Classifications

• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
• • 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
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
  • C22B26/10—Obtaining alkali metals
  • C22B26/12—Obtaining lithium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/006—Wet processes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/54—Reclaiming serviceable parts of waste accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
• • 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
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/84—Recycling of batteries or fuel cells

Definitions

• the present application refers to the field of the quantitative and safe dissolution of alkali or alkaline-earth metals, the field of the destruction and stabilization of alkali or alkaline-earth metal residues and the field of recycling of alkali metals or alkaline earth metal.
• Alkaline metals such as lithium, sodium and potassium
• Alkaline metals have similar chemical properties and possess a very reducing valence electron. As a result, they react violently with water to produce hydrogen that can be explosive according to the reaction:
• Alkaline earth metals such as magnesium, calcium, strontium, and barium
• Alkaline earth metals also react with water to produce hydrogen gas according to the following equation: M (s) + 2H20 (I) ® M 2+ (aq) + 20H (aq) + H2 (g) (2)
• alkali metals such as lithium, are therefore generally immersed in the mineral oil.
• organomagnesium or Grignard reagents involves the solution of magnesium in an anhydrous solvent.
• the solvents used may be ethers, such as oxolane (tetrahydrofuran) or diethyl ether.
• the solvent has the role of solvating the organomagnesium and stabilizing it.
• the synthesis of Grignard reagents is carried out according to the following reaction:
• organolithium reagents The synthesis of organolithium reagents is similar to that of organomagnesium compounds and involves the solution of lithium with anhydrous reagents and is carried out according to the following reaction:
• X is a halogen for example, Br, Cl or I.
• the present description relates to a method for dissolving a metal, according to which the metal is chosen from alkali metals, alkaline earth metals and alloys comprising mainly at least one of these, the method comprising a step (a) of contacting the metal with a reaction inhibitor and water; wherein the reaction inhibitor is selected from a hydrocarbon, a hydroxyl compound and a mixture comprising at least two thereof.
• the hydrocarbon is of formula C n H m where n and m are natural whole numbers; n is from 5 to 40; and m is chosen so that the molecule is stable and optionally includes one or more unsaturations.
• the hydroxylated compound is of formula R (OH) x where R is chosen from the groups Ci-alkyl and C2-3alkyl (OC2-3alkyl) y , where x is between 1 and 4, and y is between 1 and 5, it being understood that the C: O ratio of the hydroxylated compound is in the range of 1: 1 to 3: 1.
• the hydroxylated compound is of formula R (OH) x, where R and x are such that the formula defines a polyalkylene glycol of average molecular weight between 300 and 800 g / mol or a polyvinyl alcohol of molecular weight average between 7000 and 101 000 g / mol, optionally substituted with one or more ester group (s).
• the water is included in an emulsion of light mineral oil and water.
• the present description relates to a process as defined herein, in which the inhibitor is a hydroxide of the metal and step (a) comprises contacting the metal with a concentrated solution of the metal hydroxide in the water.
• the metal is selected from alkali metals lithium, sodium, potassium and alloys comprising predominantly one of these.
• the metal is lithium.
• the metal is an alloy of lithium and magnesium or aluminum, where lithium is the majority.
• the metal is selected from magnesium, calcium, strontium, barium and an alloy comprising predominantly one of these.
• the reaction inhibitor is a hydroxylated compound chosen from propylene glycol, glycerol, ethylene glycol, ethanol, dipropylene glycol, tripropylene glycol, polyvinyl alcohol and polyethylene glycol. methoxypolyethylene glycol and a mixture comprising at least two thereof.
• the hydroxylated compound is propylene glycol or lithium hydroxide.
• the reaction inhibitor is a hydrocarbon comprising mainly linear, cyclic or branched alkanes.
• the inhibitor is a mixture comprising at least one hydroxyl compound and a hydrocarbon.
• the inhibitor is a metal hydroxide and step (a) comprises contacting the metal with a concentrated hydroxide solution of the metal in the water.
• the metal hydroxide is lithium hydroxide.
• the concentrated hydroxide solution of the metal has a concentration of between 6 and 12.8% w / v.
• the concentrated metal hydroxide solution has a concentration of between 8 and 12.8% w / v.
• the concentrated solution of metal hydroxide is a saturated solution.
• the method comprises the complete or partial immersion of the metal in the reaction inhibitor followed by the addition of water or an emulsion of light mineral oil and water.
• the metal to be dissolved is attached to a nonreactive metal prior to the contacting step.
• the method is used for the quantitative solution of metals.
• said method further comprises a step of weighing the metal before contacting.
• the method may further include an optional step of separating the solution, and the quantitative analysis of the solution.
• the quantitative analysis of the solution may, for example, be carried out by inductively coupled plasma optical emission spectrometry (ICP-OES).
