EP4658631A1 - Procédé de granulation et granule améliorés - Google Patents

Procédé de granulation et granule améliorés

Info

Publication number
EP4658631A1
EP4658631A1 EP24703187.5A EP24703187A EP4658631A1 EP 4658631 A1 EP4658631 A1 EP 4658631A1 EP 24703187 A EP24703187 A EP 24703187A EP 4658631 A1 EP4658631 A1 EP 4658631A1
Authority
EP
European Patent Office
Prior art keywords
urea
granulation
gallic acid
granules
methylthioninium chloride
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
EP24703187.5A
Other languages
German (de)
English (en)
Inventor
Leonardo MARRONE
Alberto Benedetti
Cristina PIZZOLITTO
Maurizio BORIN
Carmelo MAUCIERI
Giorgia RAIMONDI
Giancarlo RENELLA
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.)
Casale SA
Original Assignee
Casale SA
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 Casale SA filed Critical Casale SA
Publication of EP4658631A1 publication Critical patent/EP4658631A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C05C9/005—Post-treatment
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes

Definitions

  • the present invention relates to a process of granulation of urea and granules of urea obtainable with said process.
  • the current agricultural system is facing the challenge of feeding the increasing world population and mitigating environmental impact.
  • the current world population is over 8 billion and is expected to reach about 10 billion in 2050.
  • the land available for food production is limited and plants have a critical nutrient uptake limit. For the above reasons, there is a strong incentive to increase yield per unit and optimize resources.
  • Fertilization has a basic role in crop production and notably affects its environmental impact, particularly soil nitrogen (N) dynamics. Furthermore, agriculture represents a significant source of human-made emissions of N2O due to fertilization.
  • N soil nitrogen
  • Urea is the most common source of nitrogen for fertilization.
  • Granules of solid urea for use as fertilizer are typically produced by means of a granulation process.
  • the granulation process is described in the literature of urea production, for example Ullmann’s encyclopaedia of industrial chemistry.
  • the known urea processes such as CO2 stripping or self-stripping, produce an aqueous urea solution having a concentration of around 65-70%.
  • This solution is treated to remove water in a suitable evaporation section, to obtain a urea melt with a concentration suitable for the urea granulation, which is typically 96% of higher (by weight).
  • the granulation process is performed in a granulation apparatus, where the urea melt is sprayed and solidifies over the granules until a target size of the granules is reached.
  • the process is also fed with small particles of solid urea called seeds, which act as starting nuclei for the granulation process.
  • Said seeds may be separately prepared or obtained by crushing a portion of the granules, for example a portion which does not meet size specification.
  • the granulation process is preferably performed in a fluid-bed condition.
  • the granulation process may include the use of additives, the most common being formaldehyde which is an anti-caking agent and increases the mechanical properties, such as crushing strength, of the granules.
  • urea During its use as fertilizer, urea easily undergoes transformation processes such as hydrolysis (i.e. urease) and nitrification. If these processes are necessary to sustain plant nutrition, they may also harm the environment by release of ammonia (NH3) into the atmosphere and contamination of groundwater through NO3 leaching after nitrification. Therefore, the nitrogen use efficiency (NUE) is among the most critical research issues. Alongside the input of nitrogen, the overall crop nutrition should be improved.
  • Nutrient uptake by crops usually follows a sigmoidal graphical pattern, which is synchronized with crop phenology such as germination, shoot formation, flowering, grain filling, and fruit formation.
  • An ideal nutrient release should fully match that sigmoidal pattern to minimize losses.
  • N-(n-Butyl) thiophosphoric triamide (NBPT) is used as urease inhibitor.
  • DCD Dicyandiamide
  • the above chemicals are normally dissolved in a solvent and the so obtained solution is sprayed onto finished urea granules or prills downstream the granulation or prilling section.
  • US 8 343 891 discloses a method of improving the properties of urea granules, by the addition of an additive to the urea.
  • the invention aims to a new urea-based fertilizer and a related process of production to overcome the above-mentioned issues in connection with the use of NBPT and/or DCD as additives.
