WO2012171117A1 - Procédé et système pour la production de sulfate de potassium à partir de chlorure de potassium - Google Patents

Procédé et système pour la production de sulfate de potassium à partir de chlorure de potassium Download PDF

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Publication number
WO2012171117A1
WO2012171117A1 PCT/CA2012/050253 CA2012050253W WO2012171117A1 WO 2012171117 A1 WO2012171117 A1 WO 2012171117A1 CA 2012050253 W CA2012050253 W CA 2012050253W WO 2012171117 A1 WO2012171117 A1 WO 2012171117A1
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WO
WIPO (PCT)
Prior art keywords
reactor
potassium
solution
sulfate
magnesium sulfate
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/CA2012/050253
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.)
Nichromet Extraction Inc
Original Assignee
Nichromet Extraction 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 CA 2743608 external-priority patent/CA2743608A1/fr
Priority claimed from US13/160,040 external-priority patent/US8409542B2/en
Application filed by Nichromet Extraction Inc filed Critical Nichromet Extraction Inc
Publication of WO2012171117A1 publication Critical patent/WO2012171117A1/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
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides

Definitions

  • the present invention relates to fertilizers. More specifically, the present invention concerns the production of a chlorine-free potassium sulfate from potassium chloride.
  • Potassium is an important fertilizer and it is found in nature as salts such as sylvinite
  • KCI sodium chloride
  • KCI. MgCI 2 . 6H 2 0 carnallite
  • KCI.MgS0 4 .3H 2 0 kainite
  • Most of the potassium made available for fertilizer uses is in the form of potassium chloride. But with intensive cultures, the chlorine combined with the potassium in potassium chloride has undesirable effects on soil, and therefore a chlorine- free potassium is desirable, generally a sulfate of potassium and magnesium. In many instances, however, pure potassium sulfate, K2SO4 , would be desirable because of its high potassium content.
  • a method for the production of potassium sulfate comprising reacting a source of water soluble potassium with a magnesium sulfate-containing substance in presence of an aqueous alcoholic solution.
  • a system for the production of potassium sulfate comprising a first reactor for dissolving a water soluble potassium in water into a first solution; a second reactor for dissolving magnesium sulfate hydrate in water and adding methanol into a second solution; a third reactor, adapted to receive the first and the second solutions, mixed then under stirring and cool them down into a slurry; a filter collecting and filtering the slurry from the third reactor; delivering, after rinsing of the solid part with methanol, chloride-free potassium sulfate, and a combined filtrate and rinsings; a column receiving and distilling the combined filtrate and rinsings, delivering methanol back to the second reactor and to the filter and a concentrated solution of magnesium chloride; a fourth reactor, adapted to receive the concentrated solution of magnesium chloride, which crystallizes upon cooling, and to treat the concentrate with sulfuric acid, delivering hydrochloric acid and a residual mass
  • Figure 1 is a flowchart of a method according to an embodiment of an aspect of the present invention.
  • Figure 2 is a schematic diagram of a system according to an embodiment of an aspect of the present invention.
  • the present invention provides a method and a system for the production of chlorine-free potassium sulfate (K2SO4) from a source of potassium, such as potassium chloride (KCI) for example, and a magnesium sulfate-containing substance, such as magnesium sulfate heptahydrate (MgS04 » 7H20) for example.
  • K2SO4 chlorine-free potassium sulfate
  • KCI potassium chloride
  • MgS04 » 7H20 magnesium sulfate-containing substance
  • the method generally comprises reacting KCI with MgS04 « 7H20 in the presence of a low boiling point alcohol such as methanol (MeOH) to yield K2SO4 and magnesium chloride hexahydrate (MgCI 2 '6H 2 0).
  • MgCI 2 '6H 2 0 is further treated with sulfuric acid (H2SO4) to yield back MgS0 4 '7H 2 0 which is re-used in the process and also hydrochloric acid (HCI).
  • H2SO4 sulfuric acid
  • HCI hydrochloric acid
  • the alcohol is distilled off and re-used in the process.
  • the method allows for the production of K2SO4 and HCI.
  • a method according to an embodiment of the present invention comprises the preparation of a saturated solution of KCI in water at 60°C (Solution A) (step 12), then the preparation of a saturated water solution of MgS04.7H 2 0 at 60°C, with addition of methanol until the apparition of cloudiness (Solution B) (step 14). Then, by mixing Solution A with Solution B at 60°C with good stirring and cooling to room temperature, a precipitation of K2SO4 is obtained (step 16), which is filtered (step 18) and rinsed with methanol (step 20). The combined filtrate and rinsings are distilled to recover the methanol and crystallize out magnesium chloride hydrate (step 22). This magnesium chloride hydrate is then treated with sulfuric acid in order to recover the initial magnesium sulfate along with hydrochloric acid, a useful product (step 24). [0018] The method is based on the following reaction (I) :
