WO2020033575A1 - Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation - Google Patents

Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation Download PDF

Info

Publication number
WO2020033575A1
WO2020033575A1 PCT/US2019/045544 US2019045544W WO2020033575A1 WO 2020033575 A1 WO2020033575 A1 WO 2020033575A1 US 2019045544 W US2019045544 W US 2019045544W WO 2020033575 A1 WO2020033575 A1 WO 2020033575A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
urea
product
iii
products
Prior art date
Application number
PCT/US2019/045544
Other languages
English (en)
Inventor
Michael Massoud Hojjatie
David Thomas FAIRWEATHER
Jeroen Van Cauwenbergh
Martijn TIMMERMANS
Heidi VAN DEN RUL
Original Assignee
Tessenderlo Kerley, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP18195470.2A external-priority patent/EP3626696A1/fr
Application filed by Tessenderlo Kerley, Inc. filed Critical Tessenderlo Kerley, Inc.
Priority to AU2019319857A priority Critical patent/AU2019319857A1/en
Priority to EA202190325A priority patent/EA202190325A1/ru
Priority to EP19759149.8A priority patent/EP3833646A1/fr
Priority to CA3107147A priority patent/CA3107147A1/fr
Priority to US17/266,590 priority patent/US20210300831A1/en
Priority to BR112021002403-4A priority patent/BR112021002403A2/pt
Publication of WO2020033575A1 publication Critical patent/WO2020033575A1/fr