  • a further aim of the invention is to provide an environmentally acceptable alternative to the above-mentioned additives used in the production of urea granules.
  • the above aims are reached with a urea granulation process according to the claims.
  • gallic acid is used as urease inhibitor and/or methylthioninium chloride, known as methylene blue, is used as nitrification inhibitor.
  • the invention provides that one or both of said additives is added directly in the granulation process. Consequently, the so obtained urea granules are not simply coated with the additive, rather the additive is contained in the urea granules according to a desired distribution.
  • At least one of said additives is added to selected steps of the granulation process. Consequently, the additive can be concentrated in a selected region of the granules, for example in a layer of the granules. In some embodiments the process results in the additive being predominantly or exclusively contained in a layer of the granules. In certain embodiments, the process results in granules with a layered structure including a layer containing most or all of the methylene blue and a layer containing the most or all of the gallic acid.
  • the gallic acid is preferably added after the methylene blue, within the granulation process, so that the gallic acid is contained in an outer layer and the methylene blue is contained in an inner layer of the granules.
  • a further aspect of the invention is a urea granulate comprising at least one of methylthioninium chloride and gallic acid according to the claims.
  • the gallic acid is added to the granulation process preferably in an amount so that the total content of gallic acid in the urea granules, obtained after the granulation process, is in the range 0.2 g/kg to 10 g/kg, preferably 0.5 to 5.0 g/kg and more preferably 1.0 to 3.0 g/kg.
  • the methylthioninium chloride (methylene blue) is added to the granulation process preferably in an amount so that its total content in the urea granules, obtained after the granulation process, is in the range 0.12 g/kg to 10 g/kg, preferably 0.5 to 5.0 g/kg and more preferably 0.8 to 1 .5 g/kg.
  • the granulation process can be performed in a granulation apparatus, wherein a feed of urea melt is sprayed in the granulation apparatus and the apparatus is fed with solid particles of urea, called seeds, suitable to act as starting nuclei for the granulation process.
  • some or all of said granulation seeds are obtained by crushing a portion of the granules obtained after the granulation process; in addition or alternatively, some or all of said granulation seeds can be separately prepared with a portion of said urea melt.
  • the crushed portion of granules may include undersize and oversize granules, separated by passing the product of the granulation apparatus (urea granules) through suitable screeners.
  • the separate production of granulation seeds is made preferably by rotoforming, wherein droplets of urea melt are deposited on a cooled belt.
  • granulation seeds may be produced by a separate prilling or granulation process. For example, a small portion of the available urea melt can be sent to a prilling equipment or to a separate granulator for the production of the seeds.
  • all granulation seeds are produced separately with a portion of the urea melt and no recycle of the product by crushing granules and reintroducing them in the granulator, is performed.
  • This once-through embodiment may be preferable to provide accurate control of the amount of additive in different layers of the granules.
  • the granulation process is preferably a fluid-bed process, wherein the urea granules are maintained in a fluidized condition by means of a suitable fluidizing medium, which is typically air.
  • a suitable fluidizing medium typically air.
  • the granules are maintained in a vortex or double-vortex condition.
  • the granulation process may include a sequence of granulation stages from a first granulation stage to a last granulation stage, wherein at each granulation stage a feed of urea melt is introduced into the granulation apparatus by means of one or more sprayers. For example, at each granulation stage an amount of the urea feed is introduced by a set of sprayers arranged around the granulation apparatus. The sprayers of different granulation stages may be fed by a urea melt header.
  • one or more initial granulation stages are performed without the addition of any of said gallic acid and methylthioninium chloride, and at least one of said gallic acid and methylthioninium chloride is added to one or more subsequent granulation stages. Accordingly, granules can be obtained wherein the core of the granules contains no or substantially no amount of the above-mentioned additives, which are predominantly or exclusively concentrated in a selected layer.
