EP3801842A2 - Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process - Google Patents

Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process

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Publication number
EP3801842A2
EP3801842A2 EP19750051.5A EP19750051A EP3801842A2 EP 3801842 A2 EP3801842 A2 EP 3801842A2 EP 19750051 A EP19750051 A EP 19750051A EP 3801842 A2 EP3801842 A2 EP 3801842A2
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EP
European Patent Office
Prior art keywords
lithium
product
forming
exchange membrane
solution
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
EP19750051.5A
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German (de)
French (fr)
Inventor
Tomas KOTALA
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Membrain SRO
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Membrain SRO
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Publication of EP3801842A2 publication Critical patent/EP3801842A2/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • 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
    • C01D5/06—Preparation of sulfates by double decomposition

Definitions

  • the present invention describes a process to produce lithium chemical compounds, such as lithium hydroxide, bicarbonate or carbonate, using electrodialysis, which involves ion exchange between lithium sulfate solution (Li 2 S0 4 ) and sodium hydroxide solution (NaOH), sodium bicarbonate (NaHCOs) or sodium carbonate (Na 2 C0 3 ).
  • the invention relates to an apparatus for performing out the method.
  • Lithium hydroxide, lithium bicarbonate, or lithium carbonate are prepared by reacting lithium sulfate (L1 2 SO4) with any of the following species: sodium hydroxide (NaOH), sodium bicarbonate (NaHCOs), or sodium carbonate (Na 2 C0 3 ). Reactions are based on the following chemical equations:
  • the first production option is double replacement reaction: chemical compound solutions are mixed in a reactor where they react together to precipitate the solid product, such as Li 2 C0 3 , using controlled heating and cooling and also neutralization principle.
  • the solid product such as Li 2 C0 3
  • Such a technical approach is the subject of the Chinese patent CN 1486931.
  • the disadvantages of the said process are level of conversion, the formation of solid deposits on the reactor surface during crystallization, and the need to refine the product to a level of applicability for batteries like battery grade lithium carbonate.
  • Electrodialytic concentrating lithium salt from primary resource where a concentrated lithium sulfate solution is mixed in a sodium carbonate solution in a reactor.
  • bipolar electrodialysis driving force is the DC voltage.
  • the cation exchange membranes, the bipolar membranes, and optionally the anion exchange membranes are in the electrodialysis stack.
  • Lithium hydroxide is formed, and the principle of bipolar electrodialysis function also forms the corresponding acids like sulfuric, hydrochloric, or nitric.
  • the lithium hydroxide production process is optimized according to the source of the raw material, such as salt lakes, or the hydrometallurgical treatment of the batteries.
  • Electrodialysis metathesis method described in this invention helps to overcome the above-mentioned drawbacks of different electrodialysis concepts while maintaining the progressive features of the process for producing lithium chemical compounds such as lithium hydroxide, bicarbonate or carbonate.
  • the invention involves the exchange of ions between the lithium sulfate solution (Li 2 S0 4 ) and the sodium hydroxide solution (NaOH), primary sodium bicarbonate (NaHCCb) or sodium carbonate (Na 2 COs), which takes place in an electric field on an ion exchange membrane system containing at least one anion exchange membrane and cation exchange membranes.
  • the repeating sequence of ion exchange membranes form at least four intermembrane spaces.
  • the basic repeating motif is visualized in Figure lb by hatching.
  • the ions forming the main product are passing through the P-labeled membranes (see Figs la and lb).
  • Lithium-ion is passing the cation exchange membrane CMP forming the main product.
  • the hydroxide, bicarbonate or carbonate anions are passing anion exchange membrane AMP forming the main product.
  • the sodium and sulfate ions are passing through the O-labeled membranes.
  • ions are forming the by-product sodium sulfate solution stream after recombination - specifically through the cation exchange membrane CMO forming by-product cation and through the anion exchange membrane AMO forming by-product sulfate anion.
  • a cation exchange membrane terminates the basic repeating motif including the four intermembrane spaces Cl, Dl, C2, D2. Source and product chemical compounds solutions flow on both sides of the membranes in the intermembrane compartments Cl, Dl, C2, D2.