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to fertilizer compositions prepared from dry (solid, powder, ..) thiosulfates, polysulifides or (bi)sulfites, and their processes of making.
  • Products of the invention are simple to make, have a wide applicability and find their use in both the liquid and solid fertilizer end markets. Products of the invention allow one to make easy-to- use NS fertilizers and/or to make a new type of stabilized fertilizers.
  • the thiosulfate ion, S2O3 2 is a structural analogue of the S0 4 2 ion in which one oxygen atom is replaced by one S atom.
  • the two sulfur atoms in S2O3 2 are not equivalent.
  • One of the S atoms is a sulfide-like sulfur atom that gives the thiosulfate its reducing properties and complexing abilities.
  • Thiosulfates are used in leather tanning, paper and textile manufacturing, flue-gas desulfurization, cement additives, dechlorination, ozone and hydrogen peroxide quenching, coating stabilizers, as an agricultural fertilizer, as a leaching agent in mining, and so on.
  • thiosulfate compounds Due to their complex-forming abilities with metals, thiosulfate compounds have been used in commercial applications such as photography, waste treatment and water treatment applications.
  • thiosulfates are used as fertilizers in combination with cations such as ammonium, potassium, magnesium and calcium.
  • the ammonium, alkali metal and alkaline earth thiosulfates are soluble in water. Water solubility of thiosulfates decreases from ammonium to alkali metals to alkaline earth thiosulfates.
  • Potassium (K) is a primary plant nutrient.
  • Potassium thiosulfate fertilizer contains the highest %K in liquid form, compared to other sources of potassium such as potassium chloride (KCI), potassium Nitrate (KNO3), and potassium sulfate (K2SO4). In addition, it combines potassium with sulfur (17%) which is also an essential plant nutrient.
  • Magnesium is an important element in the nutrition of animals and plants. It is a part of every animal cell.
  • Magnesium thiosulfate is a liquid source of Mg with up to 32% in concentration. Magnesium Thiosulfate is used in Industrial and Waste Treatment Applications, in Food Manufacturing Applications, Pharmaceutical Applications, and in Agricultural Applications.
  • Calcium is an essential plant nutrient. Calcium availability is essential in the biochemistry of plants and as it has been learned recently, in the nitrogen fertilizer efficiency of surface-applied urea.
  • Ammonium thiosulfate is a nitrogen and sulfur based liquid used commonly as 12-0- 0-26 grade fertilizer in combination with urea ammonium nitrate (UAN), and ammonium polyphosphate (APP), and other fertilizers.
  • Ammonium thiosulfate has been used in conjunction with urea and urea-containing fertilizer products for the purpose of reducing nitrogen loss due to the nitrification of urea by bacteria or conversion to ammonia by the effect of urease enzyme.
  • urea and urea-containing fertilizer products for the purpose of reducing nitrogen loss due to the nitrification of urea by bacteria or conversion to ammonia by the effect of urease enzyme.
  • UAN ammonium thiosulfate
  • 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: [0015] Thiosulfates like ammonium thiosulfates are also nitrification inhibitors, see e.g. Sallade and Sims, in Plant & Soil, December 1992.
  • Calcium and magnesium polysulfides are soil acidifying conditioners on the one hand, and capture the ammonium carbonate forms from hydrolysis of urea plus form the related carbonates on the other hand. Carbonate precipitation and resultant soil pH depression reduce the rate of hydrolysis of added urea and, therefore, reduce ammonia loss.
  • soil conditioners polysulfides are also a known source of Sulfur fertilizers.
  • Sulfite and bisulfites can react with the enzyme nickel site and prevent its activity (L. Mazzei et. al in J. of Inorg Biochem.. Jan 2016).
  • (Bi)sulfites further prevent oxygen-induced oxidation. As they are reducing agents, they can also prevent oxidation of NBPT to NBPO (which is the active mode of NBPT for urease inhibition) and hence they prolong the inhibitory effect of NBPT in the soil.
  • NBPO which is the active mode of NBPT for urease inhibition
  • fertilizers are known fertilizers.
  • Thiosulfates, polysulfides and/or (bi)sulfites are thus known to have urease and/or nitrification inhibiting properties. Plus some of these compounds also protect NBPT from oxidative degradation. Also elemental sulfur can be used as nitrogen inhibitor (Soaud et al, J of Australian Crop Science, May 2011).
  • Thiosulfates, polysulfides and (bi)sulfites are often provided in the form of saturated salt solutions in water.
  • Calcium and Magnesium thiosulfate fertilizers that are on the market contain about 75 wt% of water.
  • Ammonium and Potassium thiosulfate fertilizers typically contain from about 40-50 wt% of water.
  • Ammonium bisulfite by way of example is a 60-67% liquid solution with a pH about 5-5.8.
  • US Patent No. 5,618,658 (Fuji Hunt Photographic chemicals) describes methods to prepare a sulfur-free ammonium thiosulfate via spray draying, starting from about 60% ATS solution in water, with carbonate and sulfite components as stabilizers.
  • Dry thiosulfates are on the market (for instance for use in photography), but as fertilizers these products are often not very suitable.
  • dry thiosulfates on the market are often very hygroscopic, causing storage problems when the products are not properly stored to avoid contact with moisture. Bulk storage of goods is then difficult.
  • Another challenge is to obtain products that are not too hygroscopic, that store well and have sufficient shelf-life.
  • solid thiosulfates, polysulfides and/or (bi)sulfites in a stable form and easy to handle, plus compatible with other standard NPK fertilizers.
  • combined fertilizers (NS fertilizers) in a pre-mix form, that is end-user friendly and reduces the dosage errors.
  • stabilized/protected urea-based fertilizers Preferred are herein materials wherein N-protection of urea is provided through different kinds of mechanisms.
  • urea-containing compounds [and in particular urea]
  • liquid thiosulfates helps prevent/reduce their air oxidation.
  • Less of their degradation products such as sulfite and/or sulfate forms were forming during the drying process; meaning that the drying did not lead to significant product degradation. Plus, less elemental sulfur as degradation product seems to form.
  • a similar approach proved beneficial for the drying of liquid polysulfides and/or liquid (bi)sulfites to form solid products useful as fertilizers.
  • a first aspect of the invention relates to aqueous solutions of thiosulfates, polysulfides and/or (bi)sulfites to which one or more urea-containing compounds [and in particular urea] are added. Further compounds like e.g. the compounds (c) and/or (d) as described below can be present. When these aqueous solutions are subjected to a drying process, then solid fertilizer-grade materials could be obtained without significant signs of product degradation.
  • an aqueous composition (I) suitable for preparing a solid thiosulfate-urea product and/or a solid polysulfide-urea based product and/or a solid (bi)sulfite-urea based product comprising:
  • urea-containing compounds preferably urea (al)
  • liquid thiosulfates (bl') and/or liquid polysulfides (b2') and/or liquid
  • the sum of the weight percentages (wt%) of compounds (a) through (e) present usually is at least about 80, 81, 82, 83, 84, or 85 wt%, preferably is at least about 86, 87, 88, or 89 wt%, more preferably at least about 90, 91, 92, 93, or 94 wt% or even at least about 95 wt%; and wherein the aqueous composition (I) comprises not more than about 5 wt% of UAN (Urea Ammonium Nitrate). Weight percentages (wt%) are herein relative to the total weight of the aqueous composition (I).
  • the amount of urea in said aqueous composition (I) is at least about 1 wt% and at most about 90, 89, 88, 87, or 86 wt%, preferably at most about 85 wt%.
  • the amount of compounds (b) in said aqueous composition (I) is at least about 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5 wt% or at least about 5 wt%.
  • the amount of compounds (b) in said aqueous composition (I) is at least about 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19 wt%, even at least about 20 wt%.
  • the amount of compounds (b) in said aqueous composition (I) is at most about 90, 89, 88, 87 or 86 wt%, preferably at most about 85 wt%.
  • the sum of the weight percentages does not exceed 100 wt%.
  • an aqueous composition (I) suitable for preparing a solid thiosulfate-urea product and/or a solid polysulfide-urea based product and/or a solid (bi)sulfite-urea based product comprising:
  • urea-containing compounds preferably urea (al)
  • liquid thiosulfates (bl') and/or liquid polysulfides (b2') and/or liquid
  • urease (cl) and/or nitrification (c2) inhibitors that are different from compounds (b'), and/or
  • the sum of the weight percentages (wt%) of compounds (a) through (e) present usually is at least about 80, 81, 82, 83, 84 or 85 wt%, preferably is at least about 86, 87, 88 or 89 wt%, more preferably at least about 90, 91, 92, 93 or 94 wt%, even at least about 95 wt%; and wherein the aqueous composition (I) comprises not more than about 5 wt% of UAN.
  • Weight percentages (wt%) are herein relative to the total weight of the aqueous
  • the amount of compounds (b) in said aqueous composition (I) usually is at least about 7, 8, 9, 10, 11, 12, 13 or 14 wt%. In a particular embodiment, this amount is at least about 15, 16, 17, 18, 19 or 20 wt%. In particular embodiments of the invention, the amount of compounds (b) is at least about 25, 30, 35, 40, 45 or 50 wt%. Usually the amount of compounds (b) is at most about 92, 91 or 90 wt%. In this embodiment the amount of urea (al) is at least about 1, 2, 3 or 4 wt%, at least about 5, 6, 7, 8 or 9 wt%, even at least about 10 wt%. Of course, the sum of the weight percentages does not exceed 100 wt%.
  • Compounds (a) can be selected from urea (al, CH 4 N 2 0, MW about 60) and/or from urea-aldehyde products (a2) and/or urea-triazone compounds (a3), though 'urea' and more in particular 'dry' or 'solid' urea is preferred.
  • Aqueous compositions (I) of the invention generally are substantially free from UAN. By substantially free is meant that they comprise less than about 1 wt% of UAN. Preferably they comprise less than about 0.5 wt%, more preferably less than about 0.1 wt% of UAN, relative to the total weight of the aqueous composition (I).
  • the ratio of compounds (a) to compounds (b), and more in particular the ratio of urea (al) to compounds (b), in the aqueous compositions (I) of the invention is from 1:99 to 99:1, or from 1.5:98.5 to 98.5:1.5, or from 2:98 to 98:2.
  • the ratio of compounds (a) to compounds (b) is from 5:95 to 95:5, from 10:90 to 90:10, from 15:85 to 85:10 or from 15:85 to 85:15.
  • a preferred compound (a) is urea (al, CH4N2O, MW about 60).
