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WO2016187688A1 - Procédé et système de production d'engrais assisté par ultrasons - Google Patents

Procédé et système de production d'engrais assisté par ultrasons Download PDF

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Publication number
WO2016187688A1
WO2016187688A1 PCT/CA2015/050464 CA2015050464W WO2016187688A1 WO 2016187688 A1 WO2016187688 A1 WO 2016187688A1 CA 2015050464 W CA2015050464 W CA 2015050464W WO 2016187688 A1 WO2016187688 A1 WO 2016187688A1
Authority
WO
WIPO (PCT)
Prior art keywords
potassium
slurry
reacting
magnesium
sonication
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/CA2015/050464
Other languages
English (en)
Inventor
Jean-Marc Lalancette
Bertrand Dubreuil
David Lemieux
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.)
Dundee Sustainable Technologies Inc
Original Assignee
Dundee Sustainable Technologies 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
Application filed by Dundee Sustainable Technologies Inc filed Critical Dundee Sustainable Technologies Inc
Priority to PCT/CA2015/050464 priority Critical patent/WO2016187688A1/fr
Publication of WO2016187688A1 publication Critical patent/WO2016187688A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/12—Preparation of double sulfates of magnesium with sodium or potassium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof

Definitions

  • the present invention relates to fertilizers. More specifically, the present invention is concerned with a method and a system for sonic-assisted production of fertilizers.
  • Potassium is an essential component in fertilizers.
  • the most abundant source of potassium is potassium chloride (KCI), sometimes referred to as potash.
  • KCI potassium chloride
  • potash the most abundant source of potassium
  • KCI potassium chloride
  • K2SO4 potassium sulfate
  • KCI potassium chloride
  • Magnesium is also an element required by some cultures, such as tobacco, potatoes or corn for example. With such crops, it has been found useful to use a naturally occurring mixed sulfate of potassium and magnesium such as langbeinite (K2SO4 . 2MgS04), known as SOPM. However, the increased uses of SOPM, along with the depletion of natural sources of this naturally occurring mineral, have led to using a synthetic potassium sulfate mixed with magnesium sulfate so as to duplicate the naturally occurring SOPM.
  • SOPM naturally occurring mixed sulfate of potassium and magnesium
  • a source of phosphorus is a fluorophosphate of calcium (Cas(P04)3F) referred to as apatite, which cannot be used as a fertilizer because of its insolubility.
  • apatite fluorophosphate of calcium
  • sulfuric acid removes some calcium from the apatite and the resulting mixture of calcium monobasic phosphate, Ca(H2P04)2 and gypsum is then a convenient source of agronomic phosphorus, referred to as superphosphate.
  • More refined sources of phosphorus can be obtained with pure phosphoric acid.
  • a method for the production of a potassium-based fertilizer comprising reacting a source of magnesium or phosphorus with potassium acid sulfate in a slurry submitted to sonication.
  • a method comprising: a) producing potassium acid sulfate by reacting potash with sulfuric acid; b) recovering hydrochloric acid produced during step a); and c) reacting a source of magnesium or phosphorus with the potassium acid sulfate in a slurry submitted to sonication, thereby producing a potassium-based fertilizer.
  • KHSO4 Potassium acid sulfate
  • KCI potash
  • H2SO4 sulfuric acid
  • reaction 1 by substitution of the first hydrogen of sulfuric acid (H2SO4) with potassium, yielding potassium acid sulfate (KHSO4), at a temperature comprised within the range between 120 and 130°C.
  • hydrochloric acid (HCI) is also produced, which may be recovered as a secondary sellable product.
  • KHSO4 Potassium acid sulfate
  • Reaction 2 describes the reaction of potassium acid sulfate (KHSO4) with apatite:
  • Reaction 3 describes the reaction of potassium acid sulfate (KHSO4) with magnesium silicate: [0019] 2KHSO4 + 2(3Mg0.2Si0 2 .2H 2 0) + H2SO4 ⁇ 4(MgO.Si0 2 ) + K 2 S0 4 .2MgS0 4 +
  • Sonication of the reactants during the reactions can be achieved by using ultrasonic piezogenerators or mechanically by hydrodynamic cavitation. Both methods were tested successfully, to generate micro-bubbles in the reacting slurry either by immersing a sonic probe or by generating cavitation in the reacting slurry.
  • the resulting soluble fertilizing elements i.e. monobasic potassium phosphate (KH2PO4) in the case of reaction 2 and SOPM (K2S04.2MgS04) in the case of reaction 3, can be isolated by filtration and separation from residual insoluble products reactions 2 and 3 respectively, i.e. gypsum and magnesium silicate respectively.
  • Dibasic potassium phosphate (K2HPO4) may be obtained with sonic treatment of apatite using a larger amount of potassium acid sulfate as described by reaction 5 below:
  • magnesium sulfate (MgS04) to yield magnesium sulfate (MgS04)
  • obtaining a full substitution of both hydrogens of sulfuric acid (H 2 S04) by magnesium typically requires pressure leaching of the silicates at a temperature of at least 200° C.
  • KHSO4 potassium acid sulfate
  • H 2 S04 sulfuric acid
  • the present invention provides a method for producing chloride-free fertilisers, comprising reacting potassium acid sulfate with a source of magnesium or phosphorus in a slurry submitted to sonication during a time of the order of the minute, i.e. comprised in a range between 30s and 2 minutes.
  • potassium acid sulfate may be produced as per reaction 1 hereinabove.
  • the distillate resulting from this water addition was then combined to the 200 ml of cold water and the HCI content was determined by titration, 35.9 g of HCI or 98.4 % of the expected acid being thus recovered.
  • the residual solid in the reactor was potassium acid sulfate, 136.5 g.
  • Example 1 production of SOPM (reaction 3)
  • reaction 3 To a solution of 0.2 mole of potassium acid sulfate KHS0 4 (27.2 g), 0.1 mole of sulfuric acid (10.0 g of H 2 S0 4, 98 %) in 200 ml of water in a 300 ml beaker, was added 100 g of hydrated magnesium silicate (serpentine: 3MgO.2SiO2.2H2O) 100 % minus 60 mesh.
  • This slurry was stirred at a temperature in a range between 25 and 50°C while being submitted to a sonic treatment at 24 KHz for a period of 15 minutes, using a Hielscher apparatus, model 400S with a 7 mm titanium probe, 75 % power setting.
  • the reaction mixture was then filtered, washed with water and the combined washing and filtrate was evaporated and recrystallized in water.
  • the solid 40.9 g was submitted to elemental analysis and corresponds to the formulation K2S04.2MgS04, a mixed sulfate of potassium and magnesium known as langbeinite or SOPM.
  • the potassium recovery in the form of langbeinite was 98.5 %.
  • a method for producing a chlorine-free mixed sulfate of potassium and magnesium (see reaction 3 above) or a phosphate of potassium (see reactions 2, 4, 5 above) free of insoluble material by using potassium acid sulfate as the source of potassium.
  • the method comprises reacting, under sonic treatment, potassium acid sulfate with a source of magnesium, such as magnesium silicate for example, or with a source of phosphorus, such as apatite for example, to obtain a mixed sulfate of potassium and magnesium (K2S04.2MgSC>4) or potassium phosphate (KH2PO4) respectively.
  • potassium acid sulfate yields fast and complete reaction with these minerals, at near ambient temperature and under atmospheric pressure, opening a new and much simplified access to mixed sulfate of potassium and magnesium, or phosphate of potassium.
  • the source of magnesium may be a finely ground magnesium silicate, i.e. ground to 40-100 mesh, for example to 50 mesh.
  • the source of phosphorus may be a finely ground, i.e. ground to 40-100 mesh, for example to 50 mesh, phosphate of calcium, i.e. apatite.
  • the sonic assistance may be provided using an ultrasonic piezogenerator or by hydrodynamic cavitation.
  • the reaction is conducted in a temperature range comprised between 10 and

