EP4330263A1 - Verfahren zur herstellung von phosphoryl oder thiophosphoryltriamid und verwendung einer verbindung in stickstoffdüngemittelformulierungen - Google Patents

Verfahren zur herstellung von phosphoryl oder thiophosphoryltriamid und verwendung einer verbindung in stickstoffdüngemittelformulierungen

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Publication number
EP4330263A1
EP4330263A1 EP22720512.7A EP22720512A EP4330263A1 EP 4330263 A1 EP4330263 A1 EP 4330263A1 EP 22720512 A EP22720512 A EP 22720512A EP 4330263 A1 EP4330263 A1 EP 4330263A1
Authority
EP
European Patent Office
Prior art keywords
triamide
liquid phase
precipitate
fertilizer
phosphoryl
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP22720512.7A
Other languages
English (en)
French (fr)
Inventor
Bernard BEAL
Eric BELLEPERCHE
Bruno MONTAGNIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novaem Bbtrade
Original Assignee
Novaem Bbtrade
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novaem Bbtrade filed Critical Novaem Bbtrade
Publication of EP4330263A1 publication Critical patent/EP4330263A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/062—Organo-phosphoranes without P-C bonds
    • C07F9/065—Phosphoranes containing the structure P=N-
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
    • 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

Definitions

  • the invention relates to the field of synthetic organic chemistry, and more particularly to the synthesis of phosphoryl triamide (abbreviated PTA, Phosphoryl Tri Amide) or its thio homolog (abbreviated TPTA, Thio Phosphoryl Tri Amide). It presents a new simple and ecological process to obtain this compound in a highly enriched form, and in particular in the form of a mixture enriched in phosphoryl triamide and depleted in chlorides.
  • PTA phosphoryl triamide
  • TPTA Thio Phosphoryl Tri Amide
  • the invention also relates to the field of agrochemistry, and more particularly to the use of such a mixture enriched in PTA or TPTA and depleted in chlorides in formulations of nitrogenous fertilizers, and in particular in solid formulations of fertilizers based on urea, with the aim of inhibiting urease in order to limit the losses of ammonia by volatilization and thus increase the real coefficient of use of the nitrogenous fertilizer.
  • nitrogen fertilizers based on urea are the main nitrogen fertilizer with an overall annual volume of around 180 million tonnes; only in some countries do ammonium nitrate products containing either 33.5% ammonium nitrate (which present an explosion hazard) or 27% ammonium nitrate in the form of calcium ammonium nitrate (inerted) exceed the 'urea.
  • Urea is commonly used in the form of granules with a diameter of between approximately 2 mm and approximately 4 mm, typically containing approximately 46% by mass of nitrogen, or in the form of a nitrogenous solution which may contain, in addition to urea, ammonium nitrate.
  • urea The major disadvantage of urea is the volatilization of ammonia, which results from the action of the enzyme urease, and which leads to significant losses of nitrogen, atmospheric pollution linked to ammonia, and the eutrophication of natural environments.
  • the European Union like other countries in the world, seeks to reduce the emission of ammonia into the atmosphere.
  • the use of mineral fertilizers represents approximately 22% of ammonia emissions, 80% of which come from mineral fertilizers, knowing that 75% of ammonia emissions come from livestock farming.
  • urease inhibitors To mitigate the emission of ammonia from nitrogenous fertilizers, the use of urease inhibitors is one way among others (such as burying the fertilizer, coating grain for delayed release, and irrigation following nitrogen fertilizer application). With regard to urease inhibitors, their ecotoxicological assessment must however be taken into account insofar as they are synthetic products.
  • WO 2009/079994 describes urea-based fertilizers comprising thiophosphoryl triamine derivatives, such as N-(n-butyl) thiophosphoric triamide (abbreviated nNBPT or simply NBPT) and N-(n- propyl)-thiophosphoric (abbreviated nNMP).
  • nNBPT N-(n-butyl) thiophosphoric triamide
  • nNMP N-(n- propyl)-thiophosphoric
  • Urease is an enzyme that catalyzes the transformation of urea into carbon dioxide and ammonia (which can react to form ammonium, a highly water-soluble cation); it is present in a large number of bacteria, yeasts and plants.
  • urease hydrolyzes urea which turns into NH4 + .
  • NH4 + nitrate