  • the ratio of urea to compounds (b) is from 5:95 to 95:5, from 10:90 to 90:10, from 15:85 to 85:10 or from 15:85 to 85:15. In some embodiments of the invention this ratio will be from 1:4 to 4:1, preferably from 1:3 to 3:1 or from 2:3 to 3:2. In a particular embodiment of the invention this ratio is from 1:2 to 2:1. In a most particular embodiment of the invention compounds (a) and (b) are present in equal amounts.
  • Aqueous compositions (I) of the invention are easy to prepare by contacting and mixing the different compounds. Normally the amount of water present in the liquid thiosulfates and/or the liquid polysulfides and/or the liquid (bi)sulfites allows a thorough mixing of the different compounds. When high amounts of compounds (a) and/or of compounds (b) are being used, then it may be useful to add some extra water.
  • the total amount of water present in aqueous compositions (I) of the invention is from about 5 wt% to about 75 wt%, more preferably from about 10 wt% to about 70 wt%, more preferably from about 15 wt% to about 65 wt%.
  • a second aspect of the invention relates to 'dry', 'dried' or 'solid'
  • thiosulfate-urea based product (lla) and/or a polysulfide-urea based product (Mb) and/or a (bi)sulfite-urea based product (lie) comprising:
  • urease (cl) and/or nitrification (c2) inhibitors that are different from compounds (b), and/or
  • the amount of water (e) in the product (II) is less than about 10 wt%, preferably less than about 5 wt%;
  • compounds (a) are selected from urea (al) and/or from urea-aldehyde products (a2) and/or from urea-triazone compounds (a3);
  • compounds (b) are selected from thiosulfates (bl) and/or from polysulfides (b2) and/or from (bi)sulfites (b3);
  • said product (II) comprising, relative to its total weight, at least about 1 wt%, preferably at least about 2 wt% of urea and at most about 99, 98, 97 or 96 wt% of urea.
  • the amount of urea is at most about 95, 94, 93, 92, or 91 wt%.
  • the amount of urea present in the products (II) is at most about 90, 89, 88, 87 or 86 wt%, even at most about 85 wt%.
  • compounds (b) are herein present in an amount of at least about 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5 wt%, at least about 5 wt%.
  • compounds (b) are herein present in an amount of at most about 95, 94, 93, 92 or 91 wt%.
  • compounds (b) are present in an amount of at most about 90, 89, 88, 87, 86 or at most about 85 wt%.
  • Weight percentages are herein relative to the total weight of the product (II) and of course the sum of the weight percentages does not exceed 100 wt%.
  • thiosulfate-urea based product (lla) and/or a polysulfide-urea based product (lib) and/or a (bi)sulfite-urea based product (lie) comprising:
  • urease (cl) and/or nitrification (c2) inhibitors that are different from compounds (b), and/or - optionally, one or more additives (d) that are different from any of the above compounds;
  • the amount of water (e) in the product (II) is less than about 10 wt%, preferably less than about 5 wt%;
  • compounds (a) are selected from urea (al) and/or from urea-aldehyde products (a2) and/or from urea-triazone compounds (a3);
  • compounds (b) are selected from thiosulfates (bl) and/or from polysulfides (b2) and/or from (bi)sulfites (b3);
  • said product (II) comprising at least about 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 wt% of
  • the amount of compounds (b) is then at most about 95, 94, 93,
  • urea herein is at least about 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5 wt%, even at least about 5 wt%.
  • urea herein is present in an amount of at most about 94, 93, 92 or 91 wt%.
  • the amount of urea present in the products (II) is at most about 90, 89, 88, 87 or 86 wt%, even at most about 85 wt%. Weight percentages are herein relative to the total weight of the product (II) and of course the sum of the weight percentages does not exceed 100 wt%.
  • thiosulfate-urea based product (lla) and/or a polysulfide-urea based product (Mb) and/or a (bi)sulfite-urea based product (lie) comprising:
  • urease (cl) and/or nitrification (c2) inhibitors that are different from compounds (b), and/or
  • the amount of water (e) in the product (II) is less than about 10 wt%, preferably less than about 5 wt%;
  • compounds (a) are selected from urea (al) and/or from urea-aldehyde products (a2) and/or from urea-triazone compounds (a3);
  • compounds (b) are selected from thiosulfates (bl) and/or from polysulfides (b2) and/or from (bi)sulfites (b3);
  • compounds (a) and (b) are spread substantially homogeneously throughout the product (II); wherein in general the amount of urea in the product (II) is at least about 1 wt% and at most about 99, 98, 97, 96, 95, 94, 93, 92, or 91 wt%. Typically, however, the amount of urea in the product (II) is at most about 90, 89, 88, 87, 86 wt% or even at most about 85 wt%, when compound (b) comprises or is ammonium thiosulfate.
  • compounds (a) and (b) in products (II) of the invention are spread substantially homogeneously throughout the product (II).
  • said product (II) comprises at least about 10, 10.5, 11,
  • said product (II) comprises at most 90, 89.5, 89,
  • the ratio of compounds (a) to compounds (b) is typically from 10:90 to 90:10, from 15:85 to 85:15 or from 20:80 to 80:20.
  • the urea-containing compound (a) preferably is selected from urea itself (al, CH4N2O, MW about 60) and/or from urea-aldehyde products (a2) and/or from urea-triazone compounds (a3).
  • the urea- containing compound includes or is urea (al). Preferably it is urea (al).
  • urea (al) has different advantages: (1) urea is a source of nitrogen nutrients, so the products find use as fertilizer, (2) urea is cheap and readily available, (3) surprisingly, urea helps prevent the oxidation/degradation of the liquid fertilizers, and (4) surprisingly, urea seems to act also as a processing aid during the drying process.
  • the term 'thiosulfates' refers to the active ingredient itself, and not the aqueous solution. Impurities possibly present in the 'thiosulfate' however are included. The same applies for the term 'polysulfides' and the term '(bi)sulfites'.
  • Thiosulfates (bl), polysulfides (b2) and (bi)sulfites (b3) are generally provided in the form of a solution or suspension in water. These solutions most often are saturated solutions, meaning that the active ingredient is present dissolved or dispersed therein in the highest possible amount.
  • the ratio of compounds (a) to compounds (b), and more in particular the ratio of urea (al) to compounds (b), in products (II) of the invention is from 1:99 to 99:1, from 1.5:98.5 to 98.5:1.5, or from 2:98 to 98:2.
  • the ratio of compounds (a) to compounds (b) is from 5:95 to 95:5, from 10:90 to 90:10, from 15:85 to 85:10 or from 15:85 to 85:15 or from 20:80 to 80:20.
  • this ratio will be from 1:4 to 4:1, preferably from 1:3 to 3:1 or from 2:3 to 3:2. In a particular embodiment of the invention this ratio is from 1:2 to 2:1. In a most particular embodiment of the invention compounds (a) and (b) are present in equal amounts.
  • a third aspect of the invention relates to possible drying processes that can lead to solid products of the invention.
  • a process for making a thiosulfate- urea based product (Ilia) and/or a polysulfide-urea based product (lllb) and/or a (bi)sulfite- urea based product (II lc) with low water content comprising the steps of:
  • compounds (a) are selected from urea (al) and/or from urea-aldehyde products (a2) and/or from urea-triazone compounds (a3);
  • compounds (b) are selected from thiosulfates (bl) and/or from polysulfides (b2) and/or from (bi)sulfites (b3);
  • said product (III) comprising at least about 1 wt%, preferably at least about 2 wt% of urea and at most about 99, 98, 97 or 96 wt% of urea.
  • the amount of urea is at most about 95, 94, 93, 92, or 91 wt%.
  • the amount of urea present in the products (III) is at most about 90, 89, 88, 87 or 86 wt%, even at most about 85 wt%.
  • compounds (b) are herein present in an amount of at least about 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5 wt%, even at least about 5 wt%.
  • compounds (b) are herein present in an amount of at most about 95, 94, 93, 92 or 91 wt%.
  • compound (b) are present in an amount of at most about 90, 89, 88, 87 or 86 wt%, even at most about 85 wt%.
  • Weight percentages are herein relative to the total weight of the product (III) and of course the sum of the weight percentages does not exceed 100 wt%.
  • compounds (b) are selected from thiosulfates (bl) and/or from polysulfides (b2) and/or from (bi)sulfites (b3);
  • said product (III) comprising at least about 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 wt% of compounds (b).
  • the amount of compounds (b) is then at most about 95, 94, 93,
  • urea herein is at least about 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5 wt%, even at least about 5 wt%.
  • urea herein is present in an amount of at most about 93, 92 or 91 wt%.
  • compound (b) are present in an amount of at most about 90, 89, 88, 87 or 86 wt%, even at most about 85 wt%.
  • Weight percentages are herein relative to the total weight of the product (III) and of course the sum of the weight percentages does not exceed 100 wt%.
  • the processes of the invention often further contain one or more of the following steps: a breaking step, a grinding step, a granulation step, a sieving step, a final drying step, a polishing step, a cooling step and/or a packaging step.
  • 'granulation' is not to be interpreted in a restrictive manner, and can include a prilling process, a pelleting process, a compounding process, a fluidized bed granulation, a drum granulation, a falling curtain granulation, an agglomeration granulation, a spherodizer process, spray drying and compacting, vortex granulation, or any other suitable granulation process or means used in the art to form solid fertilizer granules, prills, pellets, tablets, etc.
  • an aqueous composition (I) of the invention is provided from which water is removed by evaporation, with or without vacuum.
  • a vacuum By applying a vacuum to the aqueous solution (I) of the invention, temperatures can be kept below about 100, 95 or 90°C. If no vacuum is applied, then temperatures of at most about 130, 120, 115 or even 110°C suffice to obtain a solid particulate product. Even at these temperatures products with an excellent shelf life were obtained. The higher temperatures did not lead to substantial discoloration and/or degradation of the compounds (b). Often the solids remaining after evaporation, were further dried at ambient temperature to remove last bits of water. If needed, then the particulate products obtained can be crushed and/or sieved to obtain granulates of a particular size.
  • An alternative way to make products (II) and (III) of the invention is to add compounds (b) to a urea melt (melt temperature of urea is about 133°C).
  • compounds (b) can be added in solid form.
  • the solid compound (b) in a preferred embodiment is a compound (II) and/or (III) of the invention.
  • liquid compounds (b') can be added to the urea melt.
