WO2021203123A1 - Procédés de fabrication de sels de phosphate - Google Patents

Procédés de fabrication de sels de phosphate Download PDF

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Publication number
WO2021203123A1
WO2021203123A1 PCT/US2021/070323 US2021070323W WO2021203123A1 WO 2021203123 A1 WO2021203123 A1 WO 2021203123A1 US 2021070323 W US2021070323 W US 2021070323W WO 2021203123 A1 WO2021203123 A1 WO 2021203123A1
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WO
WIPO (PCT)
Prior art keywords
phosphate
phosphoric acid
alcoholic solvent
salt
potassium
Prior art date
Application number
PCT/US2021/070323
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English (en)
Inventor
Paul GAUVREAU
Original Assignee
Johnson Matthey Public Limited Company
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 Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2021203123A1 publication Critical patent/WO2021203123A1/fr

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    • 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
    • C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates

Definitions

  • the present invention is directed to novel processes for the production of phosphate salts.
  • the present invention is directed to processes for the production of mono and di sodium phosphate and mono and di potassium phosphate using an alcoholic solvent.
  • U.S. Patent No. 3,697,246 is directed to a process for the production of potassium dihydrogen phosphate from phosphate rock or a solubilized form thereof, sulfuric acid and optionally phosphoric acid, and potassium hydrogen sulfate wherein the reaction may be carried out in either a batch or a continuous manner.
  • U.S. Patent No. 3,697,246 further discloses precipitation of potassium dihydrogen phosphate from a phosphoric acid solution by addition of an organic solvent, such as those that are miscible with water, for example a lower alcohol including methanol, ethanol, and isopropanol.
  • U.S. Patent No. 4,678,649 is directed to a process for the manufacture of monopotassium phosphate of a high purity without using organic solvents. More specifically, U.S. Patent No. 4,678,649 is directed to a process for the manufacture of monopotassium phosphate which comprises the steps of: (a) reacting monopotassium sulfate with a phosphate constituent selected from the group consisting of phosphate rock, dicalcium phosphate or mixtures thereof in the presence of phosphoric acid, and separating the formed calcium sulfate; (b) neutralizing the filtrate obtained in step (a) with a calcium-containing compound comprising Ca(OH)2, CaO or CaCCL or mixtures thereof, and (c) crystallizing from the filtrate obtained in step (b) substantially pure monopotassium phosphate.
  • a phosphate constituent selected from the group consisting of phosphate rock, dicalcium phosphate or mixtures thereof in the presence of phosphoric acid, and separating the formed calcium
  • U.S. Patent No. 4,836,995 is directed to a process for the manufacture of monopotassium phosphate using solvent extraction technique.
  • U.S. Patent No. 4,836,995 describes a process for manufacturing monopotassium phosphate which comprises: (a) reacting phosphoric acid with potassium chloride in the presence of an organic solvent comprising a long chain primary amine having between 6 to 28 carbon atoms, at a temperature between 0 and 100 °C; (b) separating the lower aqueous phase comprising mono- and dipotassium phosphate salts; and (c) acidulating the phosphate salts by a solution of phosphoric acid to a pH in the range of between 2 to 6, whereby crystallized monopotassium phosphate is obtained and separated.
  • U.S. Patent No. 7,601,319 is directed to a process for producing monobasic potassium phosphate by reacting potassium hydroxide and phosphoric acid to form a reaction mixture; cooling the reaction mixture to precipitate crystals of monobasic potassium phosphate; homogenizing and spray drying the reaction mixture, resulting in solid monobasic potassium phosphate.
  • U.S. Patent No. 7,601,319 fails to mention the use of any solvent other than water for use in the reaction mixture.
  • the processes of the art suffer from a number of disadvantages in preparing phosphate salts.
  • the processes for manufacturing phosphate salts are performed in an aqueous solution, and the salts have a high solubility in water, the processes generally require that the volume of water be reduced to precipitate the phosphate salts for isolation and still a substantial portion of the phosphate salts remain in solution and are not isolated.
  • the reduction of the volume of water, such as by distillation, is energy intensive and time consuming.
  • Another disadvantage with a salt isolated from water is it is more difficult to dry the salt.
  • the current invention is directed to processes for the production of phosphate salts, specifically, mono- and di-sodium phosphate and mono- and di-potassium phosphate in an alcoholic solvent. More particularly, the invention comprises reacting a solution of sodium or potassium hydroxide in an alcoholic solvent or a slurry of a carbonate base in an alcoholic solvent with phosphoric acid.