  • urease inhibitors Another problem with urease inhibitors is their ecotoxicity. For example, in certain countries such as France, urease inhibitors cannot be homologated, and in particular NBPT, mentioned above, is not considered there today as a satisfactory product in terms of ecotoxicology. Its use can only be done thanks to an extension of the EC fertilizer standard. These complex organic derivatives of TPA are moreover quite expensive, and their synthesis leads to a mixture of products, among which dimers and oligomers are often found.
  • the present invention aims to propose new preparations of inhibitors of urease, of low toxicity, which can be simply and conveniently incorporated into a solid nitrogen fertilizer, and which are inexpensive. And finally, it is desired that the process for manufacturing the urease inhibitor preparation has as low an ecological impact as possible, which prohibits the use of toxic auxiliary products, as well as processes which discourage the use of process that generate secondary products that need to be treated in a specific way.
  • a first object of the invention is a process for the manufacture of phosphoryl triamide OP(NH 2 ) 3 or of thiophosphoryl triamide SP(NH 2 ) 3 in which a) phosphoryl trichloride OPCI is reacted, respectively 3 or thiophosphoryl trichloride SPCI 3 , with gaseous ammonia in an apolar liquid phase to obtain a first precipitate comprising phosphoryl triamide and ammonium chloride, b) said first precipitate is treated with sodium carbonate or potassium carbonate, preferably with sodium carbonate, in a polar organic liquid phase, to obtain a second precipitate comprising NaCl, knowing that the phosphoryl triamide or the thiophosphoryl triamide, respectively, remain in said polar organic liquid phase, and separating said second precipitate from said polar organic liquid phase.
  • the latter can undergo a further concentration step to increase its phosphoryl triamide concentration, for example by partial evaporation of said polar organic liquid phase.
  • a step c) is added in which said organic liquid phase obtained at the end of step b) is evaporated to obtain a third precipitate comprising, respectively, phosphoryl triamide or thiophosphoryl triamide.
  • Said carbonate, sodium or potassium, is preferably anhydrous.
  • Said first precipitate typically has a mass fraction of phosphoryl triamide or thiophosphoryl triamide of at least 15%, preferably of at least at least 22%, and even more preferably at least 28%; this simplifies the purification step (step b).
  • Another object of the invention is the product capable of being obtained by the method described above and comprising steps a) and b), said product being said third precipitate.
  • This precipitate has a high concentration of PTA or TPTA, with a specific spectrum of impurities.
  • said third precipitate has a mass fraction of PTA or TPTA of at least 70%, preferably of at least 80%, and even more preferably of at least 90%; depending on the reaction conditions, said concentration of PTA or TPTA can exceed 90% by mass, and can reach 92%, 94% or even 96%.
  • Yet another object of the invention is the use of said polar organic liquid phase obtained at the end of step b), possibly diluted, to coat or impregnate granules of nitrogen fertilizer, preferably based on urea, for inhibiting and/or regulating the loss of nitrogen from a nitrogenous fertilizer, in particular for inhibiting and/or regulating the enzymatic hydrolysis of urea, and/or for inhibiting and/or regulating the microbiological oxidation of 'ammonium.
  • Yet another object of the invention is a process for the preparation of a so-called stabilized solid nitric fertilizer formulation, in which a solid nitric fertilizer is supplied, and it is impregnated with a liquid phase comprising which is said liquid phase polar organic material obtained at the end of step b), possibly diluted, or which is obtained by complete dissolution of said third precipitate in water.
  • said liquid phase is used in a quantity which does not exceed 3 L of liquid per ton of fertilizer, preferably does not exceed 2.5 L per ton of fertilizer, and even more preferably does not exceed 2 L. per ton of fertilizer. This does not alter the properties (in particular the rheological properties) of the granular solid of the fertilizer, and does not affect its storage stability.
  • OP(NH2)3 we prefer here the simplified writing OP(NH2)3 to the more common writing PO(NH2)3 because it better represents the structure of the molecule.
  • the PTA manufacturing process according to the invention comprises two steps.
  • the first step is known as such: phosphorus oxychloride OPCb is reacted with gaseous ammonia at the G interface of the apolar liquid phase to obtain a first precipitate comprising PTA and ammonium chloride.
  • This reaction typically takes place at a temperature below 20°C, preferably between -20°C and 20°C, and even more preferably between -10°C and 5°C.