• the method is used for the destruction and stabilization of metal residues.
• metal residues adhere to the surface of a piece of equipment.
• the method is carried out on the complete piece of equipment on which the metal residues adhere.
• the method is used for recycling batteries.
• the method further comprises a step of dismantling or shredding the battery before the contacting step.
• the step of dismantling or shredding the battery is carried out simultaneously with the contacting step.
• the process is used to recycle lithium as LiOH or LiOH hteO, or converted to L12CO3, or another lithium salt.
• Figure 1 shows images of the dissolution of the shaped pellet showing: (A) a lithium pellet (top metal) attached to a stainless steel pellet (bottom metal); and (B) the position of the lithium (top metal) in the graduated cylinder for the quantitative dissolution of lithium, as described in Example 1 (b).
• Figure 2 shows an image of the dissolution in mineral oil of the lithium pellet (top metal) attached to a pellet of stainless steel (bottom metal), as described in Example 2.
• the Figure 3 shows an image of the dissolution of the lithium pellet fixed to the stainless steel pellet in a saturated solution of lithium hydroxide, as described in Example 5 (a).
• hydrocarbon refers to an oil or a mixture based on oil (s) consisting exclusively of carbon and hydrogen and therefore comprising no other substitution group.
• the hydrocarbon comprises mainly linear, cyclic or branched saturated alkanes.
• the hydrocarbon can come from the distillation of oil. Alternatively, it may have been manufactured synthetically.
• hydroxylated compound refers to organic or inorganic compounds comprising at least one hydroxyl functional group (-OH).
• alkyl or “alkylene” refer to saturated hydrocarbon groups having from one to eight carbon atoms, including linear or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl and so on. When the alkyl group is located between two functional groups, then the term “alkylene” can also be used, such as methylene, ethylene, propylene, and so on.
• alkylene can also be used, such as methylene, ethylene, propylene, and so on.
• C1-C11alkyl and “C1-C18alkylene” refer respectively to an alkyl or alkylene group having number "i” to number "ii” of carbon atom (s).
• the present application describes a method of dissolving metals, wherein the metal is selected from alkali metals, alkaline earth metals and alloys comprising predominantly at least one thereof.
• the metal is an alkali metal selected from lithium, sodium and potassium.
• the metal may also be an alkaline earth metal selected from magnesium, calcium, strontium and barium.
• the metal may also be an alloy comprising predominantly an alkali metal or alkaline earth metal.
• the metal is lithium.
• the metal is an alloy of lithium and magnesium or aluminum, in which lithium is the majority.
• the method comprises a step of contacting the metal with a reaction inhibitor and water, the water optionally being in the form of an emulsion of light mineral oil and water.
• the metal is previously attached to a non-reactive metal, for example, to stainless steel.
• the dissolving can be performed on a sample (for example, a pellet) composed of a dissolving metal layer attached to a nonreactive metal layer. The metal to be dissolved is found on the top of the sample to avoid or reduce the risk that released hydrogen will accumulate beneath it.
• the reaction inhibitor may be selected from a hydrocarbon, a hydroxyl compound and a mixture comprising at least two thereof.
• the hydrocarbon is of the formula CnHm where n and m are natural whole numbers; n is from 5 to 40; and m is chosen so that the molecule is stable and optionally includes one or more unsaturations.
• the hydroxylated compound is of formula R (OH) x where R is chosen from the groups Ci-alkyl and C2-3alkyl (OC2-3alkyl) y , where x is between 1 and 4, and y is between 1 and 5, it being understood that the C: 0 molar ratio of the hydroxyl compound is in the range of 1: 1 to 3: 1.
• the hydroxylated compound is of formula R (OH) x , where R and x are chosen so that the formula defines a polyalkylene glycol of average molecular weight between 300 and 800 g / mol or a polyvinyl alcohol of molecular weight average between 7000 and 101 000 g / mol, optionally substituted with one or more ester group (s).
• Non-limiting examples of hydroxyl compounds include propylene glycol, glycerol, ethylene glycol, ethanol, dipropylene glycol, tripropylene glycol, polyvinyl alcohol, polyethylene glycol, methoxypolyethylene glycol, or a mixture comprising at least two of these.
• the reaction inhibitor is propylene glycol or paraffin oil.
• the reaction inhibitor is a mixture comprising at least one hydroxyl compound and a hydrocarbon.
• the inhibitor further comprises methanol.
• the reaction inhibitor may further comprise one or more adjuvant (s) or additive (s), for example, to modify or improve the properties thereof, such as its viscosity.
• the adjuvant may be glucose or another similar compound.
• the reaction inhibitor is a mixture including a hydroxyl compound present at a concentration of between 1 and 99% v / v, preferably between 10 and 80% v / v, or between 30 and 60% v / v, or about 50% v / v, upper and lower bounds included.