  • Phosphate salts are prepared according to the following stoichiometric reaction constituents:
  • the invention is directed to a process of preparing a phosphate salt comprising reacting a solution of sodium hydroxide or potassium hydroxide in an alcoholic solvent with phosphoric acid resulting in precipitation of the phosphate salt, wherein the phosphate salt is monopotassium phosphate, dipotassium phosphate, monosodium phosphate, or disodium phosphate.
  • the salt is monopotassium phosphate and the molar ratio of the potassium hydroxide to phosphoric acid is about 1:1. In another embodiment, the salt is dipotassium phosphate and the molar ratio of the potassium hydroxide to phosphoric acid is about 2:1. In another embodiment, the salt is monosodium phosphate and the molar ratio of sodium hydroxide to phosphoric acid is about 1:1. In yet another embodiment, the salt is disodium phosphate and the molar ratio of the sodium hydroxide to phosphoric acid is about 2:1.
  • the alcoholic solvent is a C1-3 alcohol such as methanol, ethanol, propanol, isopropanol, or mixtures thereof; more particularly, the alcoholic solvent is methanol.
  • the particular concentration of the sodium hydroxide or potassium hydroxide in the alcoholic solvent is not critical, though a particular embodiment is where the base is dissolved in the alcoholic solvent.
  • the concentration of potassium hydroxide in methanol is about 25-28% (by weight).
  • the concentration of sodium hydroxide in methanol is about 20-22% (by weight). It is advantageous to use as concentrated a solution as possible to minimize the amount of alcoholic solvent needed and thereby reduce costs.
  • the phosphoric acid is anhydrous.
  • the phosphoric acid is present in water (phosphoric acid solution), particularly a concentrated solution, more particularly about >50%, 60%, 70%, 85% phosphoric acid, more particularly about >85% phosphoric acid (by weight) as it is the standard grade and is commercially available. It is desirable to minimize the amount of water present.
  • the phosphoric acid whether anhydrous or in water, can be dissolved in an alcoholic solvent. The reaction of the alcoholic solution of potassium hydroxide or sodium hydroxide and the phosphoric acid is exothermic. In one embodiment, the reaction temperature is controlled to avoid the temperature exceeding the boiling point of the alcoholic solvent.
  • the reaction temperature when methanol is used as the alcoholic solvent, the reaction temperature should not exceed about 60 °C since methanol boils around 65 °C.
  • the reaction temperature can be controlled by means understood by one of skill in the art, e.g., by controlling the rate of the reacting such as by controlling the time period over which the reactants are reacted or the temperature of the reaction by cooling the reaction.
  • the reaction temperature is at or above the boiling point of the alcoholic solvent.
  • the reacting is carried out by mixing the solution of sodium hydroxide or potassium hydroxide in an alcoholic solvent with the phosphoric acid.
  • the length of time of the reacting varies depending upon the reaction volume and amounts of reactants. Any mixing methods known to one of skill in the art can be used.
  • the reaction mixture is optionally cooled to about 20-40 °C.
  • the precipitation of the phosphate salt is almost instantaneous upon reacting the alcoholic solution of the hydroxide base with the phosphoric acid.
  • the reacting comprises adding the alcoholic solution of the hydroxide base to the phosphoric acid. In another embodiment, the reacting comprises adding the phosphoric acid to the alcoholic solution of the hydroxide base.
  • the precipitated phosphate salt can be isolated by vacuum filtration.
  • the phosphate salt can be isolated using a centrifuge or pressure/filter dryer (PFD).
  • the isolated phosphate salt can be washed with the alcoholic solvent.
  • additional alcoholic solvent can be used to remove the precipitated phosphate salt from the reaction vessel.
  • the isolated phosphate salt can be dried under vacuum.
  • the isolated phosphate salt is dried at about 60 °C.
  • the isolated phosphate salt is dried until the amount of solvent remaining in the phosphate salt is below the acceptable limit.
  • the process comprises reacting a slurry of potassium carbonate or sodium carbonate in an alcoholic solvent with phosphoric acid to yield mono- and di- sodium or potassium phosphate.
  • the molar ratio of the potassium carbonate or sodium carbonate to phosphoric acid is about 0.5:1 to yield the corresponding monopotassium phosphate and monosodium phosphate, and about 1:1 to yield the disodium and dipotassium phosphate.
  • the alcoholic solvent is a C1-3 alcohol such as methanol, ethanol, propanol, isopropanol, or mixtures thereof; more particularly, the alcoholic solvent is methanol.