  • a solution of the by-product flows in the first intermembrane space Cl, from the positive electrode - anode + by interposing the first cation exchange product CMO forming the byproduct and the first anion-exchange AMO forming the by-product.
  • the primary anion source solution e.g., sodium hydroxide, bicarbonate, and sodium carbonate flow in the fourth intermembrane space D2 from the positive electrode (anode +), between the second anion exchange membrane AMP forming the main product and the cation exchange membrane CMO forming by-product.
  • a primary cation source solution e.g., lithium sulfate solution flows in the second intermembrane space Dl from the positive electrode (anode +), between the first anion exchange membrane AMO forming the by-product and the second cation exchange membrane CMP forming the main product.
  • the concentration of the lithium sulfate, sodium hydroxide, primary source sodium bicarbonate, or sodium carbonate feed solutions is preferably in the range from 0.1 to 1.0 mol/L.
  • the concentration of the obtained product solutions - sodium sulfate, lithium hydroxide, lithium bicarbonate, or lithium carbonate is higher than 0.1 mol/L.
  • the temperature of the solutions in operation is preferably in the range from 10 to 60 °C, preferably in the range from 20 to 50 °C. Their solubility limits the final salt solution concentration.
  • the apparatus for carrying out the method of the present invention is comprised of electrodes, between which an array of ion exchange membranes is included containing at least one sequence of anion exchange membranes AMP, AMO and cation exchange membranes CMP, CMO, alternating and forming at least four intermembrane spaces Cl, Dl, C2, D2 for solutions of input and output chemical compounds of electrodialysis double replacement reaction ion exchange system.
  • the ion exchange membranes are preferable of the homogeneous or heterogeneous type in thickness from 0.1 to 1.0 mm and with a permselectivity more than 90%.
  • Membrane spacers thickness is between 0.1 to 2.0 mm, and distributors are made from polymeric material providing solution equal distribution, source, and product solution mutual immiscibility and mechanical support of the intermembrane spaces.
  • the voltage between the electrodes is preferably from 1.0 to 2.5 V per sequence of four membranes - a membrane quadruplet at a current density in the range from 30 to 300 A/m 2 .
  • the main advantage of the lithium bicarbonate production using electrodialysis metathesis double replacement reaction process according to the invention is obtaining a straightforward first product solution - e.g., L1HCO3, which meets the purity application limits in batteries, at a high conversion rate.
  • the conversion itself takes place in an electrodialysis device made of non-corrosive polymeric materials.
  • the benefit of this technical solution is the preparation of a high concentration lithium bicarbonate/carbonate solution near saturation limit with very high purity for use in batteries.
  • An analogy of the Solvay process used in the production of sodium carbonate can be utilized for the further production of a commodity chemical like Li 2 C0 3 . Formed lithium bicarbonate formed is converted to lithium carbonate by heating (calcination).
  • Fig. la is a schematic diagram of an electrodialysis metathesis double replacement reaction method for producing lithium hydroxide, lithium bicarbonate or lithium carbonate by using one (simplest) ion exchange membrane sequence;
  • Fig. lb is a representation of an electrodialysis metathesis double replacement reaction method basic repeating motif for producing lithium hydroxide, lithium bicarbonate, or lithium carbonate using one (hatched) ion exchange membrane sequence and one ending cation exchange membrane CMO;
  • Figure 2 shows an exemplary arrangement of five series of four membranes - membrane quadruplets.
  • the electrodialysis laboratory unit P EDR-Z/4x (producer company MemBrain) in electrodialysis-metathesis configuration was used for testing.
  • the unit contained 5 tanks with a volume of 0.25 to 2.0 liters and 5 centrifugal pumps with a magnetic insert for circulation of solutions in the intermembrane spaces Cl, C2, Dl, D2 created by the anion exchange membranes of AMP, AMO and cation exchange membranes CMP, CMO (scheme of one primary sequence - see Figure lb) and also for electrode rinsing solution E.
  • Electrode solution - sodium sulfate solution (Na 2 S0 4 ).