  • a partial or full drying can be done on the liquid compounds (b') to adding of the urea melt.
  • an aqueous composition (I) according to the invention is added to the urea melt.
  • liquid compounds (b') and/or aqueous composition (I) according to the invention are added to the urea melt, then it may be necessary to remove part of the water, before the urea melt containing compounds (a) and possible compounds (c) and/or (d) prior to granulation. This can yield products having at least compounds (a) and (b) spread more or less
  • Yet another way to make products (II) and (III) of the invention is to add solid compounds (b), liquid compounds (b') and/or an aqueous solution (I) of the invention to a liquid urea at a temperature of e.g. at least about 130, 135, 140 or 145°C, and to process these into granulates via a drum coating and/or a drum coating that has some heating sufficient to remove water. Due to their high re-solubility in water, it is even possible to add solid products (II) or (III) of the invention via spray drying. This can lead to solid products wherein compounds (a) are present primarily in the outer layers of the product, or wherein compounds (a) are present in a coating that is provided onto a urea granule.
  • Yet another way to make compounds (II) or (III) of the invention is to add materials of the invention to a liquid urea in e.g. a drum granulator, preferably one equipped with a spray drier.
  • a liquid urea e.g. a drum granulator, preferably one equipped with a spray drier.
  • the temperature of the hot urea is below about 230°C, more preferably below about 200°C when adding compounds (b).
  • this is below about 230°C, more preferably below about 200°C when adding compounds (b).
  • urea- formaldehyde conditioning agent UF80 a mixture of urea/formaldehyde/water in a ratio of 23/57/20, from Dynea.
  • An advantage of the processes of the invention is that they allow the flexibility of using operating temperatures that go from low (at most about 115°C, even lower under vacuum) to minimize product degradation, to high (preferably about 250°C, more preferably about 230°C max) to optimize energy efficiency and equipment sizing still with low product degradation.
  • NBPT is temperature sensitive and may benefit from the above
  • Products (II) and (III) of the invention can vary widely in composition and have various uses:
  • Products high in urea content (preferably those with an N content > 40 wt%) can be used directly as urea fertilizer. If needed they can be blended with standard urea. These materials are suitable for blending with standard NPK fertilizers.
  • Products low in urea content and low in thiosulfate and/or polysulfide and/or (bi)sulfite content can be used as carrier materials for nitrogen stabilizers like NBPT and/or DCD.
  • Re-solubilized in water they can be added to standard liquid fertilizers like e.g. UAN (Urea Ammonium Nitrate). Or they can be used as an intermediate product to add to a urea melt (see below).
  • Products high in urea content and high in thiosulfate and/or polysulfide and/or (bi)sulfite content can be used as such as solid fertilizers, or they may be combined with some other solid fertilizers. Due to a high solubility in water they can also be blended with liquid fertilizers.
  • the solid products (II) or (III) can be provided in many different forms and sizes going from hydrate to crystals, powder, pearls, granule, prill, pellet, pastille, tablet form of a granule, a prill, pellet, tablet, etc. They can be stored or transported in bulk or they can be packed in bags, containers, cubicles, etc. of various sizes that preferably are well sealed. Though the solid products of the invention are less hygroscopic in nature then the products sold for photographic applications, it is recommended to avoid contact with moisture and/or atmospheric gasses such as oxygen, nitrogen, etc., or to provide a suitable moisture- repellent coating.
  • products (II) and (III) of the invention are properly packaged in sealed containers, bags, etc., with little to no head space (e.g. head space of less than about 1%).
  • Products (II) and (III) of the invention can also vary widely in composition. In an embodiment of the invention (any of the above), these products contain compounds (c). As compounds (b) can exert urease and/or nitrification inhibiting effects, the addition of compounds (c) is optional. And if the aim is not to provide a stabilized urea, then compounds (c) are optional anyhow.
  • products (II) and (III) of the invention do not comprise any NBPT, and preferably also no DCD.
  • Products (II) and (III) were found to contain little to no degradation products of compounds (b). Generally products (II) and (III) of the invention contain less than about 5 wt% of oxidation by-products of compounds (b) like the corresponding sulfates and/or sulfites, or like elemental sulfur.
  • Products (II), and (III) of the invention have a wide applicability but are in particular highly suited for use in or as fertilizers. They are generally compatible with standard liquid and/or solid fertilizers or fertilizer ingredients.
  • a fourth aspect of the invention hence relates to a fertilizer (IV) comprising a product (II) or (III) of the invention.
  • the fertilizer is a liquid fertilizer.
  • the fertilizer is a solid fertilizer.
  • a fifth aspect of the invention Products (II) and (III) of the invention can serve as liquid carriers or as solid carriers for nitrogen inhibitors like NBPT and/or DCD.
  • Such carrier materials for NBPT and/or DCD can be added to liquid and/or to solids fertilizers.
  • An advantage of materials of the invention is that they require less or even no organic solvents like NMP (N-methyl-2-pyrrolidone), DMSO (dimethyl sulfoxide), etc.
  • products (II) and (III) of the invention are re-dissolved in water or any other suitable liquid, possibly UAN, prior to their addition to a liquid fertilizer.
  • a sixth aspect of the invention relates to a protected urea containing at least one thiosulfate (bl) and/or at least one polysulfide (b2) and/or at least one (bi)sulfite (b3) in an amount that they exert urease and/or nitrification inhibitory effects.
  • a urea-containing material in particular urea is a good carrier for nitrogen inhibitors such as NBPT (N-(n-butyl)-thiophosphoric triamide) and/or DCD (dicyandiamide).
  • urea-containing compounds in particular urea
  • the amount of organic solvents otherwise used as liquid carrier materials for NBPT and/or DCD can hereby be significantly reduced, even avoided.
  • a still further aspect of the invention relates to the use of an aqueous composition (I) of the invention and/or the use of a product (II) or (III) of the invention for adding to hot urea, like a urea melt.
  • the urea granules as such produced also comprise NBPT and/or DCD, though the presence of the latter is optional as the compounds (b) can exert sufficient urease and/or nitrification inhibitory effects.
  • Yet another aspect of the invention use of aqueous composition (I) of the invention and/or the use of a product (II) or (III) of the invention the coating of granular urea.
  • a last aspect relates to a kit-of-parts comprising a product (II) and/or (III), together with a nitrogen stabilizing composition that contains NBPT and/or DCD, and optionally, some directions on how to mix and apply these materials as liquid or solid fertilizer.
  • Compounds (II) and/or (III) then typically contain no compounds (c).
  • An addition of a dye to the different products and/or solutions can then be handy to help monitor dosage.
  • a first aspect of the invention relates to an aqueous composition (I) having a urea- containing compound (a) added to a liquid thiosulfate (bl') and/or a liquid polysulfide (b2') and/or a liquid (bi)sulfite (b3').
  • the aqueous composition (I) of the invention can further contain urease inhibitors (cl) and/or nitrification inhibitors (c2) and/or additives (d) like dyes, colorants, buffers, surfactants, stabilizers, etc.
  • Aqueous compositions (I) of the invention are simple and cheap materials that can be used for the making of solid thiosulfates, polysulfides and/or (bi)sulfites, for the making of protected urea, and they can serve as carrier materials for nitrogen inhibitors like NBPT and/or DCD. Below, the aqueous compositions (I) of the invention are described as well as their constituents.
  • a second aspect of the invention relates to products (II) or (III) as shortly described above and their ways of making.
  • weight percentages (wt%) are always relative to the total weight of the product/composition in question.
  • weight percentages (wt%) are relative to the total amount of urea nitrogen present in the product/composition.
  • weight percentages (wt%) are relative to the total amount of urea & ammonium nitrogen present in the product/composition.
  • an 'urea-containing compound' (a) is meant herein a compound that contains a certain amount of free urea or a urea-derivative.
  • This term in particular refers to urea itself (al, CH 4 N 2 O, MW around 60) and/or to a urea-aldehyde product (a2) and/or to a urea- triazone compound (a3).
  • Preferred in the context of the invention is urea (CH 4 N 2 O, MW around 60).
  • the 'urea' can be a 'dry urea' (all), a 'liquid urea' (al2) and/or an 'urea melt' (al3).
  • 'dry' or 'solid' urea is often preferred. Any type of dry urea can be used including but not limited to urea granules, prills, pellets, pastilles, tablets, pearls, powders, crystals, etc. - as all of these urea forms are readily soluble in water.
  • 'liquid urea' refers to solutions of urea in water. Liquid urea products on the market in general contain from about 40-60 wt% of urea in water.
  • the term 'liquid urea' in the context of the present invention, does not cover a 'molten urea' or an 'urea melt', having urea in molten form at elevated temperatures (above about 130°C typically).
  • a 'urea' is used with a purity of at least about 50%, preferably at least about 70%, more preferably at least about 90% and most preferably at least about 95%.
  • the urea has a purity of at least about 99, 99.1, 99.2, 99.3, 99.4, 99.5, or 99.6 or up to about 99.7%.
  • Dry urea can have up to about 1 wt% Biuret.
  • Compounds (b) in the context of the invention can be thiosulfates and/or polysulfides and/or (bi)sulfites.
  • compounds (b) include or are (bi)sulfites and/or polysulfides.
  • compounds (b) include or are thiosulfates and/or polysulfides. Most preferred are compounds that include or are thiosulfates.
  • Compounds (b) are usually provided as solutions or dispersions in water. The latter are herein referred to as compounds (b').
  • Thiosulfates are typically provided in the market as liquid thiosulfates (bl') containing the active compound (bl) in water.
  • thiosulfate solutions are preferably used at their maximum concentrations.
  • the thiosulfates in thiosulfate solutions are in general salts of alkali metals, alkali earth metals, and transition metals such as zinc, iron, manganese and/or copper.
