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WO2016115613A1 - Engrais à base d'urée micronisée et son procédé d'obtention - Google Patents

Engrais à base d'urée micronisée et son procédé d'obtention Download PDF

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Publication number
WO2016115613A1
WO2016115613A1 PCT/BR2016/050003 BR2016050003W WO2016115613A1 WO 2016115613 A1 WO2016115613 A1 WO 2016115613A1 BR 2016050003 W BR2016050003 W BR 2016050003W WO 2016115613 A1 WO2016115613 A1 WO 2016115613A1
Authority
WO
WIPO (PCT)
Prior art keywords
urea
nitrogen fertilizer
nbpt
fertilizer
additive
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.)
Ceased
Application number
PCT/BR2016/050003
Other languages
English (en)
Portuguese (pt)
Inventor
José Carlos POLIDORO
Ioná RECH
Paulo Sergio PAVINATO
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.)
Universidade de Sao Paulo USP
Empresa Brasileira de Pesquisa Agropecuaria EMBRAPA
Original Assignee
Universidade de Sao Paulo USP
Empresa Brasileira de Pesquisa Agropecuaria EMBRAPA
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 Universidade de Sao Paulo USP, Empresa Brasileira de Pesquisa Agropecuaria EMBRAPA filed Critical Universidade de Sao Paulo USP
Publication of WO2016115613A1 publication Critical patent/WO2016115613A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • 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
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to fertilizers used in agricultural crops, describing the synthesis and preparation of fertilizer compositions characterized by slow release of nitrogen.
  • the compositions are prepared based on micronized urea, containing urease and / or clay mineral inhibitors incorporated into the nitrogen fertilizer.
  • Nitrogen (N) is a primary macronutrient and plants generally need it in greater quantities.
  • the forms in which N is present in nitrogen fertilizers can be: nitric (as in calcium nitrate), ammonia (as in ammonium sulfate), or both (as in ammonium nitrate), organic (in waste animals and vegetables, organic compounds), and amidic (urea).
  • Urea as a nitrogen fertilizer has received much attention from agricultural research, as it represents about 60% of the nitrogen fertilizers used in Brazil.
  • the main advantages of using urea are its high N concentration (44 to 46%), lower costs per N unit, high solubility, low corrosivity and ease of mixing with other sources.
  • the main disadvantage of urea is the loss of N from ammonia volatilization compared to other nitrogen fertilizers, especially when the fertilizer is applied to the soil surface and also by ammonium and nitrate leaching.
  • Ammonium carbonate formed is unstable and decomposes rapidly, resulting in ammonium, bicarbonate and hydroxyl.
  • the hydroxyl and bicarbonate molecule react with hydrogen atoms, raising the pH of the soil around the fertilizer granules.
  • part of the ammonium becomes ammonia, which is easily lost to the atmosphere.
  • N-ammonia N-NH4 +
  • Another transformation of N-ammonia (N-NH4 +) from urea transformations in the soil is the nitrification process, which from an agronomic point of view is unfavorable because Brazilian soils have a predominance of negative electric charges in the values of pH used for agricultural production.
  • Nitrification is the transformation of ammonium N (N-NH4 +) to nitrite (NO2-) and nitrate (N-NO3-). This transformation is carried out in two steps, respectively by bacteria of the genus Nitrosomonas and Nitrobacter. Thus, it can be said that because nitrate has a negative charge, it does not bind to the solid phase in strong bonds, remaining in the soil solution and can be leached.
  • NO3- can be transformed into gaseous forms of N by some microorganisms that have an enzymatic system that makes it possible to use NO3- as an electron receptor (denitrification process), releasing gases into the atmosphere.
  • Urease is a naturally occurring enzyme in soils, derived from the synthesis carried out by microorganisms and also from plant residues and is responsible for the enzymatic hydrolysis of urea, releasing ammoniacal N into the medium. Inhibition of the urease enzyme to assist in reducing the rate of urea hydrolysis may occur by heavy metal ions, but these ions inhibit both plant development and urease enzyme activity. The order of effectiveness of these ions in inhibiting the enzyme is known in the following sequence: Hg + 2 ⁇ Ag +> Cu + 2 »Ni + 2> Cd + 2> Zn + 2> Co + 2> Fe + 3> Pb + 2> Mn + 2 (ZABORSKA, W. et al. J. Enzyme Inhib. Med. Chem., V. 19, p. 65-69, 2004.).
  • the mechanism for controlling the release of N through polymeric coating and elemental sulfur in urea is by protecting against the ingress of water that the polymer provides to the granules and together with the microbiological degradation of elemental sulfur that reduces soil pH thus decreases the possibility of formation of NH3.
  • the acidification reaction occurs through the oxidation of elemental sulfur (S0), carried out by soil specific microorganisms.
  • S0 elemental sulfur
  • urease inhibitors such as triamidathiophosphoric N- (n-butyl) (NBPT), micronutrients such as copper, boric acid, which interfere with urea hydrolysis, polymers that interfere with the solubilization of urea and elemental sulfur. being reported in the prior art as urea additives to control and reduce N losses through volatilization.
  • Triamidathiophosphoric N- (n-butyl) (NBPT) is one of the main products employed to inhibit the action of urease. However, to inhibit the urease enzyme, it must be converted to the N-n-butyl triamide phosphate compound (NBPTO), its oxygen analogue. This conversion is quick in well-ventilated soils, but may take several days in flooded soil conditions. Thus, this compound is a competitive inhibitor that resembles the urea molecule and binds to the active site of the urease enzyme.
  • NBPT has been described in US4530714 as a waxy solid compound with poor water solubility, which makes it difficult for the compound to adhere to urea, also because the compound is hydrolyzed and thermally unstable.
  • US5698003 describes the dissolution of NBPT in glycol, preferably a glycerol, which may contain an amide such as N-methyl-2-pyrrolidone and a surfactant or dispersant;
  • US5352265 and US5364438 teach liquid amine dissolution for both solid and liquid formulations.
  • US2004 / 0163434 teaches the formation of sulfur-coated urea, which may contain the NBPT urease inhibitor supplied from a liquid formulation sold as Agrotain®, distributed by Koch Agronomic Services, Kansas, USA.
