertilizers (II) of the invention help stimulate plant growth, and reduce ammonia loss and slow down nitrification.
  • formulations of the current invention are for illustration only and not limited to just these formulations but includes all known formulations that are suitable for obtaining good inhibition of urease and of nitrification.
  • the products listed below are not limited to just these products but includes all liquid fertilizers and suspension fertilizers commonly used in the liquid fertilizer industry that would require the use of NBPT as an urease inhibitor to reduce or minimize ammonia loss or the use of DCD as a nitrification inhibitor to slow or reduce nitrification reaction in the soil.
  • compositions can be made by mixing concentrated additive solutions with urea and/or UAN solutions.
  • nitrogen content can range from about 1% N as UAN1 to about 31.9% N as UAN32, preferably between about 5 and about 31.9% and more preferably between about 16 and about 31.9%.
  • nitrogen content can range about 1% to about 23%, preferably between about 5% and about 23% and more preferably between about 15 and about 20%.
  • Ranges for liquid phosphate are from about 0.1% to about 33.9% while ranges for potassium are from about 0.1% to about 24.9% using potassium thiosulfate and from about 0.1% to about 22.9% using potassium bi/sulfite.
  • Ranges for NBPT are from about 0.01% to about 5%, for DCD from about 0.1 to about 20% and for Thio-Sul from about 1.0% to about 25.9% sulfur.
  • Other nutrients and micronutrients that can be added include zinc, boron, calcium, iron, copper, molybdenum, manganese, and magnesium.
  • compositions are relatively high strength compositions, and particularly preferred are high strength compositions with a relatively high amount of sulfur.
  • Urea is dissolved in the same amount of water by stirring. Thereafter - if applicable - the co- solvent is mixed, and thereafter the urease and/or nitrification inhibitor.
  • the amounts are given in the Table below.
  • N-Sure® an urea-triazone fertilizer contains about 8% water; hence, of the 20 wt% about 1.6 wt% is water.
  • the resulting solutions are clear to the eye.
  • the solutions are storage stable at temperatures between about 15 °C and about 40 °C.
  • the solution can be used to add a required amount of NBPT and/or DCD to a liquid fertilizer as wanted.
  • Example 9 As an alternative to Example 9, a stock solution of 10 kg urea and 10 L of water 10 kg of ethanol with 5 kg DCD and 1.25 kg NBPT was prepared by stirring first water and urea, adding ethanol and thereafter adding DCD and NBPT and further stirring, till a clear solution was obtained.
  • a solution of 187.6 kg urea, 52.4 kg ammonium thiosulfate and 189.46 kg water was prepared. To this mixture, the 25 kg of stock solution was added. The resulting solution was clear and storage stable.
  • the additive solutions (I) of the invention could be stored for several months, even up to 1 year without phase separation and/or precipitation.
  • An additive solution according to the invention containing about 20 wt% of NBPT in urea/ethanol, was subjected to a HPLC method to see if the NBPT had remained stable.
  • Gradient HPLC was used for these purposes. Were used herein: a propylamine column, a Diode Array Detector set at 2014 nm, and acetonitrile : water as mobile phase.
  • the gradient table is the one below: [00180] Gradient Table:
  • Additive solutions (I) of the invention are thus both chemically and physically stable when stored in closed containers under normal conditions of pressure and temperature (about 1 bar, about l8-25°C). This is surprising, as water was thought to facilitate the decomposition of NBPT into a non-effective substance. Without being bound by theory, it is believed that compounds (a) protect compounds (d) from destabilization, even sensitive compounds like NBPT.

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  • Fertilizers (AREA)

Abstract

La présente invention concerne des solutions additives d'au moins un inhibiteur d'uréase et/ou d'au moins un inhibiteur de nitrification, la solution comprenant : de l'urée, un adduit urée-aldéhyde et/ou un engrais à base d'urée-triazone, de l'eau et au moins un co-solvant, et en outre au moins environ 2,5 % en poids, de préférence au moins environ 5 % en poids d'inhibiteurs d'uréase et/ou de nitrification. Jusqu'à environ 30 % en poids et plus des inhibiteurs peuvent être dissous en tant que tels. Les solutions additives selon l'invention sont très appropriées pour l'ajout à des engrais liquides N et/ou S. Un engrais liquide 28-0-0-5S peut par exemple être fabriqué à partir de matériaux selon l'invention.
PCT/US2019/027346 2018-04-20 2019-04-12 Compositions d'engrais à base d'azote liquide et additifs associés WO2019204163A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057522A (zh) * 2021-11-17 2022-02-18 中化农业（临沂）研发中心有限公司 含双效缓释氮的生物刺激素组合物及其制备方法
FR3113811A1 (fr) 2020-09-08 2022-03-11 VALORISATION DES INNOVATIONS EN AGROFOURNITURES VEGETALES par abréviation VIA VEGETALE Composition d’engrais azoté destiné à être appliqué par voie racinaire

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WO2016054012A1 (fr) 2014-09-30 2016-04-07 Iannotta Leahann Solvant pour solutions de triamide thiophosphorique ou de dicyandiamide, et procédés associés
WO2017031186A1 (fr) 2015-08-17 2017-02-23 Rhodia Operations Systèmes de solvants à base de dcd et/ou de triamide thiophosphorique d'alkyle stabilisés par des amines à haute température et leur utilisation dans des applications agricoles
WO2017081183A1 (fr) 2015-11-12 2017-05-18 Yara International Asa Composition mixte améliorée à base d'urée et son procédé de fabrication
WO2017083714A1 (fr) 2015-11-11 2017-05-18 Koch Agronomic Services, Llc Composition contenant des produits d'addition de triamide n-(n-butyl)-thiophosphorique et des produits de réaction
EP3210959A1 (fr) * 2016-02-24 2017-08-30 YARA International ASA Formulation d'inhibiteur d'uréase liquide, procédé de fabrication et particules solides
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WO2014028767A1 (fr) 2012-08-15 2014-02-20 Koch Agronomic Services, Llc Compositions liquides améliorées contenant des inhibiteurs d'uréase et des alkyléthers de glycol
US20140090432A1 (en) 2012-10-01 2014-04-03 Gary David McKnight Liquid Formulations of Urease Inhibitors for Fertilizers
WO2014100561A1 (fr) 2012-12-20 2014-06-26 Rhodia Operations Compositions liquides de dicyandiamide et/ou de triamide alkylthiophosphorique et leur utilisation dans des applications agricoles
US8888886B1 (en) * 2013-08-06 2014-11-18 Garnett B Whitehurst NBPT solutions for preparing urease inhibited urea fertilizers prepared from N-substituted morpholines
WO2016054012A1 (fr) 2014-09-30 2016-04-07 Iannotta Leahann Solvant pour solutions de triamide thiophosphorique ou de dicyandiamide, et procédés associés
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3113811A1 (fr) 2020-09-08 2022-03-11 VALORISATION DES INNOVATIONS EN AGROFOURNITURES VEGETALES par abréviation VIA VEGETALE Composition d’engrais azoté destiné à être appliqué par voie racinaire
CN114057522A (zh) * 2021-11-17 2022-02-18 中化农业（临沂）研发中心有限公司 含双效缓释氮的生物刺激素组合物及其制备方法
CN114057522B (zh) * 2021-11-17 2023-02-24 中化农业（临沂）研发中心有限公司 含双效缓释氮的生物刺激素型液体肥及其制备方法

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