  • Preferred in the invention are ammonium thiosulfates and/or potassium thiosulfates and/or calcium thiosulfates and/or magnesium thiosulfates and/or manganese thiosulfates and/or iron thiosulfates.
  • ammonium thiosulfates and/or potassium thiosulfates and/or calcium thiosulfates and/or magnesium thiosulfates More preferred are ammonium thiosulfates and/or magnesium thiosulfates and/or calcium thiosulfates.
  • Magnesium thiosulfates and/or calcium thiosulfates have the strongest urease inhibitory effect. Thus most preferred are magnesium thiosulfates and/or calcium thiosulfates.
  • Potassium thiosulfate can be used, but then preferably in combination with compounds (c). Ammonium thiosulfate can be used too but preferably together with some extra iron and/or molybdenum to increase its efficiency.
  • Thiosulfate based liquid fertilizers are well known, and comprise for example:
  • polysulfides are typically provided in the market as liquid polysulfides (b2') containing the active compound (b2) in water. Also polysulfide solutions are preferably used at their maximum concentrations.
  • Polysulfides (b2) are preferably chosen from calcium polysulfides and/or potassium polysulfides and/or sodium polysulfides and/or iron polysulfides. Preferred are calcium polysulfides and/or potassium polysulfides and/or ammonium polysulfides. Particularly preferred are calcium polysulfides and/or potassium polysulfides because of their good urease inhibiting effect.
  • (bi)sulfites are typically provided in the market as liquid (bi)sulfites (b3') containing the active compound (b3) in water.
  • '(bi)sulfite' is meant to designate sulfites, bisulfites and mixtures of both.
  • (bi)sulfite liquid solutions are preferably used as their maximum concentration.
  • compounds (b3) that can be used in the context of the invention are potassium sulfite, potassium bisulfite, ammonium sulfite and/or ammonium bisulfite and/or iron sulfite and/or iron bisulfite.
  • Preferred are potassium sulfite, potassium bisulfite, ammonium sulfite and/or ammonium bisulfite. More preferred are potassium sulfite and/or potassium bisulfite.
  • compounds (b) include or are selected from thiosulfates (bl). In another embodiment of the invention, compounds (b) include or are selected from polysulfides (b2). In another embodiment of the invention, compounds (b) include or are selected from (bi)sulfites (b3). Mixture of any of these can also be used. In a particular embodiment of the invention, at least two compounds (b) are present.
  • urease inhibitors (cl) like NBPT and/or nitrification inhibitors (c2) like DCD can be added to products of the invention without negative impact on the stability of the thiosulfates and/or polysulfides and/or (bi)sulfites during drying. They can help protect and stabilize the urea present in products (I), (II) and (III) of the invention.
  • N-(n-butyl)-thiophosphoric triamide (NBPT) and phenylphosphorodiamidate (PPD) are two examples of urease inhibitors that are widely studied and/or used.
  • NBPT is commercially available under the trademark Agrotain ® available from Agrotain International, St. Louis, MO (Koch). Recently KOCH has been launching DUROMIDETM technology based on new powerful urease inhibitors like ANVOLTM.
  • Dicyandiamide (DCD) and 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin) are two examples of widely used nitrification inhibitors.
  • the urease inhibitor (cl) can be a liquid at room temperature, a liquid at elevated temperature, or a solid which is dissolved, dispersed or suspended into a liquid carrier. The same for the nitrification inhibitor (c2).
  • urease (cl) and/or nitrification (c2) inhibitors can be added as such.
  • cl urease
  • c2 nitrification
  • the NBPT used has a purity of at least about 90 wt%, preferably at least about 95, 96, 97, 98 or 99 wt%. Highly pure grades are available, for instance in powder from Sunfit Chemical Co. (China).
  • a urease inhibitor (cl) is used that includes or is NBPT.
  • a nitrification inhibitor (c2) is used that includes or is DCD.
  • other types of urease and/or nitrification inhibitors as described in the art can be added too if wanted.
  • compound (cl) and (c2) are different from each other and differ from the compounds (b) being used/present.
  • Additives or additional compounds (d) that optionally may be present in the products and the compositions of the invention include but are not limited to dyes, colorants, odor masking agents, flow aids, processing aids (such as, for example, a granulating binder), conditioning agents (like e.g. mineral oil), anti-caking agents (such as, for example, lime, gypsum, silicon dioxide, kaolinite and/or PVA), hardening agents (such as, for example, UF 85), surfactants, silicas, thickeners, viscosity modifiers, pH control agents, buffers, copper, molybdenum, elemental sulfur, additives to lower the urea melt
  • processing aids such as, for example, a granulating binder
  • conditioning agents like e.g. mineral oil
  • anti-caking agents such as, for example, lime, gypsum, silicon dioxide, kaolinite and/or PVA
  • hardening agents such as, for example, UF 85
  • Compounds (d) in the invention are different from any of compounds (a), (b), (c), and (e).
  • Processes of the invention for making compounds (II) or (III) of the invention preferably comprise at least the following steps:
  • Processes of the invention often further contain one or more of the following additional steps: a breaking step, a grinding step, a granulation step, a sieving step, a final drying step, a polishing step, a cooling step and/or a packaging step.
  • an aqueous composition (I) of the invention is provided from which water is then removed by evaporation, with or without vacuum.
  • temperatures can be kept below about 100°C which is beneficial for product stability , below about 95°C, below about 90, 89, 88,
  • temperatures of at most about 130°C, at most about 120°C, even at most about 115, 114, 113, 112, 110 or 110°C suffice to obtain a solid particulate product. Even at these temperatures products with excellent shelf life were obtained. The higher
  • urea is preferably added to liquid thiosulfates (bl') and/or to liquid polysulfides (b2') and/or liquid (bi)sulfites (b3').
  • the liquid compounds (b') are preferably pre-heated to a temperature of at least about 40, 45 or 50°C.
  • one or more compounds (cl) and/or (c2) and/or (d) can be added.
  • a 'dry' urea is used, though in some case the use of a liquid urea as available on the market can be handy too. This for instance, if high amounts of compounds (a) and/or of compounds (b) are used.
  • An alternative is to use a 'dry' urea and to add a minimal amount of extra water, just enough to allow a sufficient mixing of the compounds present.
  • An alternative way to make products (II) and (III) of the invention is to add compounds (b) to a urea melt (melt temperature of urea is about 133°C). This can be done in various ways, compounds (b) can be added in solid form.
  • the solid compound (b) in a preferred embodiment is a compound (II) and/or (III) of the invention. It is also possible to add liquid compounds (b') to the urea melt.
  • an aqueous composition (I) according to the invention is added to the urea melt.
  • liquid compounds (b') and/or aqueous composition (I) according to the invention are added to the urea melt, then it may be necessary to remove at least part of the water prior to granulation. This can yield products having at least compounds (a) and (b) spread substantially
  • Yet another way to make products (II) and (III) of the invention is to add solid compounds (b), liquid compounds (b') and/or an aqueous solution (I) of the invention to a liquid urea at a temperature of e.g. least about 130, 135, 140 or 145°C and to process these into granulates via a drum coating and/or a drum coating that has some heating sufficient to remove water. Due to their high solubility in water, it is even possible to add solid products (II) or (III) of the invention via spray drying. This can lead to solid products wherein compounds (a) are present primarily in the outer layers of the of the product, or wherein compounds (a) are present in a coating that is provided onto a urea granule.
  • any urea granule produced this way further contains a coating that provided moisture-repellent and/or anti-caking properties.
  • suitable anticaking and/or moisture repellent coatings are vegetable oil (rapeseed or neem), paraffin and Novoflow anti-caking and/or moisture repellence agent s (Novochem Fertilizer Additives, The Netherlands).
  • NBPT When NBPT is being present in combination with elemental sulfur, then it may be advantageous to have some stabilizers present like the alkaline or alkaline forming inorganic or organic compounds disclosed in WO 2018/069486. Otherwise the use of stabilizers is not really needed.
  • the mixture is heated to a temperature of for instance from about 40°C to about 70°C to facilitate dissolution of the urea-containing compound (in particular urea) added.
  • the urea-containing compound (in particular urea) preferably is added slowly, either continuously or in different steps.
  • a heating to at least about 40°C, preferably at least about 45°C (oil or heating fluid temperature) suffices to have compounds (a) dissolve.
  • Removal of water can be done at ambient pressure and/or by using vacuum (at least partly). Air drying is also possible (for instance at the end of the drying process) or via a fluidized bed drying equipment.
  • An advantage of the processes of the invention is that a heating to at most about 150, 149, 148, 147, 146 or 145°C, often at most about 140, 139, 138, 137, 136, 135, 134, 133, 132 or 131°C, preferably at most about 130, 129, 128, 127, 126 or 125°C, often at most 120, 119, 118, 117 or 116°C, even at most about 115°C can suffice to dry the products.
  • liquid thiosulfates, polysulfides and/or (bi)sulfites are in general susceptible to thermal and/or oxidative degradation.
  • NBPT optional compound cl
  • NBPT is sensitive to some extend to high thermal degradation.
  • a vacuum is applied during at least part of the drying step.
  • additional compounds (c) and/or (d) can be admixed. They can be provided in step (i) or at a later stage, depending on their nature and function. For instance process aids like a granulation binder (d) can be added at a later stage.
  • liquid compounds (b') When using liquid compounds (b') in a method of the invention, then in some occasions it may be handy to remove at least part of the water prior to their mixing with urea-containing compounds (a), for instance via evaporation. This applies in general but is useful in particular in the following embodiments.
  • materials (I), (II) and/or (III) of the invention are added to a standard urea production process, either to the molten urea in the urea synthesis unit or to the prilling tower.
  • Materials (I), (II) and/or (III) of the invention are preferably added to molten urea just before the urea leaves the urea synthesis unit, or just after the urea has left the urea synthesis unit, before it passes to granulation.