  • the ratio of the amount (g) of potassium or sodium carbonate to quantity (mL) of alcoholic solvent is not critical, as long as a slurry of the carbonate is formed. It is advantageous to use lower volumes of the alcoholic solvent for cost reasons; however, a sufficient volume of solvent should be used for ease of transfer of the reaction mixture to/from the reaction vessel.
  • the phosphoric acid is anhydrous.
  • the phosphoric acid is present in water (phosphoric acid solution), particularly a concentrated solution, more particularly about >50%, 60%, 70%, 85% phosphoric acid, more particularly about >85% phosphoric acid (by weight) as it is the standard grade and is commercially available. It is desirable to minimize the amount of water present.
  • the phosphoric acid, whether anhydrous or in water can be dissolved in an alcoholic solvent.
  • the reaction between the potassium or sodium carbonate and the phosphoric acid is exothermic.
  • the reaction temperature is controlled to avoid temperatures exceeding the boiling point of the alcoholic solvent.
  • the reaction temperature should not exceed about 60 °C.
  • the reaction temperature can be controlled by means understood by one of skill in the art, e.g., by controlling the rate of the reacting such as by controlling the time period over which the reactants are reacted or the temperature of the reaction by cooling the reaction.
  • the reaction temperature is at or above the boiling point of the alcoholic solvent.
  • the reacting is carried out by mixing the slurry of potassium or sodium carbonate in an alcoholic solvent with the phosphoric acid.
  • the length of time of the reacting varies depending upon the reaction volume and amounts of reactants. Any mixing methods known to one of skill in the art can be used.
  • the reacting comprises adding the slurry of potassium or sodium carbonate in alcoholic solvent to the phosphoric acid.
  • the reacting comprises adding the phosphoric acid to the slurry of potassium or sodium carbonate in alcoholic solvent.
  • the reaction mixture is held for a period of time to ensure that the reaction has gone to completion, i.e., that all the solid potassium or sodium carbonate is replaced by the desired mono- or di- potassium or sodium phosphate.
  • the length of time for the hold varies depending upon the reaction volume.
  • the reaction mixture is optionally cooled to about 20-40 °C.
  • the mono- or di- potassium or sodium phosphate can be isolated by vacuum filtration.
  • the phosphate salt can be isolated using a centrifuge or pressure/filter dryer (PFD).
  • the isolated mono- or di- potassium or sodium phosphate can be washed with the alcoholic solvent.
  • additional alcoholic solvent can be used to remove the mono- or di- potassium or sodium phosphate from the reaction vessel.
  • the isolated mono- or di- potassium or sodium phosphate can be dried under vacuum.
  • the isolated mono- or di- potassium or sodium phosphate salt is dried at about 60 °C.
  • the isolated phosphate salt is dried until the amount of solvent remaining in the phosphate salt is below the acceptable limit.
  • a sodium hydroxide or potassium hydroxide alcoholic solution as the base component is preferred in the process of preparing mono- or di- potassium or sodium phosphate because the hydroxide bases are less expensive than carbonate bases and because sodium hydroxide and potassium hydroxide are soluble in the alcoholic solvent.
  • the processes of the current invention offer advantages over prior art processes for preparing phosphate salts.
  • the low solubility of the phosphate salts in C1-3 alcohols facilitates the precipitation of the phosphate salts for isolation and results in virtually none of the salt remaining in the reaction solution and not isolated versus the prior art processes wherein the reaction solvent is substantially aqueous.
  • the phosphate salts can be isolated in high yield without concentration of the reaction solvent as opposed to the prior art wherein concentration of the aqueous solvent is effected, e.g., by distillation of water. Distillation of water is energy intensive and time consuming.
  • Another advantage of the current processes is that drying the phosphate salts isolated from an alcoholic solvent takes place faster than drying the phosphate salts isolated from water.
  • 150 g of 28% by weight potassium hydroxide in methanol (0.75 moles) is added to 86.5 g 85% phosphoric acid (0.75 moles) in 250-mL reactor with maximum batch temperature of about 50 °C.
  • the base addition funnel is rinsed with 10 g methanol into the batch.
  • the batch is cooled to approximately 20 °C and the solid is isolated by vacuum filtration.
  • the vessel and filter cake are rinsed with methanol to remove solid from the vessel.
  • the collected solid is dried under vacuum at 60 °C to yield 100.6 g product, 98.5% yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