  • the precipitated K 2 SC>4 is filtrated and the resulting filtrate contains magnesium chloride in methanol and water. Methanol can be distilled off and recycled, and magnesium chloride crystallized out after evaporation of excess water. It has been noted that the hydrate of magnesium chloride reacts smoothly with sulphuric acid to give magnesium sulfate and hydrochloric acid at a temperature comprised in a range between about 1 10 °C and about 120°C, as per reaction (II) below:
  • reaction (II I) By combining reaction )l) and reaction (I I), reaction (II I) below is obtained:
  • KCI potassium chloride
  • the present invention thus provides a closed-loop method for the production of K2SO4 using a source of potassium such as KCI and a magnesium sulfate-containing substance such as MgS04'7H20, in the presence of a low boiling point alcohol such as MeOH, and which involves recycling and re-using MgS04'7H20.
  • a source of potassium such as KCI
  • a magnesium sulfate-containing substance such as MgS04'7H20
  • a source of water soluble potassium 10 is dissolved in a first reactor 20 with a minimum amount of water 30, for example at a ratio of water to KCI of about 2:8, at a temperature in a range comprised between about 50°C and about 65°C.
  • magnesium sulfate hydrate 50 is dissolved in a minimum amount of water 60, for example with a ratio of 0.7 water to MgS04'7H20 of about 0.7 w/w, at a temperature in a range comprised between about 50 °C and about 65°C and an amount of methanol 70 at a temperature in a range comprised between about 35°C and 45°C, for example 40°C, is added to the second reactor 40 so as to be near precipitation point.
  • the content of the first 20 and second 40 reactors are then rapidly, i.e.
  • the concentrate 170 is placed in a fourth reactor 180 and is treated there at a temperature in a range comprised between about 90°C and about 120°C with sulfuric acid 190.
  • the resulting hydrochloric acid 200 is absorbed in a collector 210 as a 32 % HCI solution 220.
  • the residual mass in the fourth reactor 180 is collected with a minimum (at a ratio of 0.4 w/w water to MgSC hkO for example), of hot water 230, between about 90°C and 100°C for example, and allowed to crystallize in a fifth reactor 240 and recycled to the second reactor 40 as magnesium sulfate heptahydrate 250.
  • This system allows the production of potassium sulfate of high purity, containing less than 1 % chlorides.
  • the temperatures of operation are low, typically below about 65°C, and the recycling of magnesium sulfate takes places at temperatures typically below about 120°C, with the production of hydrochloric acid as a useful secondary product.
  • 121 g of potassium chloride is dissolved in 335 ml_ of water at 60 °C in a 1 .4 L beaker.
  • a 200 g sample from (1 ) is dissolved in 142 mL of water at 60 °C, in a one litre beaker. Then, 230 mL of warm methanol (40 °C) is added slowly with good stirring to the solution of magnesium sulfate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé et un système pour la production de sulfate de potassium. Le procédé comprend la mise en réaction d'une source de potassium soluble dans l'eau avec une substance contenant du sulfate de magnésium en présence d'une solution alcoolique aqueuse. Le système comprend un premier réacteur pour dissoudre un potassium soluble dans l'eau dans de l'eau dans une première solution ; un deuxième réacteur pour dissoudre un hydrate de sulfate de magnésium dans de l'eau et ajouter du méthanol dans une deuxième solution ; un troisième réacteur, conçu pour recevoir la première et la deuxième solution, les mélanger sous agitation et les refroidir pour former une suspension ; un filtre qui recueille et filtre la suspension issue du troisième réacteur ; fournissant, après rinçage de la partie solide avec du méthanol, un sulfate de potassium exempt de chlorure, et un filtrat et produit de rinçage combiné ; une colonne recevant et distillant le filtrat et produit de rinçage combiné, recyclant le méthanol dans le deuxième réacteur et dans le filtre et fournissant une solution concentrée de chlorure de magnésium ; un quatrième réacteur, conçu pour recevoir la solution concentrée de chlorure de magnésium, qui cristallise par refroidissement, et pour traiter le concentré avec de l'acide sulfurique, fournissant de l'acide chlorhydrique et une masse résiduelle ; un collecteur, conçu pour absorber l'acide chlorhydrique fourni par le quatrième réacteur ; et un cinquième réacteur, conçu pour recueillir et cristalliser la masse résiduelle issue du quatrième réacteur, pour la recycler dans le deuxième réacteur en tant qu'heptahydrate de sulfate de magnésium.
PCT/CA2012/050253 2011-06-14 2012-04-20 Procédé et système pour la production de sulfate de potassium à partir de chlorure de potassium Ceased WO2012171117A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CA 2743608 CA2743608A1 (fr) 2011-06-14 2011-06-14 Methode et systeme de production de sulfate de potassium a partir de chlorure de potassium
CA2,743,608 2011-06-14
US13/160,040 2011-06-14
US13/160,040 US8409542B2 (en) 2011-06-14 2011-06-14 Method and system for the production of potassium sulfate from potassium chloride