  • methylene blue is added to a first set of granulation stages and gallic acid is added to a subsequent second set of granulation stages, so that granules are obtained with a core substantially free of said additives; an inner layer containing the methylene blue; an outer layer containing the gallic acid.
  • a layered structure of the urea granules is advantageous because a desired release of nutrients is achieved and meanwhile urease and the nitrification reaction are prevented.
  • the methylthioninium chloride is added to a first sequence of one or more granulation stages
  • the gallic acid is added to a second sequence of one or more granulation stages, wherein the stages of the second sequence are performed after and downstream the stages of the first sequence, wherein methylthioninium chloride is not added to the steps of the second sequence, and gallic acid is not added to the steps of the first sequence.
  • the methylthioninium chloride and/or gallic acid can be introduced directly in the granulation apparatus or added to a urea melt stream before said stream is introduced in the granulation apparatus. Adding said additives to one or more urea melt stream(s) is a preferred embodiment.
  • each of the above-mentioned additives may be added to a urea melt header which feeds different stages of granulation, or to an individual set of sprayers which introduce the urea melt into a single stage of granulation.
  • Said residence time is preferably not greater than 30 s, preferably not greater than 15 s and most preferably not greater than 10 s.
  • the methylthioninium chloride and/or gallic acid is introduced in the granulation process so that the methylthioninium chloride or gallic acid is added to a layer of the urea granules, said layer having a volume which is 0.2 to 0.4 the total volume of the urea granule, preferably 0.3 or around 0.3.
  • the total volume of the urea granules is understood as the volume of the granule including the above-mentioned layer containing the methylthioninium chloride or gallic acid, and any coating layer.
  • the process is controlled so that the urea granules exiting the granulate apparatus have a spherical shape.
  • the urea granules have an average diameter which is in the range of 2.8 mm to 3.5 mm, preferably 2.9 mm to 3.1 mm. or more preferably of 3.0 mm or about 3.0 mm. Said average diameter refers to the granules including any additive-containing layer and coating layer.
  • the urea melt has a content of urea of at least 96% by weight and the nitrogen content in the urea granules is at least 46% by weight.
  • Each of the additives gallic acid and methylene blue, prior to being injected into the granulator apparatus or into a urea melt stream, is preferably mixed with an aqueous solution of urea to form an aqueous dispersion.
  • concentration of the additive in the aqueous urea dispersion is selected in order to minimize the water input to the urea melt and avoid the precipitation of urea from the dispersion especially when the dispersion is stored at a relatively low temperature.
  • the above-mentioned aqueous urea solution which is mixed with the gallic acid or with the methylene blue to form the dispersion, has a urea concentration in the range of 40% to 80% by weight.
  • the gallic acid and said methylthioninium chloride are introduced in the granulation process in the form of a dispersion in an aqueous urea solution.
  • methylthioninium chloride is dispersed in said aqueous solution in a concentration of 15% to 30%.
  • said gallic acid is dispersed in said aqueous solution of urea in a concentration of 20% to 35%.
  • a further aspect of the invention is a urea granulate comprising methylthioninium chloride and/or gallic acid added as additive in the granulate.
  • the methylthioninium chloride is in an amount of 0.12 to 10 grams of methylthioninium chloride per kg of urea granule, more preferably 0.5 to 5.0 g/kg and particularly preferably 0.8 to 1 .5 g/kg.
  • the gallic acid is in an amount of 0.2 to 10 grams of gallic acid per kg of urea granule, more preferably 0.5 to 5.0 g/kg and particularly preferably 1 .0 to 3.0 g/kg.
  • the urea granulate consists of a multi-layered structure comprising a nucleus of urea, a first layer of methylthioninium chloride mixed with urea and a second layer of gallic acid mixed with urea.
  • the first layer of the granule surrounds the nucleus and the second layer surrounds the first layer.
  • said nucleus of the granulate is free of additive; accordingly, methylthioninium chloride and gallic acid are only added in the layers surrounding the nucleus.
  • the urea granulate is spherical and the average diameter of the granulate is between 2.8 and 3.5 mm, preferably 2.9 mm to 3.1 mm and more preferably is 3.0 mm or about 3.0 mm.