  • Sutton et al. (US50247689) teach the formation of a liquid fertilizer including such as NBPT urease inhibitors and nitrification inhibitors such as dicyandiamide in aqueous mixtures of ammonium and urea polyphosphate, ammonium thiosulfate and other compounds.
  • US 2007/0295047 teaches the formation of a solid urea fertilizer and a urea formaldehyde polymer, which may additionally include a urease inhibitor such as NBPT.
  • US2007 / 0157689 describes a fertilizer composed of urea, a urea formaldehyde polymer and NBPT dissolved in an N-alkyl-2-pyrrolidone.
  • WO2014022174 teaches the addition of NBPT to urea.
  • AU2012250293 claim the use of urease inhibitors (e.g. NBPT) in the urea coating.
  • urease inhibitors e.g. NBPT
  • Volatilization N losses can also be reduced by using aluminosilicates as a fertilizer additive, controlling NH4 + retention and release.
  • EP1379558 reports a zeolite urea coating technology but does not cite any type of zeolite incorporation technology with micronized urea.
  • the granulation process of urea with natural coated zeolites has also been found in the state of the art (LUZ, AB Zeolitas: industrial properties and uses.
  • CETEM / CNPq 1995. 35p. (Mineral Technology Series, 68) and KISS, S .; SIMIHAIAN, M.
  • the present invention relates to fertilized compositions based on additive micronized urea of ureaase and / or clay mineral inhibitor compounds, with micronutrients incorporated within the granule.
  • the present invention relates to fertilizer compositions made from micronized urea produced with additive incorporation technology.
  • Micronized urea of particles smaller than 10 microns should be mixed with urease activity inhibiting additives, which may be triamidathiophosphoric N- (n-butyl) (NBPT) and / or micronutrients such as copper and / or boron and / or clay mineral of the group of zeolites.
  • NBPT triamidathiophosphoric N- (n-butyl)
  • micronutrients such as copper and / or boron and / or clay mineral of the group of zeolites.
  • NBPT is added during the pelletizing process through an aqueous solution or suspension containing at least 0.0062% NBPT which is sprayed onto the micronized urea.
  • Micronutrients should be added as a powder with particles smaller than 0.015 mm in diameter as boric acid (H3BO3) and copper sulphate (CuSO4), with concentrations of 0.6-1.5% of copper sulfate and 1.5-2.4% boric acid.
  • the clay mineral of the zeolite group can be used to achieve the lowest volatilization of nitrogen if added to the formulation containing micronized urea and NBPT at a concentration of 20% zeolite.
  • the present invention relates to chemical compositions for the production of stabilized nitrogen fertilizers characterized by their controlled nitrogen release dynamics when applied to the soil.
  • Fertilizer formulations are produced from urea granules.
  • the urea is micronized, ie the urea granules are reduced to particles smaller than 10 microns before fertilizer formulations are prepared.
  • All additives are added to the mixture with the ratio defined in relation to the total urea mass contained in the formulation. Fertilizer formulation compositions are produced with the theoretical percentages of each additive. All additives are incorporated within the fertilizer granule.
  • Micronized urea is the differential that allows the incorporation of the additives used within the fertilizer granule. The compositions are described below and in Table 1.
  • the U_NBPT-i * formulation is produced with the N- (n-butyl) triamidathiophosphoric urease inhibitor (NBPT) and is embodied in the mixture of micronized urea and NBPT aqueous solution or suspension using a spray near the micronized urea.
  • NBPT N- (n-butyl) triamidathiophosphoric urease inhibitor
  • NBPT can be obtained and applied from the Agrotain® commercial product, in which case it is used in a proportion corresponding to 2,5 L of product per tonne of urea. NBPT can also be added to liquid urea for later pelleting or pelleting.
  • Table 1 Examples of formulations made with micronized urea and additive incorporation technology.
  • the formulation U_BCu-i * is produced with micronized urea (97.21%) with the additives boron (B) and copper (Cu) added as boric acid (H3B03) and copper sulfate (CuSO4). Boron and copper micronutrients are used as a powder with a diameter of less than 0.015mm in the micronized urea mass, with concentrations of 0.6-1.5% copper sulfate and 1.5-2.4%. of boric acid. Boron and copper are incorporated into the micronized urea for further granulation or added to the liquid urea for later pelleting or pelleting.
  • the formulation U_NBPT_Z-i * is produced from the mixture of micronized urea, clay mineral from the zeolite group according to Example 2 and NBPT.
  • formulations can be obtained so that they comprise micronized urea and any combinations of urease activity inhibiting additives such as NBPT, copper, boron, sulfur, and clay minerals such as zeolite.
  • Urea formulations with additives incorporated into their mass may be mixed in a V-type mixer and then granulated.
  • the equipment used for granulation may be a pelletizer or large scale industrial fertilizer production equipment.
  • the clay mineral (zeolite) used as an additive for micronized urea formulations was characterized according to its particle size characteristics, CTC, density, surface area, volume and diameter. pores.
  • the particle size analysis was performed according to ABNT NBR ISO 4701 Standard, by wet sieving.
  • Table 5 The formulations of Table 5 were laboratory produced from micronized urea using the technology of incorporating additives into the granule. The commercial products reported in table 5 have been tested for efficiency comparison of the claimed products. The chemical analyzes of the fertilizers were performed by determining the total contents of N, S, B and Cu in the urea mixtures with the additives, as well as in the other commercial products to be used in the experiments (Table 5).
  • the fertilizers tested were: pearly urea; 2) FH Nitro Mais® (urea + Cu 0.15% + B 0.4%); 3) Super N® (urea + 0.062% NBPT); 4) 100% micronized urea + 0.062% NBPT; 5) 97.21% micronized urea + 0.4% B + 0.15% Cu and 6) 80% micronized urea + 20% zeolite + 0.062% NBPT.
  • Nitrogen fertilizers were applied to the soil surface of the pots filled with 6kg of soil described in Example 1 at a dose equivalent to 120kg ha-1 of N at 12 days after sowing (this time for germination and thinning, keeping only two seedlings per pot). The soil was moistened prior to fertilizer application, being moistened again after the third day of application. Moisture was maintained at 70 to 90% of field capacity throughout the crop cycle, with daily control.