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Fertilizers (AREA)

Abstract

L'invention concerne un procédé de production d'engrais à base de potassium, comprenant l'utilisation de sulfate d'acide de potassium en tant que source de potassium, et l'utilisation d'une sonication dans des réactions avec du silicate de magnésium ou d'apatite à basse température, avec un rendement quasi quantitatif, pour obtenir dans des temps de l'ordre de minutes le potassium magnésium sulfate ou le potassium di-hydrogène phosphate correspondants.
PCT/CA2015/050464 2015-05-22 2015-05-22 Procédé et système de production d'engrais assisté par ultrasons Ceased WO2016187688A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CA2015/050464 WO2016187688A1 (fr) 2015-05-22 2015-05-22 Procédé et système de production d'engrais assisté par ultrasons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CA2015/050464 WO2016187688A1 (fr) 2015-05-22 2015-05-22 Procédé et système de production d'engrais assisté par ultrasons

Publications (1)

Publication Number Publication Date
WO2016187688A1 true WO2016187688A1 (fr) 2016-12-01

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PCT/CA2015/050464 Ceased WO2016187688A1 (fr) 2015-05-22 2015-05-22 Procédé et système de production d'engrais assisté par ultrasons

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2712689C1 (ru) * 2018-11-29 2020-01-30 Федеральное Государственное Унитарное Предприятие "Институт Химических Реактивов И Особо Чистых Химических Веществ Национального Исследовательского Центра "Курчатовский Институт" (Ниц "Курчатовский Институт" - Иреа) Способ получения высокочистого калия дигидрофосфата
US11021411B2 (en) 2017-05-24 2021-06-01 Ksm Inc. Potassium magnesium fertilizer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3197302A (en) * 1962-11-02 1965-07-27 Grace W R & Co Soluble fertilizer composition
US4045543A (en) * 1975-11-12 1977-08-30 Pennzoil Company Production of potassium sulfate and hydrogen chloride
US6863826B2 (en) * 2002-11-25 2005-03-08 Richard G. Sheets Animal waste effluent treatment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3197302A (en) * 1962-11-02 1965-07-27 Grace W R & Co Soluble fertilizer composition
US4045543A (en) * 1975-11-12 1977-08-30 Pennzoil Company Production of potassium sulfate and hydrogen chloride
US6863826B2 (en) * 2002-11-25 2005-03-08 Richard G. Sheets Animal waste effluent treatment

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11021411B2 (en) 2017-05-24 2021-06-01 Ksm Inc. Potassium magnesium fertilizer
RU2712689C1 (ru) * 2018-11-29 2020-01-30 Федеральное Государственное Унитарное Предприятие "Институт Химических Реактивов И Особо Чистых Химических Веществ Национального Исследовательского Центра "Курчатовский Институт" (Ниц "Курчатовский Институт" - Иреа) Способ получения высокочистого калия дигидрофосфата

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