  • the retention time that is the time passing between the addition of these products/composition to the urea melt and the mixture proceeding to granulation, is kept short (below about 30 minutes, below about 15, 10, 5 minutes, below about 60, 50, 40, 30 or even 20 seconds).
  • the temperature of the urea melt can be kept low by adding an additive that allows to lower the urea melt temperature, like for instance UF80.
  • a solid product (II) and/or (III) is added to the molten urea, in the urea synthesis unit or in the prill tower.
  • a liquid thiosulfate and/or a liquid polysulfide and/or a liquid (bi)sulfite is added to the a molten urea, in the urea synthesis unit or in the prill tower.
  • materials (I), (II) and/or (III) of the invention may be added to a heated liquid urea having in a granulation drum, preferably one that is equipped with a spray drier.
  • the process often further contains one or more of the following steps: a compacting step, a granulation step, a sieving step, a grounding step and/or a packaging step.
  • compounds (b) are generally provided in such amounts that the final product (III) contains compounds (b) in an amount from about 1, 1.5, 2, 2.3 or 2.5 wt%. Preferably this amount is at least about 3, 3.5, 4, 4.5 or 5 wt%. In a particular embodiment of the invention, the amount of compounds (b) is at least about 10 wt%, more preferably at least about 15 wt%. Generally the amount of compounds (b) in the final product (III) is at most about 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 34, 33, 32, or 31 wt%.
  • the amount of compounds (b) is at most about 30, 29, 29, 28, 27, 26, or 25 wt%, or is at most about 24, 23, 22, 21, 21, 20, 19, 18, 17, 16, 15 wt%, or is even at most about 14, 13, 12, 11, or 10 wt%.
  • compounds (a) are generally provided in such amounts that the final product (III) contains compounds (a) in an amount from about 1, 1.5,
  • the amount of compounds (a) is at least about 15, 20, 25, 30 or 35 wt%. In another particular embodiment of the invention, the amount of compounds (a) is at least about 60, 65, 66, 67, 68, 69 or 70 wt%. Often the amount of compounds (a) is at most about 95, 94, 93, 92, 91, or 90 wt%, or at most about 89, 88, 87, 87 or 86 wt%, or even at most about 85 wt%.
  • the preferred compound (a) is urea (al).
  • products (II) and (III) that have compounds (a) and (b) spread substantially homogeneously within the solid particulate being produced. When present, then preferably also compounds (c), and (d) are spread substantially homogeneous over the product. When the latter are added at later stages, for instance by spraying the compounds on top of solid granules within a drying process (coating process), then a core-shell type kind of product is possible with compounds (c) and/or (d) and/or (e) present in the outer layers of the solid particulate formed, e.g. a urea granule.
  • the product (II) or (III) is a solid thiosulfate-urea based product.
  • the product (II) or (III) is a polysulfide-urea based product.
  • the product (II) or (III) is a (bi)sulfite-urea based product.
  • the product (II) or (III) can contain a mixture of compounds (b): a mixture of compounds (bl) and (b2), of compounds (bl) and (b3), of compounds (b2) and (b3) or of compounds (bl), (b2) and (b3). Information on preferred compounds (bl), (b2) and (b3) can be found above.
  • products (II) and (III) of the invention contain water (e), urea- containing compounds (a) and compounds (b) only. Preferred ratios of compounds (a) to compounds (b) have been provided above. [00113] Generally the amount of compounds (a), relative to the total of a+b, is at least about 2, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7 or 3 wt%. Typically this amount is at most about 98, 97, 96,
  • the amount of compounds (a) is at least about 4 wt%, relative to the total of a+b. In a particular embodiment, this amount is at least about 20, 30, or 40 wt%, relative to the total weight of a+b.
  • the amount of compounds (b), relative to the total of a+b is at least about 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7 or 3 wt%. Typically this amount is at most about 98,
  • the amount of compounds (b) is at least about 4 wt%, relative to the total of a+b. In a particular embodiment, this amount is at least about 20, 30, or 40 wt%, relative to the total weight of a+b.
  • compounds (a) are present in product (II) or (III) of the invention in an amount of at least about 3, 4, 5, or 6 wt%, preferably at least about 7, 8, 9, or 10 wt%, or more preferably at least about 11, 12, 13, 14, or 15 wt% and more.
  • compounds (a) are present in these products in an amount of at least about 85, 86, 87, 88 or 89 wt%, or even at least about 90 wt%.
  • compounds (a) are present in an amount of at most about 15, 14, 13, 12, 11, or 10 wt%, or even at most about 9, 8, 7, 6 or 5 wt%.
  • Compounds (b) are generally present in products (II) or (III) the invention in an amount of from about 1 to about 99 wt%, more preferably from about 2 to about 98 wt%, and most preferably from about 2.3 to about 97.7 wt%, from about 2.4 to about 97.6 wt% or from about 2.5 to about 97.5 wt%.
  • this amount is at most about 95, 94, 93, 92 or 91 wt%, more preferably at most about 90, 89, 88, 87 or 86 wt%, even more preferably at most about 85, 84, 83, 82 or 81 wt%, and most preferably at most about 80 wt%.
  • the amount of compounds (b) in these products is at least about 2, 3, 4, or 5 wt%, even at least about 10, 11, 12, 13, 14, of 15 wt%, up to at most about 25 wt%, more preferably at most about 20 wt%.
  • compounds (b) in this embodiment are chosen from those compounds that have a well-established urease and/or nitrification inhibiting effect so that no compounds (c) are needed.
  • the amount of compounds (b) in these products is at most about 15, 14, 13, 12, or 11 wt%, more preferably at most about 10, 9 or 8 wt%. In this embodiment, the amount of compounds (b) is often at least about 1, 2, 3, 4 or 5 wt%.
  • urease inhibitors (cl) are generally present in an amount from about 0.001 wt% to about 85 wt%. Preferably this amount is at most about 80, 75, 70, 60 or 50 wt%. Usually this amount is at least about 0.01, 0.02, 0.03, or 0.04 wt%. Usually this amount is at most about 40, 39, 38, 37, or 36 wt%, most often at most about 35, 34, 33, 32, 31 or 30 wt%.
  • a person skilled in the art will know how to adapt the amounts of NBPT in function of the way the solid products of the invention are made and used in the field, so that the quantity of NBPT added is about 900mk/kg urea.
  • the amount of compounds (cl) being present in products (II) and (III) of the invention is from about 0.001 to about 1.5 wt%, preferably from about 0.01 to about 1 wt%.
  • the concentration of NBPT in urea granules is generally from about 0.04 to about 0.1 wt%. When present in outer layers only, then this amount may be at most about 0.5, 0.4, 0.3 or 0.2 wt%, even at most about 0.1, 0.09, 0.08, 0.07 or 0.06 wt%. Often at least about 0.0001, preferably at least about 0.02, 0.03 or 0.04 wt% of NBPT is present.
  • carrier materials for compounds (cl) can contain from about 0.1 wt% to about 85, 80, 75, 70, 65, 60, or 55 wt%, or preferably to about 50, 45, 40, 39, 38, 36, 37, 35, 34, 33, 32, 31 or 30 wt% of compounds (cl).
  • Compounds (cl) are herein preferably present in an amount of at least about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 wt%.
  • nitrification inhibitors (c2) are generally present in an amount from about 0.01 to about 85 wt%, often to about 80 wt%. Preferably this amount is at most about 75, 70, 65, 60, 55 or 50 wt%. Often compounds (c) are present in an amount from about 0.04 to about 40 wt%. Preferably this amount is at least about 0.1 wt%, more preferably at least about 0.2 wt%. Usually this amount is at most about 39, 38, 37, or 36 wt%, most often at most about 35, 34, 33, 32, 31 or 30 wt%.
  • the amount of compounds (c2) is often from 0.01 to about 4 wt%, more preferably from about 0.1 to about 3 wt%. When present in outer layers only, then this amount may be lower. Higher amounts can be present, for instance in carrier materials for compounds (c2). These materials can contain from about 0.5 to about 85, 80, 75, 70, 65, 60, or 55 wt%, preferably to about 50, 45, 40, 39, 38, 36, 37, 35, 34, 33, 32, 31 or 30 wt% of compounds (c2). In a particular embodiment of the invention, this amount is at least about 1, 1,5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 wt%.
  • the total amount of compounds (c) is at most about 85, 80, 75, 70, 65,
  • compounds (c) are present in an amount of from about 15 to about 50 wt%, from about 20 to about 50 wt%, more preferably from about 25 to about 40 wt%.
  • compounds (cl) and/or (c2) are present in an amount from about 0.01 to about 20 wt%.
  • a preferred compound (cl) is NBPT
  • a preferred compound (c2) is DCD
  • the term 'NBPT' is used to refer not only to N-(n-butyl) thiophosphoric triamide in its pure form but also to commercial grades that may contain a given amount of impurities. The same applies for 'DCD'.
  • a particular embodiment of the invention relates to products (II) or (III) of the invention that have NBPT but no DCD.
  • Another particular embodiment of the invention relates to products (II) or (III) that have DCD but no NBPT.
  • Yet another particular embodiment of the invention relates to products (II) or (III) that have DCD but no NBPT.
  • embodiment of the invention relates to products (II) or (III) that have both NBPT and DCD.
  • Another embodiment of the invention relates to products (II) or (III) that have no NBPT and no DCD.
  • a particular embodiment of the invention relates to products (II) or (III) wherein no compounds (c) are present. Even if compounds (c) are present then it is possible and preferred to have products that are substantially free from organic solvents including having a boiling point above about 150°C. Preferably they are also substantially free from organic solvents including having a boiling point above about 125°C.
  • compounds (cl) and/or (c2) are present in an amount from about 2.5 to about 50 wt%.
  • compounds (cl) and/or (c2) are then present in an amount of at least about 10, 11, 12, 13 or 14 wt%, preferably at least about 15, 16, 17, 19, 19 or 20 wt%, often at least about 25 wt%.
  • the amount of compounds (a) is usually from about 1 to about 15, 14, 13, 12, 11 or 10 wt% at most.
  • the amount of compounds (b) is usually from about 1 to about 15, 14, 13, 12, 11 or 10 wt% at most. The sum of the weight percentages of course does not exceed 100 wt%.
  • compounds (b) are present in an amount of at least about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or about 5 wt%. Most of the amount of compound (b) in products (II) or (III) of the invention is from about 2 wt% to about 90, 85,
  • the amount of compounds (b) is often at most about 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 wt%. In a particular embodiment of the invention, the amount of compound (b) is between about 2 wt% and about 90, 85, or 80 wt%.