  • EDM module was equipped with eleven pcs of cation exchange membranes RALEX ® (CM-PP) and with ten pcs of anion exchange membranes RALEX ® (AM-PP), alternating and forming five membrane sequences (quadruplets) - see scheme in Figure 2.
  • CM-PP cation exchange membranes
  • AM-PP anion exchange membranes
  • Each of the membrane repeating sequence had the arrangement of the hatched part from Figure lb.
  • One active membrane area was 64 cm 2 . The test was performed in a batch process.
  • the EDM solutions were circulated at 0.5 L/min, and the temperature was kept at 30 °C.
  • the working voltage was in the range from 6.7 to 12.0 V and the current was set at 1.28 A.
  • 1000 mL of L1HCO3 solution main product was obtained in the third intermembrane space C2 of with concentration 0.69 mol/L and 1100 ml of the secondary product Na 2 S0 4 in the first intermembrane space Cl with concentration 0.38 mol/L in this design of experiment.
  • the main product was dosed with demineralized water to prevent precipitation by reaching the solubility level.
  • the sulfur content in the main product was 0.115 g/L, and the lithium content was 4.78 g/L.
  • the product purity in terms of the molar content of lithium in the numerator relative to the sum of lithium and sulfur in the denominator was 99.5%.
  • a sodium sulfate solution with 0.07 mol/L concentration was circulated in the electrode chambers during the experiment.
  • Lithium chemical compounds production like lithium hydroxide, bicarbonate, or carbonate which are widely used in the battery industry.

Abstract

A process for producing lithium chemical compounds, such as lithium hydroxide, bicarbonate or carbonate, by electrodialysis metathesis acting as double reaction replacement system, which involves ion exchange between a solution of lithium sulfate and a solution of sodium hydroxide, sodium bicarbonate or sodium carbonate, in an array of ion exchange membranes (see Fig. 1a) comprising at least one anion exchange membrane sequence (AMP, AMO) and cation exchange membranes (CMP, CMO) alternating and forming at least four intermembrane spaces (C1, D1, C2, D2). A solution of the by-product flows in the first intermembrane space Cl, from the positive electrode by interposing the first cation exchange product CMO forming the by-product and the first anion-exchange AMO creating the by- product. A solution of the main product of lithium hydroxide, lithium bicarbonate or lithium carbonate flows in the third intermediate membrane space C2 from the positive electrode, between the second cation exchange membrane CMP forming the main product and the second anion exchange membrane AMP forming the main product. A primary anion source solution, e.g., sodium hydroxide, bicarbonate, and sodium carbonate flows in the fourth intermembrane space D2 from the positive electrode, between the second anion exchange membrane AMP forming the main product and the cation exchange membrane CMO forming by-product. A primary cation source solution, e.g., lithium sulfate solution flows in the second intermembrane space D1 from the positive electrode, between the first anion exchange membrane AMO forming the by-product and the second cation exchange membrane CMP forming the main product. The invention relates to an apparatus for carrying out the method.

Description

PROCESS FOR PREPARING LITHIUM CHEMICAL COMPOUNDS BY ELECTRODIALYSIS METHOD AND APPARATUS FOR PERFORMING THIS PROCESS
Field of application
The present invention describes a process to produce lithium chemical compounds, such as lithium hydroxide, bicarbonate or carbonate, using electrodialysis, which involves ion exchange between lithium sulfate solution (Li2S04) and sodium hydroxide solution (NaOH), sodium bicarbonate (NaHCOs) or sodium carbonate (Na2C03). The invention relates to an apparatus for performing out the method.
State of the art
Lithium hydroxide, lithium bicarbonate, or lithium carbonate are prepared by reacting lithium sulfate (L12SO4) with any of the following species: sodium hydroxide (NaOH), sodium bicarbonate (NaHCOs), or sodium carbonate (Na2C03). Reactions are based on the following chemical equations:
There are two obvious ways to implement the synthesis of lithium salts at present:
The first production option is double replacement reaction: chemical compound solutions are mixed in a reactor where they react together to precipitate the solid product, such as Li2C03, using controlled heating and cooling and also neutralization principle. Such a technical approach is the subject of the Chinese patent CN 1486931. The disadvantages of the said process are level of conversion, the formation of solid deposits on the reactor surface during crystallization, and the need to refine the product to a level of applicability for batteries like battery grade lithium carbonate.