  • Said apolar liquid phase advantageously comprises anhydrous chloroform as solvent. Any trace of water in the reaction medium risks promoting the hydrolysis of phosphoryl chloride to phosphoric acid.
  • the gaseous NH 3 is introduced into a reactor in which the said apolar liquid phase and the OPCI 3 are located.
  • the PTA which represents, with the secondary product NH4Cl, the first precipitate.
  • the introduction of gaseous NH 3 into the reactor is industrially easy to carry out, and makes it possible to control the reaction well, which can be stopped at any time without danger of explosion or release of ammonia, the ammonia being consumed quickly by the reaction with phosphorus oxychloride.
  • said apolar liquid phase is chloroform, preferably anhydrous. It can be easily recycled, and can in particular be reused in this first step of the process.
  • the NH 3 gas can be introduced, preferably with an overpressure of the order of 0.1 bar to 0.3 bar, into the reactor in which the chloroform and the phosphorus oxychloride are found, preferably at a temperature between about 2°C and 6°C.
  • the separation of said first precipitate can be done with known methods, in particular by filtration or centrifugation.
  • the product represented by the first precipitate advantageously comprises at least 15% by weight of PTA; this supposes in particular the use of an anhydrous apolar solvent and to work at a temperature not not exceeding 20°C.
  • the mass fraction of PTA is at least 22% or even at least 28%; it can typically reach about 35%.
  • this first precipitate as it is as a preparation of urease inhibitor in a nitrogenous fertilizer, because it comprises a large quantity of ammonium chloride, highly soluble, the anion of which is undesirable in a agricultural soil, and the cation, a nitrogen carrier, which is difficult for certain plants to assimilate.
  • this first precipitate which contains a high concentration of ammonium chloride a fairly large quantity of water must be used, which will entail the need to impregnate the fertilizer with a quantity of liquid greater than 4 liters per ton of treated fertilizer, which is undesirable.
  • the process according to the invention comprises a second step which aims to separate the PTA from the ammonium chloride.
  • step b) said first precipitate is treated first with a polar organic liquid phase (such as methanol or ethanol), to dissolve it. This is advantageously done with stirring, until a homogeneous suspension is obtained.
  • sodium carbonate preferably anhydrous
  • This operation can take place at room temperature.
  • a second precipitate is thus obtained.
  • the latter mainly comprises NaCI; the PTA remaining in said polar organic liquid phase.
  • Said second precipitate is separated from said polar organic liquid phase with known separation methods, which may be filtration.
  • the addition of sodium carbonate leads to the reaction NhUCI + Na 2 C0 3 NH 3 (g) + NaCl (s) + NaHCOs (s), which takes place in suspension, preferably with stirring; the duration of this reaction can be several hours, typically between 1 h and 20 h. At room temperature, the reaction time is advantageously between 1 h and 10 h, preferably between 2 h and 6 h. In all cases, the gaseous N H3 is recovered which can be reintroduced into the stage of the process according to the invention. It is noted that the sodium carbonate used during this step b) is an inexpensive and non-toxic convenience product.
  • the polar organic liquid phase containing the PTA can undergo a further concentration step to increase its PTA concentration, for example by partial evaporation of said polar organic liquid phase.
  • a step c) is added in which the said organic liquid phase obtained at the end of step b) is evaporated until a third precipitate comprising PTA is obtained.
  • the PTA can also be recrystallized in the cold from said organic liquid phase, or it can be precipitated by adding chloroform, followed by filtration and drying of the residue (step c2)).
  • said polar liquid phase is ethanol, which is a common solvent, low in toxicity, not too volatile, easy to recover and purify.
  • ethanol is used in the process according to the invention in its anhydrous form.
  • methanol preferably anhydrous, which is more toxic and more volatile, but which dissolves the first precipitate better.
  • the PTA obtained at the end of the second step has good purity.
  • the main impurities are the hydrolysis products of PTA, in particular OP(NH 2 ) 2 OH (which can be easily identified on an NMR spectrum centered on the 31 P isotope), the dimers or oligomers of PTA, and other PTA derivatives. These typical impurities partly also show urease inhibiting activity. However, it is preferred to minimize the level of impurities in such a product, because the behavior of the impurities is not necessarily the same as that of the targeted product.