  • at least 90% by mass of the granular urea has a diameter in the range 2.0 to 4.0 mm.
  • Fig. 1 is a diagram of a urea granulation process according to an embodiment of the invention, wherein the granulation process is a once-through process.
  • Fig. 2 is a diagram of a urea granulation process according to an embodiment of the invention wherein part of the urea granules is recycled into the granulation apparatus.
  • Figs. 1 and 2 disclose the following main items:
  • Fig. 1 shows a process for generating urea granules 100 containing methylthioninium chloride and gallic acid as additives. The process works as follow.
  • An aqueous solution of urea 50 is fed via line 1 to a first evaporator 2 to generate a more concentrated urea solution or urea melt; a first portion of the concentrated urea solution is sent via line 63 to the granulator 9; a second and minor portion of the concentrated urea solution is sent via line 4 to a second evaporator 5 for further concentration, to produce a highly concentrated urea melt 6 which feeds a seeds producer such as the rotoformer 7.
  • the water 53, 54 removed by the evaporators 2 and 5 is processed in the waste water treatment section 3.
  • the first portion of urea solution 63 is added with formaldehyde or with a formaldehyde-containing additive 17 to generate a formaldehyde-containing urea melt 44 supplied to the urea granulator 9.
  • the highly concentrated urea melt 6 is used in the rotoformer 7 to generate granulation seeds 8 of solid urea.
  • the seeds 8 are then fed to the granulator 9 to be used as precursors for the growth of the granules 100.
  • said urea melt 6 is added with a recycle stream 16 obtained from the processing of the granulation offgas 11 .
  • the granulator 9 receives a urea solution 23 containing methylene blue and a urea solution 31 containing gallic acid.
  • Said solutions 23, 31 are preferably a dispersion of the additive in a urea solution of a suitable concentration, as explained below.
  • the granulator 9 in the depicted embodiment is a fluidized bed apparatus wherein a fluid-bed condition of the urea granules is maintained by fluidizing air 25.
  • the granulator 9 has a longitudinal direction 160 and is provided with multiple injection nozzles (or sprayers) 150 arranged lengthwise and located at multiple granulation stages of the apparatus.
  • Fig.1 shows a first granulation stage 150a, a second granulation stage 150b and a third granulation stage 150c in sequence.
  • Each granulation stage may include one or more nozzles 150.
  • Fig. 1 is for illustrative purpose and the actual number of granulation stages may vary, in particular it may be greater.
  • the first granulation stage 150a is fed with the urea melt 44, which is introduced into the granulator 9 by means of the nozzles 150 located at said first stage 150a; the second granulation stage 150b is fed with the urea melt 44 added with the methylthioninium chloride dispersion 23, being downstream the injection point of the dispersion 23; the third granulation stage 150c is fed with the urea melt 44 added with the gallic acid dispersion 31 . Having a separate urea melt header 102, the third granulation stage does not receive the methylene blue dispersion 23.
  • Fig. 1 shows that a main header carrying the urea melt 44 is separated into a first header 101 carrying a first portion of the urea melt and a second header 102 carrying a second portion of the urea melt.
  • the first header 101 feeds the nozzles of the first stage 150a and of the second stage 150b, and the second header 102 feeds separately the nozzles of the third stage 150c.
  • the first granulation stage 150a receives the urea melt 44 as in the main header, added with the formaldehyde additive 17.
  • the second granulation stage 105b receives the urea melt 44 further added with the methylthioninium chloride dispersion 23.
  • the third granulation stage 150c being fed by the second header 102, receives the urea melt 44 further added with the gallic acid dispersion 31 .
  • the urea melt is introduced in the granulator 9 via the sprayers 150.
  • the depicted configuration of the granulator 9 is particularly advantageously because it allows to form granules 100 having a core of urea containing formaldehyde (obtained by the spraying of the urea melt 44) surrounded by a first layer of urea containing methylthioninium chloride, formed in the second stage 150b due to the injection of the urea melt mixed with the dispersion 23, and further surrounded by a second layer of urea containing gallic acid, formed in the third stage 150c after injection of the urea melt mixed with the dispersion 31 .
  • the formaldehyde initially added to the urea melt 63 is present in all layers of the granules.