A similar procedure for the third chemical equation mentioned above is described in a paper called Electrodialytic concentrating lithium salt from primary resource, where a concentrated lithium sulfate solution is mixed in a sodium carbonate solution in a reactor.
In the technical solution described in the patent CN 1486931, the main disadvantage is the multistep final cleaning of the product. After the reaction
Li2S04 + 2 NaOH -> 2 LiOH + Na2S04 It is necessary to cool the reaction mixture down to a temperature in the range from -10 ° C to -5 0 C to crystallize solid Na2S04. Crude LiOH solution is obtained after sodium sulfate crystals filtration. Sulfates have to be removed from the mother liquor after crystallization to get high purity product. The mother liquor is mixed with barium hydroxide. The goal of this operation is to perform a reaction
Na2S04 + Ba(OH)2 -» 2 NaOH + BaS04 (s)
Subsequent filtration steps are followed by concentration steps. Evaporation of the purified lithium hydroxide solutions is followed by crystallization thereof to separate the wet cake in the form of LiOH.H20. Final production step is product drying. A similar purification sequence will be necessary also for the procedure presented in paper called Electrodialytic concentrating lithium salt from primary resource.
With the known membrane technology production - using cation exchange, anion exchange, or even bipolar membranes, the separation of lithium-ion is occurring through the cation exchange membrane from the source salt. Proposed lithium source salts are lithium sulfate, lithium chloride, or lithium nitrate. Target of these concepts is pure lithium hydroxide or lithium carbonate production. Such technical solutions are the subject of Chinese patents CN 103882468, CN 106946275, CN 107298450 or German patent DE 102013016671.
Ion exchange using bipolar membranes is described in patents CN 103882468, CN 106946275, CN 107298450 or DE 102013016671. The bipolar electrodialysis driving force is the DC voltage. The cation exchange membranes, the bipolar membranes, and optionally the anion exchange membranes are in the electrodialysis stack. Lithium hydroxide is formed, and the principle of bipolar electrodialysis function also forms the corresponding acids like sulfuric, hydrochloric, or nitric. The lithium hydroxide production process is optimized according to the source of the raw material, such as salt lakes, or the hydrometallurgical treatment of the batteries. The disadvantage of this method, however, is that the product (Li2C03) is not formed directly but only by subsequent neutralization. Another drawback is the need for a robust pre-treatment to eliminate unwanted multivalent metals such as magnesium, which can destroy the bipolar membrane. It is also necessary to pay attention to the selectivity of the membranes in the processes since the pollution of the produced LiOH by the sulfate ions induces the need for the application of barium hydroxide precipitation. The above patents describe the production of lithium hydroxide hydrate or the production of lithium carbonate. Japanese Patent JP2004083324A discloses electrodialysis metathesis configuration for the lithium nitrite production due to the double replacement reaction of lithium sulfate and sodium nitrite. It is possible to achieve minimal pollution of LiN02 by sodium ions and sulfate anions by appropriate control of concentration ratios of individual chemical components. The disadvantage of this process is the asymmetry of the membranes at the end and beginning of the electrodialysis stack. The reason for this situation is to prevent oxidation of nitrite to nitrate and transfer of sodium to the product. Standard electrodialysis stacks beams are commonly terminated in both anolyte and catholyte by either cation exchange, anion exchange, or bipolar membranes because they hold the ionic balance between cations and anions.
The principle of electrodialysis metathesis is demonstrated for the oxidizing agent's preparation in US patent US20060000713A1. The main disadvantage of this concept is the necessity of special PTFE or PVDF -based membranes application that are chemically resistant to oxidation. Furthermore, electrode reactions that generate acidic and basic products must also be counted during the double replacement reaction, since the oxidation potential of the compounds produced decreases with increasing pH of the resulting oxidant solution.
No technical solution has been found to date to obtain the lithium bicarbonate intermediate using electrodialysis metathesis acting as a double replacement reaction system.