La présente invention concerne de nouveaux procédés pour la production de sels de phosphate de sodium ou de potassium. En particulier, la présente invention concerne des procédés de production de phosphate monosodique et disodique et de phosphate monopotassique et dipotassique à l'aide d'un solvant alcoolique.
PCT/US2021/070323 2020-03-31 2021-03-26 Procédés de fabrication de sels de phosphate WO2021203123A1 (fr)

Applications Claiming Priority (2)

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US202063002626P 2020-03-31 2020-03-31
US63/002,626 2020-03-31

Publications (1)

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WO2021203123A1 true WO2021203123A1 (fr) 2021-10-07

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3697246A (en) 1970-10-16 1972-10-10 Pennzoil United Inc Potassium phosphate manufacture
US3993733A (en) * 1975-08-14 1976-11-23 Stauffer Chemical Company Food grade alkali metal phosphates from wet process H3 PO4
US4678649A (en) 1985-07-10 1987-07-07 Negev Phosphates Ltd. Process for the manufacture of monopotassium phosphate
US4751066A (en) * 1986-05-08 1988-06-14 Fmc Corporation Process for preparing alkali metal phosphate
US4836995A (en) 1986-06-04 1989-06-06 Haifa Chemicals Ltd. Process for the manufacture of monopotassium phosphate
US7601319B2 (en) 2007-09-21 2009-10-13 J.I. Enterprises, Inc. Process for the manufacture of monobasic potassium phosphate
CN105174236B (zh) * 2015-08-11 2017-06-23 贵州师范学院 一种用湿法磷酸制备磷酸钾盐的方法及设备

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3697246A (en) 1970-10-16 1972-10-10 Pennzoil United Inc Potassium phosphate manufacture
US3993733A (en) * 1975-08-14 1976-11-23 Stauffer Chemical Company Food grade alkali metal phosphates from wet process H3 PO4
US4678649A (en) 1985-07-10 1987-07-07 Negev Phosphates Ltd. Process for the manufacture of monopotassium phosphate
US4751066A (en) * 1986-05-08 1988-06-14 Fmc Corporation Process for preparing alkali metal phosphate
US4836995A (en) 1986-06-04 1989-06-06 Haifa Chemicals Ltd. Process for the manufacture of monopotassium phosphate
US7601319B2 (en) 2007-09-21 2009-10-13 J.I. Enterprises, Inc. Process for the manufacture of monobasic potassium phosphate
CN105174236B (zh) * 2015-08-11 2017-06-23 贵州师范学院 一种用湿法磷酸制备磷酸钾盐的方法及设备

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