  • the methylthioninium chloride and the gallic acid dispersions 23, 31 are obtained as follows.
  • Methylthioninium chloride denoted as MB is added vie line 19 to a stirred mixing tank 21 together with aqueous urea solution 20 to generate the dispersion 23.
  • gallic acid GA is added via line 52 to a stirred mixing tank 28 together with aqueous urea solution 29 to generate the dispersion 31 .
  • the urea solution 20 and the urea solution 29 preferably contain 50% urea by weight.
  • the dispersions 23, 31 are fed to the respective granulation stages 150b, 150c by pumps 22, 30.
  • the granulator 9 of Fig. 1 is operated according to a once-through process wherein all the urea seeds 8 are obtained by converting the highly concentrated urea solution 6 into small granules or pastilles of solid urea and no seed material is obtained by recycling output granules into the process.
  • a byproduct offgas 11 is removed from the granulator 9.
  • the offgas 11 may contain fluidizing air, urea dust and small amounts of the additives used in the granulation process.
  • the offgas 11 is purified in the scrubber 12 using a scrubbing medium such as water 13.
  • Outputs of the scrubber 12 are an aqueous solution of urea 45 and a purified gas 32 which is vented into the atmosphere.
  • the aqueous solution 45 is concentrated in the evaporator 14 coupled to a vacuum unit 15 to generate the recovery urea stream 16 which is mixed with the highly concentrated urea melt 6 to produce the input for the rotoformer 7.
  • the granules 68 obtained in the granulator 9 are subjected to a screening step in the screeners 41 to separate undersized or oversized granules 70 which are crushed in the crusher 40 to form seeds 71.
  • the granules which meet size specifications and are not discarded by the screeners 41 form the granular product 100.
  • the granules 100 have a uniform or nearly uniform distribution of additives within the granules, as a consequence of the additives being added with the same dispersion 105.
  • the urea melt 50 is fed via line 1 to an evaporator 2 to remove water 53 and generate a concentrated urea melt 4.
  • the concentrated urea melt 4 is added with recycle stream 16 and formaldehyde-containing additive 17 to generate the urea melt 44.
  • the methylthioninium chloride dispersion 23 and the gallic acid dispersion 31 are obtained following the same procedural steps as above described in connection with the embodiment of Fig. 1.
  • the methylthioninium chloride dispersion 23 and the gallic acid dispersion 31 are then mixed to form the mixed dispersion 105 which is added to the urea melt 44.
  • the so obtained urea melt feed is supplied to all stages of the granulator 9 via a common header 70 with feeds all the urea sprayers 150.
  • urea solution 50 60’200 kg/h of urea solution 50 are sent to the first evaporator 2 to generate 41 ’570 kg/h (97%w) of urea melt 63.
  • Said urea melt 63 is mixed with 209 kg/h of formaldehyde-containing additive 17 to generate the urea melt 44 supplied to the urea granulator 9.
  • the highly concentrated melt 6 from the second evaporator 5 is mixed with 1 ’306 kg/h of recycled urea melt 16 to generate 2’446 kg/h of highly concentrated urea melt (99.7%w) which feeds the rotoformer 7.
  • the rotoformer 7 produces granulation seeds 8 having a diameter of 1 .20 mm.
  • the offgas 11 removed from the granulator 9 contains urea dust equivalent to around 3% of the sprayed urea melt.
  • the offgas 11 is treated in the scrubber 12 to generate 3’255 kg/h of an aqueous solution of urea 45 (40%w) which is then evaporated in the evaporator 14 to generate the recycle urea melt 16.
  • Example 2
  • urea melt 50 60’200 kg/h of urea melt 50 are fed via line 1 to the first evaporator 2; the urea melt produced in the evaporator 2 receives 1 ’328 kg/h of urea melt 16 from the evaporator 14 to generate 44’080 kg/h of urea melt 4 at 97 %w.
  • the urea melt 4 is added with 209 kg/h of the formaldehyde-containing additive 17.
  • 89 kg/h of gallic acid are added to the mixing tank 28 together with 214 kg/h of urea solution (50%w) to generate 306 kg/h (29.0 %w) of gallic acid dispersion 31.
  • the methylthioninium chloride dispersion 23 is then mixed with the gallic acid dispersion 31 to generate 610 kg/h of the urea melt feed 105.
  • the third field trail was carried out on hemp.
  • Future 75 which is a monoecious variety of Cannabis sativa was used for the trail.
  • Different dosage regimes 50, 100 and 150 kg N/ha were investigated.
  • the dosage at which the fertilization treatment has returned the best performance is reported in table 3.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Soil Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Fertilizers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Glanulating (AREA)