Invention description
Electrodialysis metathesis method described in this invention helps to overcome the above-mentioned drawbacks of different electrodialysis concepts while maintaining the progressive features of the process for producing lithium chemical compounds such as lithium hydroxide, bicarbonate or carbonate. The invention involves the exchange of ions between the lithium sulfate solution (Li2S04) and the sodium hydroxide solution (NaOH), primary sodium bicarbonate (NaHCCb) or sodium carbonate (Na2COs), which takes place in an electric field on an ion exchange membrane system containing at least one anion exchange membrane and cation exchange membranes. The repeating sequence of ion exchange membranes form at least four intermembrane spaces. The basic repeating motif is visualized in Figure lb by hatching.
Summary of the invention can be described in the following configuration. To perform a double replacement reaction system using ion exchange membranes, the ions forming the main product are passing through the P-labeled membranes (see Figs la and lb). Lithium-ion is passing the cation exchange membrane CMP forming the main product. The hydroxide, bicarbonate or carbonate anions are passing anion exchange membrane AMP forming the main product. The sodium and sulfate ions are passing through the O-labeled membranes. These ions are forming the by-product sodium sulfate solution stream after recombination - specifically through the cation exchange membrane CMO forming by-product cation and through the anion exchange membrane AMO forming by-product sulfate anion. A cation exchange membrane terminates the basic repeating motif including the four intermembrane spaces Cl, Dl, C2, D2. Source and product chemical compounds solutions flow on both sides of the membranes in the intermembrane compartments Cl, Dl, C2, D2.
A solution of the by-product flows in the first intermembrane space Cl, from the positive electrode - anode + by interposing the first cation exchange product CMO forming the byproduct and the first anion-exchange AMO forming the by-product.
A solution of the main product of lithium hydroxide, lithium bicarbonate or lithium carbonate flows in the third intermediate membrane space C2 from the positive electrode (anode +) between the second cation exchange membrane CMP forming the main product and the second anion exchange membrane AMP forming the main product.
The primary anion source solution, e.g., sodium hydroxide, bicarbonate, and sodium carbonate flow in the fourth intermembrane space D2 from the positive electrode (anode +), between the second anion exchange membrane AMP forming the main product and the cation exchange membrane CMO forming by-product.
A primary cation source solution, e.g., lithium sulfate solution flows in the second intermembrane space Dl from the positive electrode (anode +), between the first anion exchange membrane AMO forming the by-product and the second cation exchange membrane CMP forming the main product.
The concentration of the lithium sulfate, sodium hydroxide, primary source sodium bicarbonate, or sodium carbonate feed solutions is preferably in the range from 0.1 to 1.0 mol/L. The concentration of the obtained product solutions - sodium sulfate, lithium hydroxide, lithium bicarbonate, or lithium carbonate is higher than 0.1 mol/L. The temperature of the solutions in operation is preferably in the range from 10 to 60 °C, preferably in the range from 20 to 50 °C. Their solubility limits the final salt solution concentration.
The apparatus for carrying out the method of the present invention is comprised of electrodes, between which an array of ion exchange membranes is included containing at least one sequence of anion exchange membranes AMP, AMO and cation exchange membranes CMP, CMO, alternating and forming at least four intermembrane spaces Cl, Dl, C2, D2 for solutions of input and output chemical compounds of electrodialysis double replacement reaction ion exchange system. The ion exchange membranes are preferable of the homogeneous or heterogeneous type in thickness from 0.1 to 1.0 mm and with a permselectivity more than 90%. Membrane spacers thickness is between 0.1 to 2.0 mm, and distributors are made from polymeric material providing solution equal distribution, source, and product solution mutual immiscibility and mechanical support of the intermembrane spaces.
The voltage between the electrodes is preferably from 1.0 to 2.5 V per sequence of four membranes - a membrane quadruplet at a current density in the range from 30 to 300 A/m2.