  • Products (II) and (III) to be used as N&S fertilizer often contain at most about 85, 84, 83, 82 or 81 wt%, even at most about 80, 79, 78, 77, 76 or 75 wt% of urea.
  • N&S fertilizer is for instance a 25-0-0-6S fertilizer.
  • compounds (cl) and/or (c2) can be present too though this is not needed.
  • Compounds (cl), where present are then typically present in an amount from about 0.01 to about 0.1 wt%.
  • Compounds (c2), where present are then typically present in an amount from about 0. 1 to about 4 wt%. The sum of the weight percentages of course does not exceed 100 wt%.
  • a particular embodiment of the invention relates to urea granules that comprise compounds (b) and compounds (cl) and/or (c2).
  • the urea granule of the invention has a N (nitrogen) content of at least about 35, 36, or 37 wt%, preferably at least about 38 or 39 wt%, or more preferably at least about 40, 41, or 42 wt%.
  • the amount of water (e) in products (II) or (III) of the invention, after drying, usually is from about 0.01 to about 10 wt%, preferably from about 0.02 to about 8 wt%.
  • the final water content in products (II) or (III) preferably is less than about 8 wt%, preferably less than about 7, 6, 5, 4 or 3 wt%. More preferably the water content is less than about 2, 1.5, or 1 wt%. In a particular embodiment, the water content is less than about 0.5, 0.4, 0.3, or even 0.2 wt%.
  • the 'water content' refers herein to the free water content as can be determined by a Karl Fischer method.
  • water and compounds (a)+(b) are the primary constituents of products (II) or (III) of the invention.
  • the sum of their weight percentages (of a+b+e) is at least about 80 wt%, most often at least about 85 wt%.
  • this sum is at least about 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt% and in particular this sum may equal 100 wt%.
  • the sum of the weight percentages of a+b+c+d+e will not exceed 100 wt%.
  • Products (II) or (III) of the invention in general contain less than about 5 wt% of oxidation by-products of compounds (b).
  • oxidation by-products include the corresponding sulfates and/or sulfites and also elemental sulfur.
  • Preferably less than about 3 wt%, more preferably less than about 2 wt%, or even more preferably less than about 1 wt% of these oxidation by-products of compounds (a) are formed during the drying process.
  • the products (II) and (III) of the invention can be easily combined with UAN, the products themselves typically contain little to no UAN. They are sufficiently stable in themselves. Usually, they comprise less than about 1 wt% of UAN. Preferably, they comprise less than about 0.5 wt%, more preferably less than about 0.1 wt% of UAN, relative to the total weight of the product [in case of a product (I), (II) or (III)].
  • Products (II) or (III) of the invention in general have higher amounts of N and S. In any case, there will be an increased amount of nutrients (N,S, Ca, Mg and K) in the final products due to evaporation and concentration.
  • products (II) or (III) of the invention are solid thiosulfates, solid polysulfides and/ or a solid (bi)sulfites depending on the type of compounds (b) present.
  • the amounts of compounds (a) and where present compounds (c) and/or (d) are generally low.
  • At least compounds (a) and (b) are spread substantially homogeneously within the products (II) or (III) of the invention.
  • compounds (c) and/or (d) when present can be spread substantially homogeneously within the products (II) or (III).
  • compounds (c) and/or (d) can be present primarily in the outer layers of the solid particulates being formed and/or they can be present in a coating applied onto the solid particulate formed, e.g. a urea granule.
  • compounds (a) and (b), and where present (c) and/or (d), can all be present primarily in the outer layers of the solid particulates being formed and/or they can be present in a coating applied onto the solid particulate formed, e.g. a urea granule.
  • a coating applied onto the solid particulate formed e.g. a urea granule.
  • Products (I), (II), and (III) of the invention have a wide applicability but are in particular highly suited for use in or as fertilizer compositions. They were found highly compatible with standard liquid and solid NPK fertilizers or fertilizer ingredients.
  • a fertilizer composition liquid or solid, comprising an aqueous composition (I) and/or a product (II) or (III) of the invention.
  • this fertilizer composition comprises at least one further fertilizer compound that is different from compounds (I), (II), and (III) of the invention.
  • That other fertilizer can be a standard NPK fertilizer, either liquid or solid.
  • Suitable fertilizers with which products of the invention can be blended are set forth above.
  • a liquid fertilizer composition that comprises materials (I), (II) or (III) of the invention.
  • Products (I), (II) or (III) of the invention when added to a liquid fertilizer preferably are re-solubilized in water or another suitable liquid, possibly UAN (urea ammonium nitrate fertilizer) before adding them to a liquid fertilizer.
  • UAN urea ammonium nitrate fertilizer
  • the liquid fertilizer composition of the invention can contain further standard ingredients like UAN (like UAN 28, UAN 32, etc.).
  • Other liquid fertilizers with which products of the invention are compatible are liquid ammonium polyphosphates (APP),
  • liquid fertilizer can also contain a certain amount of solid fertilizers like additional urea, a solid ammonium sulfate, a solid magnesium sulfate, a solid potassium sulfate, a solid ammonium nitrate, a solid calcium nitrate, a solid potassium nitrate, etc.
  • a solid fertilizer composition that comprises materials of the invention, in particular products (II) or (III) of the invention.
  • materials of the invention can be easily blended with standard solid fertilizers such as dry urea, a solid ammonium sulfate, a solid magnesium sulfate, a solid potassium sulfate, a solid ammonium nitrate, a solid calcium nitrate, a solid potassium nitrate, etc.
  • a particular fertilizer of the invention is a protected urea containing at least one thiosulfate (bl) and/or at least one polysulfide (b2) and/or at least one (bi)sulfite (b3) in an amount that they exert urease and/or nitrification inhibitory effects.
  • This kind of urea fertilizer is typically provided under the form of a urea granule.
  • this urea granule can further contain NBPT and/or DCD.
  • the urea granule contains NBPT, DCD or a mixture of both.
  • the urea granule contains NBPT.
  • the urea granule is substantially free from NBPT, preferably contains no NBPT.
  • the urea granule does not contain any NBPT or DCD.
  • a particular embodiment of the invention relates to products (I), (II) or (III) of the invention that can be characterized as liquid or solid carriers for nitrogen inhibitors like NBPT and/or DCD. These carrier materials can be incorporated into liquid and/or to solid fertilizers.
  • An advantage of products of the invention is that they require less organic solvents like NMP, DMSO, etc. It is even possible and preferred to use 'dry' NBPT and/or dry DCD, without any liquid or solid carrier to make materials of the invention.
  • thiosulfate such as ammonium thiosulfate, potassium thiosulfate, calcium thiosulfate, magnesium thiosulfate, calcium polysulfide or ammonium (bi)sulfite.
  • DCD and NBPT were added in dry form. Solid products with varying amounts of compounds (a), (b) and (c) were prepared and all were found to have a good shelf life when stored in a sealed container.
  • the amount of sulfur (S) is determined by AOAC Gravimetric Method No 980.02 [00151] If not otherwise mentioned, the amount of thiosulfates is determined via ion chromatography using an AS 11 4x250 mm with guard column AG11 4x50 mm. Mobile phase: 20 mM KOH (isocratic). Flow rate: 1 ml/min. Detection: conductivity.
  • Amount of potassium (K) was determined by AAS (Atomic Absorption
  • the thiosulfate, urea and some extra water are loaded in the reactor. At about 60°C, when everything is in solution, the water is evaporated under vacuum while stirring at low speed. After evaporation, the reactor is cooled to about 25°C and the vacuum is broken with a stream of N 2 . To avoid bigger clumps, the product is sieved (5 mm sieve).
  • Ammonium bisulfite is a 60-67% liquid solution with a pH about 5-5.8.
  • a solid product was obtained by mixing this ammonium bisulfite solution with dry urea in a 1:1 weight ratio (i.e., 100 grams dry urea was added to 100 grams of this 60-70 wt% ammonium bisulfite solution in water). Addition of the urea was done as described before using some preheating (about 50-60°C). Water was removed by heating to about 100°C. A white solid was obtained after a slow drying for about 2 hours at this temperature.
  • the amount of compounds (b) on a dry weight basis is about 16.7 wt% in Example 8; about 20 wt% in Example 9, about 9.5 wt% in Example 10 and about 17.8 wt% in Example 11.
  • 'CaTs®' refers to the Tradename of a commercial 24-25 wt% calcium thiosulfate
  • ' KTS®' refers to the Tradename of a commercial 50 wt% potassium thiosulfate solution
  • 'MagThio®' refers to the Tradename of a commercial 24 wt% magnesium thiosulfate solution
  • 'Thio-Sul ®' refers to a commercial 57-60 wt% ammonium thiosulfate solution.
  • Ammonium thiosulfate-urea based product containing 20 wt% (NH 3 ) 2 S 2 0 3
  • the products were measured for their storage stability in terms of stability of the content of CaS 2 0 3 or of (NH 3 ) 2 S 2 0 3 in the product. Measurements are made at 0 month after production (i.e. the initial content of CaS 2 0 3 or of (NH 3 ) 2 S 2 0 3 , 2 months after production, 4 months after production.) Samples are stored at room temperature (about 18°C to 25°C) in closed polyethylene containers.
  • the amount of thiosulfates is measured according to following method from American National Standards Institute: SPECIFICATION FOR PHOTOGRAPHIC GRADE AMMONIUM THIOSULFATE SOLUTION; Procedure # ANSI-PH4.252-1980; 1980.
  • Calcium thiosulfate-urea based products are evaluated to determine whether elemental sulfur is formed upon storage.
  • Samples are made by dissolving 12, 5g, 25g and 50g of dry calcium thiosulfate/urea product of different CaTs ® /urea ratios (see table below) in 87, 5g, 75g and 50g of water respectively, to produce a 12,5%, 25% and 50% solution respectively. After dissolution, all samples are clear without any visible particles. The samples are kept in closed glass containers for 5 months. At 5 months, the samples are observed for the presence of elemental sulfur. When present, elemental sulfur is visible with the naked eye as precipitated particles. A clear solution means that substantially no elemental sulfur is formed. The results are shown in table below.
  • the amount of thiosulfates is measured according to following method from American National Standards Institute; SPECIFICATION FOR PHOTOGRAPHIC GRADE AMMONIUM THIOSULFATE SOLUTION; Procedure # ANSI-PH4.252-1980; 1980.