  • said third precipitate has a mass fraction of phosphoryl triamide of at least 70%, preferably of at least 80%, and even more preferably of at least 90%; one can reach a content that exceeds 94%, and even 96%.
  • steps c1) and c2) facilitates the production of a third precipitate which comprises PTA with a purity greater than 90%.
  • the third precipitate resulting from the process according to the invention can be used, as it is or diluted in a solid material, in a solid formulation of nitric fertilizer, preferably based on urea, to inhibit and/or regulate the loss of nitrogen of a nitrogenous fertilizer, in particular for inhibiting and/or regulating the enzymatic hydrolysis of urea, and/or for inhibiting and/or regulating the microbiological oxidation of ammonium.
  • the product according to the invention is preferably in the form of said third precipitate or in the form of said apolar liquid phase. As indicated above, it is enriched in PTA and depleted in chloride. This has various advantages. The introduction of chloride into soil for agricultural use is generally undesirable.
  • the Applicant has found that a quantity of PTA of the order of 0.05% to 0.3%, preferably between 0.05% and 0.2%, incorporated into a urea-based fertilizer, decreases by significantly the production of ammonia.
  • the addition of the urease inhibitor in a solid formulation of nitrogen fertilizer can be done with an inhibitor which is in the form of a solid phase (preferably powder) or liquid (generally in the form of form of a solution).
  • the addition of the solid inhibitor requires particularly efficient mechanical mixing means.
  • the powdered inhibitor can be diluted in another solid additive, or in a quantity of granular fertilizer, before adding it to the volume of fertilizer to be treated.
  • the addition of the initiator in the liquid phase can be done by directly using the polar organic liquid phase resulting from the second stage of the process, after separation of the NaCl; it is also possible to dilute the polar organic liquid phase resulting from the second stage of the process according to the invention, if this is desired for any reason. Even if the solubility of PTA in ethanol is good, this approach consisting in using an alcoholic solution is not preferred because it requires managing in the workshop in which this impregnation is carried out a risk of explosion linked to the gas, something the fertilizer industry is not used to.
  • a liquid phase laden with PTA can be obtained by dissolving said third precipitate, which comprises a high proportion of solid PTA, in a suitable solvent, which is preferably aqueous.
  • a liquid phase comprising a urease inhibitor to a solid nitrogenous fertilizer is usually done by impregnating said solid fertilizer, which is typically in a granular form, with said liquid phase; said liquid phase is preferably applied by spraying.
  • the quantity of this liquid phase is critical: generally speaking, it is not desired to impregnate a solid formulation of nitrogenous fertilizer with more than 3 L of liquid per ton of fertilizer, so that said solid formulation does not lose its character of dry granular solid. It is preferred that this quantity does not exceed 2.5 L per ton, and even more preferably it does not exceed 2 L per ton. This objective can only be achieved if the urease inhibitor initially presents itself in the liquid phase in a fairly concentrated form.
  • an aqueous solution obtained by complete dissolution of the third precipitate comprising a PTA content greater than 85% and preferably greater than 88%, and even more preferably of at least 90%, at at the rate of at most 3 L of liquid per tonne of fertilizer, and preferably at most 2.5 L of liquid per tonne, and even more preferably at most 2 L of liquid per tonne.
  • the concentration of PTA in the fertilizer is preferably between 0.05% and 0.3%, more preferably between 0.05% and 0.2%; a concentration of about 0.1% gives good results.
  • aqueous solution to a solid fertilizer can be done at room temperature. Adding such a small amount of liquid to a solid, granular fertilizer does not alter its rheological properties, and it does not need to be dried before use. This avoids unnecessary energy expenditure.
  • the addition of a liquid phase comprising a urease inhibitor to a liquid nitrogen fertilizer does not raise any particular problem.
  • the third precipitate can be added in solid form to a solid or liquid nitrogen fertilizer.
  • the addition of the third precipitate to a solid nitrogenous fertilizer can be done by any appropriate means, for example using a mixing screw.