The main advantage of the lithium bicarbonate production using electrodialysis metathesis double replacement reaction process according to the invention is obtaining a straightforward first product solution - e.g., L1HCO3, which meets the purity application limits in batteries, at a high conversion rate. The conversion itself takes place in an electrodialysis device made of non-corrosive polymeric materials. The benefit of this technical solution is the preparation of a high concentration lithium bicarbonate/carbonate solution near saturation limit with very high purity for use in batteries. An analogy of the Solvay process used in the production of sodium carbonate can be utilized for the further production of a commodity chemical like Li2C03. Formed lithium bicarbonate formed is converted to lithium carbonate by heating (calcination). Compared to patent CN 1486931, when the product L12CO3 is freeze-dried, a newly proposed purification process is associated with an ever-increasing temperature that controls both the crystallization of lithium bicarbonate during evaporation and the subsequent calcination of lithium carbonate as the final product.
Technical figures explanation
The attached drawings clarify the technical field of invention, where:
Fig. la is a schematic diagram of an electrodialysis metathesis double replacement reaction method for producing lithium hydroxide, lithium bicarbonate or lithium carbonate by using one (simplest) ion exchange membrane sequence;
Fig. lb is a representation of an electrodialysis metathesis double replacement reaction method basic repeating motif for producing lithium hydroxide, lithium bicarbonate, or lithium carbonate using one (hatched) ion exchange membrane sequence and one ending cation exchange membrane CMO;
Figure 2 shows an exemplary arrangement of five series of four membranes - membrane quadruplets.
Example 1
The electrodialysis laboratory unit P EDR-Z/4x (producer company MemBrain) in electrodialysis-metathesis configuration (from now on referred to as EDM) was used for testing. The unit contained 5 tanks with a volume of 0.25 to 2.0 liters and 5 centrifugal pumps with a magnetic insert for circulation of solutions in the intermembrane spaces Cl, C2, Dl, D2 created by the anion exchange membranes of AMP, AMO and cation exchange membranes CMP, CMO (scheme of one primary sequence - see Figure lb) and also for electrode rinsing solution E.
Working solutions were as follows:
Diluate 1 - a solution of lithium sulfate feed (L12SO4) flowing through the second intermembrane space Dl between the first anion exchange membrane AMO and the second cation exchange membrane CMP,
Diluate 2 - sodium hydroxide (NaOH), primary sodium bicarbonate (NaHC03) or sodium carbonate (Na2C03) solution flowing through the fourth intermembrane space D2 between the second AMP anion exchange membrane with the CMO cation exchange membrane
Concentrate 1 - sodium by-product solution (Na2S04) flowing through the first intermembrane space Cl between the first cation exchange membrane CMO and the second anion exchange membrane AMO,
Concentrate 2 - a solution of the main product - lithium hydroxide (LiOH), primary lithium bicarbonate (L1HCO3) or lithium carbonate (Li2C03) flowing through the third intermembrane space C2 between the second CMP cation exchange membrane and the second AMP anion exchange membrane.
Electrode solution - sodium sulfate solution (Na2S04).
The unit was equipped with flow, temperature, conductivity, and pH measurement for each working loop individually and with a 90 Watt DC power supply. EDM module was equipped with eleven pcs of cation exchange membranes RALEX® (CM-PP) and with ten pcs of anion exchange membranes RALEX® (AM-PP), alternating and forming five membrane sequences (quadruplets) - see scheme in Figure 2. Each of the membrane repeating sequence had the arrangement of the hatched part from Figure lb. One active membrane area was 64 cm2. The test was performed in a batch process. Input solution of Li2S04 to second intermembrane space Dl, volume 0.5 liter, concentration 0.92 mol/L and NaHC03 to fourth intermembrane space D2, volume 1.1 liter, concentration 0.92 mol/L were processed.
The EDM solutions were circulated at 0.5 L/min, and the temperature was kept at 30 °C. The working voltage was in the range from 6.7 to 12.0 V and the current was set at 1.28 A. 1000 mL of L1HCO3 solution main product was obtained in the third intermembrane space C2 of with concentration 0.69 mol/L and 1100 ml of the secondary product Na2S04 in the first intermembrane space Cl with concentration 0.38 mol/L in this design of experiment. The main product was dosed with demineralized water to prevent precipitation by reaching the solubility level. The sulfur content in the main product was 0.115 g/L, and the lithium content was 4.78 g/L. The product purity in terms of the molar content of lithium in the numerator relative to the sum of lithium and sulfur in the denominator was 99.5%. A sodium sulfate solution with 0.07 mol/L concentration was circulated in the electrode chambers during the experiment.