Publications (1)

Publication Number Publication Date
WO2012171117A1 true WO2012171117A1 (fr) 2012-12-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2012/050253 Ceased WO2012171117A1 (fr) 2011-06-14 2012-04-20 Procédé et système pour la production de sulfate de potassium à partir de chlorure de potassium

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WO (1) WO2012171117A1 (fr)

Cited By (1)

* 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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615174A (en) * 1968-06-28 1971-10-26 Nl Industries Inc Process for the selective recovery of potassium and magnesium values from aqueous salt solutions containing the same
US4341752A (en) * 1980-04-18 1982-07-27 Norsk Hydro A.S. Method for purification and concentration of MgCl2 -brines
US4533536A (en) * 1982-03-11 1985-08-06 Mines De Potasse D'alsace S.A. Process for the manufacture of potassium sulphate by treating solutions containing magnesium chloride and potassium chloride
CA2464642A1 (fr) * 2001-10-22 2003-05-01 Council Of Scientific And Industrial Research Extraction du chlorure de sodium et des autres sels contenus dans de la saumure
US7780941B1 (en) * 2009-04-06 2010-08-24 Nichromet Extraction Inc. Potassium magnesium fertilizer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615174A (en) * 1968-06-28 1971-10-26 Nl Industries Inc Process for the selective recovery of potassium and magnesium values from aqueous salt solutions containing the same
US4341752A (en) * 1980-04-18 1982-07-27 Norsk Hydro A.S. Method for purification and concentration of MgCl2 -brines
US4533536A (en) * 1982-03-11 1985-08-06 Mines De Potasse D'alsace S.A. Process for the manufacture of potassium sulphate by treating solutions containing magnesium chloride and potassium chloride
CA2464642A1 (fr) * 2001-10-22 2003-05-01 Council Of Scientific And Industrial Research Extraction du chlorure de sodium et des autres sels contenus dans de la saumure
US7780941B1 (en) * 2009-04-06 2010-08-24 Nichromet Extraction Inc. Potassium magnesium fertilizer

Cited By (1)

* 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

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