  • the invention can also be carried out with thiophosphoryl triamide SP(NH 2 ) 3 (abbreviated as TPTA), synthesized from thiophosphoryl trichloride SPCI 3 (CAS No. 3982-91-0) by following the same reaction as that described for PTA, and following the same purification route; for each of these steps, it is possible to use operating conditions very similar to those described for the PTA.
  • TPTA can be used in the same way as the PTA. It has two major disadvantages compared to PTA: its very unpleasant smell, and thiophosphoryl trichloride is more expensive than phosphoryl trichloride.
  • Example 1 Synthesis and purification of phosphoryl triamide (PT A).
  • the first step is the synthesis according to the formula 6 NH 3 (g) + OPC 3NH 4CI(s)+
  • the white precipitate was recovered by filtration on a frit.
  • the white precipitate is a mixture of NH 4 CI and PTA . After drying the white precipitate, the reaction yield was approximately 96% to 98% relative to the POCI 3 consumed.
  • the white precipitate obtained in the first step was partially dissolved in anhydrous ethanol (CAS No. 64-17-5) at ambient temperature.
  • Anhydrous Na 2 CC> 3 (CAS No. 497-19-8) was added with a molar ratio of 1/1 relative to the NH 4 Cl.
  • the filtrate is a solution of ethanol with PTA. After evaporation of the ethanol from the filtrate, a white solid remains with a PTA concentration of approximately 96% to 98%.
  • PTA was identified by 31 P-NMR.
  • the gaseous NH 3 released during the second step can be reused.
  • the two organic solvents namely that of the first stage and that of the second stage, can be collected, distilled, stripped of their traces of water and reused.
  • the PTA was the “third precipitate” within the meaning of the object of the present invention. It contained at least 75% by mass of PTA; the indication "0.1% by mass of PTA” refers here to the total mass of the third precipitate and not to the pure PTA which it contains.
  • Each soil sample was treated with 250 g of water before depositing the urea samples treated or not with PTA on the surface.
  • the volatilization of urea was determined after four days, expressed in mass percent. For this, we sent a current of air above each sample using a membrane pump, and we led this air through a solution of citric acid which fixes the ammonia by transforming it in ammonia. The citric acid solution was then titrated with a sodium hydroxide solution to calculate the amount of ammonia that reacted with the citric acid solution. From the quantity of ammonia, the quantity of urea having generated it is calculated.
  • PTA can be applied directly to urea-based fertilizers through a system of nozzles that allow the spray application of a precise amount of PTA per ton of fertilizer.
  • a conveyor is used which makes it possible to determine the flow of fertilizer in tonnes and, depending on this flow, a quantity of PTA is applied which can typically range from 2 to 3 U tonnes on the urea fertilizer granules. This application is done in a mixing screw thanks to several nozzles allowing the application of the PTA.
  • a first sample of this earth was treated with a urea fertilizer containing 0.2% by weight of the third precipitate.
  • This precipitate contained at least 75% by weight of PTA; the indication "0.2% by mass of PTA” refers here to the total mass of the third precipitate and not to the pure PTA which it contains.
  • a second sample of this soil was treated with the same quantity of the same fertilizer comprising 0.2% by mass of TPTA (in the sense indicated above for PTA).
  • the third soil sample was treated with the same amount of the same fertilizer containing no urease inhibitor. The rate of urea volatilization was determined after four days of exposure:
  • the dose effect of the PTA was determined by treating identical agricultural soil samples with a urea fertilizer comprising 0.05%, 0.1% and 0.2% by mass of PTA (in the sense indicated above: quantity of third precipitate).
  • the rate of urea volatilization was determined after four days of exposure:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)
EP22720512.7A 2021-04-27 2022-04-27 Verfahren zur herstellung von phosphoryl oder thiophosphoryltriamid und verwendung einer verbindung in stickstoffdüngemittelformulierungen Pending EP4330263A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2104347A FR3122179A1 (fr) 2021-04-27 2021-04-27 Procédé de fabrication de triamide de phosphoryleou de thiophosphoryle, et utilisation de composé dans des formulations d’engrais azotiques
PCT/IB2022/053887 WO2022229859A1 (fr) 2021-04-27 2022-04-27 Procede de fabrication de triamide de phosphoryle ou de thiophosphoryle, et utilisation de compose dans des formulations d'engrais azotiques