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

Abstract

La présente invention concerne un procédé de production d'engrais azoté à base d'urée, consistant d'abord à microniser l'urée (particules inférieures à 10 μm), puis à additionner un agent inhibiteur de l'uréase (H3BO3, CuSO4 ou N-(n-butyl)-triamide thiophosphorique (NBPT)) et/ou un minéral argileux (zéolite), le produit étant alors granulé. L'invention concerne également l'engrais en granules, pastilles ou comprimés ainsi obtenu.
PCT/BR2016/050003 2015-01-21 2016-01-19 Engrais à base d'urée micronisée et son procédé d'obtention Ceased WO2016115613A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRBR102015001331-0 2015-01-21
BR102015001331A BR102015001331A2 (pt) 2015-01-21 2015-01-21 fertilizante à base de ureia micronizada e seu processo de obtenção

Publications (1)

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WO2016115613A1 true WO2016115613A1 (fr) 2016-07-28

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WO (1) WO2016115613A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1142002A (en) * 1965-03-24 1969-02-05 Fisons Ltd Granulation
US5352265A (en) * 1993-11-12 1994-10-04 Freeport-Mcmoran Resource Partners, Limited Partnership Granular urea-based fertilizer
BRPI0707108A2 (pt) * 2006-01-12 2011-04-19 Agrotain International L L C composição de fertilizante fluido, aditivo escoável, seco, e, método de preparação de um aditivo escoável, seco
BRPI0904949A2 (pt) * 2009-10-09 2011-06-14 Timac Agro Ind E Com De Fertilizantes Ltda processo para a fabricaÇço de aditivo para fertilizante inibidor de atividade de enzima urease e o produto assim obtido
US8888886B1 (en) * 2013-08-06 2014-11-18 Garnett B Whitehurst NBPT solutions for preparing urease inhibited urea fertilizers prepared from N-substituted morpholines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1142002A (en) * 1965-03-24 1969-02-05 Fisons Ltd Granulation
US5352265A (en) * 1993-11-12 1994-10-04 Freeport-Mcmoran Resource Partners, Limited Partnership Granular urea-based fertilizer
BRPI0707108A2 (pt) * 2006-01-12 2011-04-19 Agrotain International L L C composição de fertilizante fluido, aditivo escoável, seco, e, método de preparação de um aditivo escoável, seco
BRPI0904949A2 (pt) * 2009-10-09 2011-06-14 Timac Agro Ind E Com De Fertilizantes Ltda processo para a fabricaÇço de aditivo para fertilizante inibidor de atividade de enzima urease e o produto assim obtido
US8888886B1 (en) * 2013-08-06 2014-11-18 Garnett B Whitehurst NBPT solutions for preparing urease inhibited urea fertilizers prepared from N-substituted morpholines

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