Abstract

L'invention concerne des produits à base de thiosulfate-urée (IIa) et/ou des produits à base de polysulfure-urée (IIb) et/ou des produits à base de (bi)sulfite-urée (IIc) appropriés pour être utilisés dans des engrais et comprenant un ou plusieurs composés contenant de l'urée (a), un ou plusieurs composés (b), éventuellement, un ou plusieurs inhibiteurs d'uréase (c1) et/ou de nitrification (c2) qui sont différents des composés (b), et/ou éventuellement, un ou plusieurs additifs (d) qui sont différents de l'un quelconque des composés ci-dessus, la quantité d'eau (e) dans le produit (II) étant inférieure à environ 10 % en poids, de préférence inférieure à environ 5 % en poids, les composés (a) étant sélectionnés parmi des produits à base d'urée (a1) et/ou d'urée-aldéhyde (a2) et/ou parmi des composés à base d'urée-triazone (a3), les composés (b) étant sélectionnés parmi les thiosulfates (b1) et/ou parmi les polysulfures (b2) et/ou les (bi)sulfites (b3). Un avantage des produits de l'invention est que seules des quantités minimales de produits de dégradation des composés (b) sont formées. Les produits de l'invention peuvent être réalisés sous diverses formes et de différentes manières. Tous les matériaux de l'invention sont appropriés pour être utilisés dans des engrais et se mélangent bien avec les engrais solides et liquides classiquement utilisés.
PCT/US2019/045544 2018-08-08 2019-08-07 Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation WO2020033575A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2019319857A AU2019319857A1 (en) 2018-08-08 2019-08-07 Compositions comprising solid thiosulfates, polysulfides and/or (bi)sulfites with an urea compound and methods for preparing same
EA202190325A EA202190325A1 (ru) 2018-09-19 2019-08-07 Композиции, включающие твердые тиосульфаты, полисульфиды и/или (би)сульфиты, и способы их получения
EP19759149.8A EP3833646A1 (fr) 2018-08-08 2019-08-07 Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation
CA3107147A CA3107147A1 (fr) 2018-08-08 2019-08-07 Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un compose uree et leurs procedes de preparation
US17/266,590 US20210300831A1 (en) 2018-08-08 2019-08-07 Compositions comprising solid thiosulfates, polysulfides and/or (bi)sulfites and methods for preparing same
BR112021002403-4A BR112021002403A2 (pt) 2018-08-08 2019-08-07 composições que compreendem tiossulfatos sólidos, polissulfetos e/ou (bi)sulfitos com um composto de ureia e métodos para preparar as mesmas

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201862716243P 2018-08-08 2018-08-08
US62/716,243 2018-08-08
EP18195470.2A EP3626696A1 (fr) 2018-09-19 2018-09-19 Compositions comprenant des thiosulfates, polysulfures solides et/ou des (bi)sulfites et procédés pour leur préparation
EP18195470.2 2018-09-19

Publications (1)

Publication Number Publication Date
WO2020033575A1 true WO2020033575A1 (fr) 2020-02-13

Family

ID=67766314

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/045544 WO2020033575A1 (fr) 2018-08-08 2019-08-07 Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation

Country Status (1)

Country Link
WO (1) WO2020033575A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112292366A (zh) * 2018-06-04 2021-01-29 欧洲化学农业有限公司 用于处理含尿素肥料的乳液
WO2023161232A1 (fr) 2022-02-22 2023-08-31 Tessenderlo Group Nv Procédés de production d'engrais azoté et d'engrais azoté-soufré
WO2023161236A1 (fr) 2022-02-22 2023-08-31 Tessenderlo Group Nv Procédés de production d'un engrais solide à base d'urée-thiosulfate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289757A2 (fr) * 1987-05-02 1988-11-09 SKW Trostberg Aktiengesellschaft Inhibiteur de nitrification
EP0376853A1 (fr) * 1988-12-29 1990-07-04 FREEPORT McMORAN RESOURCE PARTNERS LIMITED PARTNERSHIP Engrais azoté granulé homogène
US5618658A (en) 1995-02-22 1997-04-08 Fuji Hunt Photographic Chemicals, Inc. Process for producing an ammonium thiosulfate product
WO2005075602A1 (fr) * 2004-02-09 2005-08-18 Ballance Agri-Nutrients Limited Compositions d'engrais
US7494525B2 (en) 2005-02-22 2009-02-24 Tessenderlo Kerley, Inc. Calcium polysulfide, potassium polysulfide, calcium thiosulfate, and magnesium thiosulfate as urease inhibitors
CN106673907A (zh) * 2016-12-27 2017-05-17 贵州大学 一种大头菜专用肥及制备方法
WO2018069486A2 (fr) 2016-10-13 2018-04-19 Yara International Asa Composition améliorée à base d'urée contentant du soufre élémentaire et son procédé de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289757A2 (fr) * 1987-05-02 1988-11-09 SKW Trostberg Aktiengesellschaft Inhibiteur de nitrification
EP0376853A1 (fr) * 1988-12-29 1990-07-04 FREEPORT McMORAN RESOURCE PARTNERS LIMITED PARTNERSHIP Engrais azoté granulé homogène
US5618658A (en) 1995-02-22 1997-04-08 Fuji Hunt Photographic Chemicals, Inc. Process for producing an ammonium thiosulfate product
WO2005075602A1 (fr) * 2004-02-09 2005-08-18 Ballance Agri-Nutrients Limited Compositions d'engrais
US7494525B2 (en) 2005-02-22 2009-02-24 Tessenderlo Kerley, Inc. Calcium polysulfide, potassium polysulfide, calcium thiosulfate, and magnesium thiosulfate as urease inhibitors
WO2018069486A2 (fr) 2016-10-13 2018-04-19 Yara International Asa Composition améliorée à base d'urée contentant du soufre élémentaire et son procédé de fabrication
CN106673907A (zh) * 2016-12-27 2017-05-17 贵州大学 一种大头菜专用肥及制备方法

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 201747, Derwent World Patents Index; AN 2017-32674L, XP002795377 *
HE ET AL., SOIL SCIENCE, vol. 164, 1999, pages 750 - 758
JOHN AMBROSE: "Contributions from Gibbs Chemical", September 1949, LABORATORY OF HARVARD UNIVERSITY, article "Inhibition of Urease By Sulfur Compounds"
L. MAZZEI, J. OF INORG BIOCHEM., January 2016 (2016-01-01)
SALLADESIMS, PLANT & SOIL, December 1992 (1992-12-01)
SOAUD ET AL., J OF AUSTRALIAN CROP SCIENCE, May 2011 (2011-05-01)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112292366A (zh) * 2018-06-04 2021-01-29 欧洲化学农业有限公司 用于处理含尿素肥料的乳液
WO2023161232A1 (fr) 2022-02-22 2023-08-31 Tessenderlo Group Nv Procédés de production d'engrais azoté et d'engrais azoté-soufré
WO2023161236A1 (fr) 2022-02-22 2023-08-31 Tessenderlo Group Nv Procédés de production d'un engrais solide à base d'urée-thiosulfate

Similar Documents

Publication Publication Date Title
US3725029A (en) Preparation of ammonium sulfate fertilizer constituent
WO2020033575A1 (fr) Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation
FI118598B (fi) Lannoiterae ja menetelmä sen valmistamiseksi
EP2890662B1 (fr) Technique de passivation d'urée et nouveau produit urée passivée, pour fabriquer de l'urée ou un composé à base d'urée pouvant être mélangé de façon universelle
CN106414373B (zh) 在基于尿素的颗粒的外壳中结合微量营养素的方法
AU2009271213A1 (en) Methods for preparing compositions comprising ammonium nitrate double salts
CA3107176A1 (fr) Compositions d'engrais a base d'uree stabilise et procedes de preparation associes
AU2013307322B2 (en) Method for limiting the use of an ammonium nitrate fertilizer as a precursor for an explosive and composition therefor
EP3833646A1 (fr) Compositions comprenant des thiosulfates, des polysulfures et/ou des (bi)sulfites solides avec un composé urée et leurs procédés de préparation
RU2162073C2 (ru) Удобрение на основе нитрата кальция и способ его получения
EP4015491A1 (fr) Procédé de fabrication d'une composition à base d'urée comprenant l'addition d'un additif solide sans liquide
PL241460B1 (pl) Kompozycja nawozu wieloskładnikowego w postaci granulek oraz sposób jej wytwarzania
WO2020033576A1 (fr) Compositions d'engrais à base d'urée stabilisé et procédés de préparation associés
WO1995021689A1 (fr) Uree granulaire
RU2769477C2 (ru) Улучшение антислеживающих свойств частиц нитрата аммония при хранении в закрытом контейнере
EP4157808A1 (fr) Procédé pour la fabrication d'une composition à base de nitrate d'ammonium et produits associés
EP4341232A1 (fr) Engrais à co-cristal
JP2002053382A (ja) 肥 料
JPH0114197B2 (fr)
CN106220438A (zh) 一种含腐植酸硝酸钙镁肥料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19759149

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3107147

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112021002403

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 2019319857

Country of ref document: AU

Date of ref document: 20190807

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2019759149

Country of ref document: EP

Effective date: 20210309

ENP Entry into the national phase

Ref document number: 112021002403

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20210208