Publications (1)

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EP4330263A1 true EP4330263A1 (de) 2024-03-06

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EP22720512.7A Pending EP4330263A1 (de) 2021-04-27 2022-04-27 Verfahren zur herstellung von phosphoryl oder thiophosphoryltriamid und verwendung einer verbindung in stickstoffdüngemittelformulierungen

Country Status (8)

Country Link
EP (1) EP4330263A1 (de)
AR (1) AR125464A1 (de)
AU (1) AU2022266247A1 (de)
BR (1) BR112023022495A2 (de)
CA (1) CA3214284A1 (de)
FR (1) FR3122179A1 (de)
IL (1) IL307736A (de)
WO (1) WO2022229859A1 (de)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596935A (en) 1948-12-30 1952-05-13 Monsanto Chemicals Nitrogen-phosphorus composition and process for same
US2661264A (en) 1950-06-21 1953-12-01 Monsanto Chemicals Nitrogen and phosphorus containing product and process for producing same
US4676822A (en) 1986-07-24 1987-06-30 Tennessee Valley Authority Fluid fertilizers containing thiophosphoryl triamide
DE10014532A1 (de) 1999-03-25 2000-10-26 Piesteritz Stickstoff (Thio-)Phosphorsäuretriamide, Verfahren zu ihrer Herstellung und deren Verwendung als Mittel zur Regulierung bzw. Hemmung der enzymatischen Harnstoff-Hydrolyse
CN101434503A (zh) * 2007-11-16 2009-05-20 中国科学院沈阳应用生态研究所 增效缓释尿素肥料及制备方法
DE102007062614C5 (de) 2007-12-22 2019-03-14 Eurochem Agro Gmbh Mischung zur Behandlung von harnstoffhaltigen Düngemitteln, Verwendungen der Mischung und harnstoffhaltiges Düngemittel enthaltend die Mischung

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BR112023022495A2 (pt) 2024-01-16
FR3122179A1 (fr) 2022-10-28
IL307736A (en) 2023-12-01
AU2022266247A1 (en) 2023-11-02
CA3214284A1 (fr) 2022-11-03
WO2022229859A1 (fr) 2022-11-03
AR125464A1 (es) 2023-07-19

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