Industrial usage
Lithium chemical compounds production like lithium hydroxide, bicarbonate, or carbonate, which are widely used in the battery industry.

Claims

P A T E N T C L A I M S
1. A process for producing lithium chemical compounds, such as lithium hydroxide, bicarbonate or carbonate, by electrodialysis metathesis acting as double reaction replacement system, which involves ion exchange between a solution of lithium sulfate and a solution of sodium hydroxide, sodium bicarbonate or sodium carbonate, in an array of ion exchange membranes comprising at least of one anion exchange membrane sequence (AMP, AMO) and cation exchange membranes (CMP, CMO) alternating and forming at least four intermembrane spaces (Cl, Dl, C2, D2), where the double replacement reaction using electrodialysis is occurring due to specific ionic transport through the index-labeled membranes (P) after which the ions are forming the primary product after recombination - specifically lithium cations migrate through the cation exchange membrane (CMP) and the hydroxide, bicarbonate or carbonate anions migrate through the anion exchange membrane (AMP) and they recombine into the main product lithium hydroxide, lithium bicarbonate or lithium carbonate, and through the membranes by index designation (O), after which the ions recombine into the by-product sodium sulfate - specifically sodium ions migrate through the cation exchange membrane (CMO) and sulphate ions migrate through the anion exchange membrane (AMO) and they recombine into the byproduct sodium sulfate, further that a cation exchange membrane terminates the basic repeating motif of the four intermembrane spaces (Cl, Dl, C2, D2), where a solution of the by-product flows in the first intermembrane space Cl, from the positive electrode by interposing the first cation exchange product CMO forming the by-product and the first anion-exchange AMO forming the by-product, a solution of the main product of lithium hydroxide, lithium bicarbonate or lithium carbonate flows in the third intermediate membrane space C2 from the positive electrode between the second cation exchange membrane CMP forming the main product and the second anion exchange membrane AMP forming the main product, a primary anion source solution e.g. sodium hydroxide, bicarbonate, and sodium carbonate flows in the fourth intermembrane space D2 from the positive electrode, between the second anion exchange membrane AMP forming the main product and the cation exchange membrane CMO forming by-product and a primary cation source solution e.g. lithium sulfate solution flows in the second intermembrane space Dl from the positive electrode, between the first anion exchange membrane AMO forming the by-product and the second cation exchange membrane CMP forming the main product.
2. A process according to claim 1, input solutions concentrations of lithium sulfate, sodium hydroxide, sodium bicarbonate or sodium carbonate are in the range from 0.1 to 1.0 mol/L and the concentrations of the products like sodium sulfate, lithium hydroxide, lithium bicarbonate or lithium carbonate solution are more significant than 0.1 mol/L.
3. The method according to claim 1, the temperature of the working solution during operation is in the range from 10 to 60 °C, more preferably in the range from 20 to 50 ° C, the most preferably in the range from 30 to 40 °C.
4. The apparatus according to claim 1 is comprised of electrodes, between which an array of ion exchange membranes, preferably of the homogeneous or heterogeneous type with thickness from 0.1 to 1.0 mm and with a permselectivity of more than 90%, are included containing at least one sequence of anion exchange membranes AMP, AMO and cation exchange membranes CMP, CMO, alternating and forming at least four intermembrane spaces Cl, Dl, C2, D2 for solutions of input and output chemical compounds of electrodialysis double replacement reaction ion exchange system ending with cation exchange membrane and membrane spacers with thickness ranging from 0.1 to 2.0 mm.
5. The apparatus according to claim 4, applied driving force is a voltage from 1.0 to 2.5 V per sequence of four membranes - membrane quadruplet between the electrodes at a current density from 30 to 300 A/m2.
EP19750051.5A 2018-05-29 2019-05-24 Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process Pending EP3801842A2 (en)

Applications Claiming Priority (2)

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CZ2018-250A CZ2018250A3 (en) 2018-05-29 2018-05-29 A method of producing lithium chemical compounds by an electrodialysis method and a device for carrying out the method
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