Abstract

L'invention concerne un procédé de granulation d'urée et de granulés relatifs dans lequel des granulés d'urée sont produits à partir d'une masse fondue d'urée, au moins un additif comprenant de l'acide gallique et/ou du chlorure de méthylthioninium étant utilisé dans le procédé de granulation.
EP24703187.5A 2023-02-03 2024-02-02 Procédé de granulation et granule améliorés Pending EP4658631A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23154996 2023-02-03
PCT/EP2024/052606 WO2024161008A1 (fr) 2023-02-03 2024-02-02 Procédé de granulation et granule améliorés

Publications (1)

Publication Number Publication Date
EP4658631A1 true EP4658631A1 (fr) 2025-12-10

Family

ID=85174215

Family Applications (1)

Application Number Title Priority Date Filing Date
EP24703187.5A Pending EP4658631A1 (fr) 2023-02-03 2024-02-02 Procédé de granulation et granule améliorés

Country Status (5)

Country Link
EP (1) EP4658631A1 (fr)
CN (1) CN120641377A (fr)
AU (1) AU2024214920A1 (fr)
MX (1) MX2025009100A (fr)
WO (1) WO2024161008A1 (fr)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60039075D1 (de) * 1999-12-08 2008-07-10 Richard O W Hartmann Calciumcyanamid zusammensetzung mit verbesserter kontrollierbarer effizienz
CA2541450C (fr) 2003-10-06 2011-02-08 Yara International Asa Procede permettant d'ameliorer les proprietes de granules d'uree
EP1935482A1 (fr) 2006-12-22 2008-06-25 Urea Casale S.A. Procédé de granulation en lit fluidisé
EP2077147A1 (fr) 2008-01-04 2009-07-08 Urea Casale S.A. Procédé et appareil de granulation en lit fluidisé
US8048189B2 (en) * 2009-02-17 2011-11-01 Whitehurst Associates Inc. Buffered amino alcohol solutions of N-(n-butyl)thiophosphoric triamide (NBPT) and urea fertilizers using such solutions as urease inhibitors
EP2431346A1 (fr) * 2010-09-15 2012-03-21 Uhde Fertilizer Technology B.V. Procédé de production d'engrais d'urée avec des faibles tendances d'absorption d'humidité
EP2489429A1 (fr) * 2011-02-21 2012-08-22 Urea Casale S.A. Granulation d'urée en lit fluidisé et appareil correspondant
AU2016223099B2 (en) * 2015-02-24 2019-11-21 Koch Agronomic Services, Llc Granular urea fertilizer with nitrogen stabilizer additives
CN109438139A (zh) * 2018-11-09 2019-03-08 中国农业科学院农业资源与农业区划研究所 一种具有减缓尿素转化的海藻酸增效载体的制备方法
CN112645754A (zh) * 2020-12-07 2021-04-13 甘肃中医药大学 以中药废弃物为原料的缓释材料、缓释肥及其制备方法

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MX2025009100A (es) 2025-09-02
CN120641377A (zh) 2025-09-12
WO2024161008A1 (fr) 2024-08-08
AU2024214920A1 (en) 2025-07-24

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