• the step of contacting the metal with a reaction inhibitor and water comprises complete immersion. or partial metal in the reaction inhibitor followed by addition of water or emulsion of light mineral oil and water.
• the metal is immersed in a volume of reaction inhibitor equivalent to about 14 ⁇ l per milligram of metal to be dissolved.
• the water or emulsion of light mineral oil and water may be added in portions at regular intervals, for example, from about 0.10 to about 6.0 ⁇ L per milligram of metal to be dissolved per period of time. minutes, terminals upper and lower included.
• it may be added continuously and at a controlled low flow rate, for example, at a rate of between about 0.05% v / v and about 1% v / v per minute, including upper and lower limits.
• the water or the emulsion of light mineral oil and water can be added until the solution reaches a concentration of between about 50% v / v and about 90% v / v. water or until complete dissolution of the metal.
• the reaction inhibitor of the process as defined herein is a hydroxide of the metal and step (a) comprises bringing the metal into contact with a concentrated solution of metal hydroxide in the metal. 'water.
• the metal hydroxide is lithium hydroxide.
• the concentrated solution of the metal hydroxide has a concentration of from about 4 to about 12.8% w / v, or from about 6 to about 12.8% w / v, or from about 8 to about 12.8% w / v. and about 12.8% w / v, upper and lower bounds included.
• the concentrated solution is a saturated solution.
• the present description also proposes the use of the method of the present application for the quantitative solution of metals.
• the method may further include a step of weighing the metal prior to contacting and a step of quantitatively analyzing the solution.
• the step of quantitative analysis of the solution can be carried out, for example, by inductively coupled plasma optical emission spectrometry (ICP-OES).
• ICP-OES inductively coupled plasma optical emission spectrometry
• the present description also proposes the use of the method of the present application for the safe destruction and stabilization of metal residues.
• the process of the present application can make it possible, inter alia, to reduce the rate of reaction and release of hydrogen gas, to reduce the local atmosphere of hydrogen gas, to avoid local warming and / or to avoid reaching the melting point of lithium.
• a slower release may allow, by using adequate ventilation, to remain below the lower limit of flammability of gaseous hydrogen, which is about 4% by volume.
• Metal residues such as metallic lithium can also adhere to the surface of pieces of equipment.
• the complete piece of equipment on which the metal residues adhere is treated with the method of the present application in order to dissolve or stabilize them.
• the present description also proposes the use of the method of the present application for recycling batteries.
• the method may further include a step of dismantling or shredding the battery prior to the contacting step.
• the step of dismantling or shredding the battery can be performed during the step of contacting.
• the lithium oxidizes in the aqueous solution to form LiOH.
• the lithium can then be recycled from the aqueous LiOH solution as LiOH H20 or converted to U2CO3 or other lithium salt.
• electrochemically active materials such as, for example, LiFePO4, LUTi50i2, lithium metal, or lithium salts used in the manufacture of liquid electrolytes, solids or gels.
• the reaction inhibitor may also be a lithium hydroxide solution.
• Solid LiOH is commercially available in its anhydrous form (LiOH) or monohydrate form (LiOH H20).
• the maximum solubility of anhydrous LiOH in water is about 128 g / L at a temperature of 20 ° C (concentration equivalent to about 12.8% w / v).
• the dissolution of lithium metal in a concentrated aqueous solution of LiOH occurs very slowly and therefore, it can be used to solubilize lithium metal safely.
• the solution resulting from this controlled dissolution can then be used to recover the lithium in a form having a substantially significant commercial value (such as anhydrous LiOH, LiOH-hteO or U2CO3).
• this inhibitor comes from its high chemical purity since no other chemical is introduced into the process.
• This inhibitor can also be used in the destruction of lithium metal residues, for the recycling of lithium metal batteries or for quantitative chemical analysis of the impurities contained in lithium and / or the determination of the purity thereof. .
• the lithium sample to be dissolved was prepared in an anhydrous room with a dew point below -40 ° C.
• a clean, dry stainless steel pellet was first weighed on an analytical balance and inserted into a pellet mold (eg, Evacuable Pellet Die 13 mm GS03000, Specac brilliant spectroscopy TM) so that the unpolished surface is in contact with the sample to promote the adhesion of lithium on the stainless steel pellet.
• a metal lithium strip was then taken and inserted into the pelletized mold.
• a clean, dry, high molecular weight polyethylene (UHMW-PE) pellet (12.90 mm x 6.0 mm) was then inserted into the pellet mold so that its polished side was in contact with the sample.
• UHMW-PE high molecular weight polyethylene
• the mold assembly was then performed and placed in a manual hydraulic press (YLJ-15, MTI Corporation).
• a vacuum line was connected to the base of the pellet mold to remove air from the sample and the mold evacuated for one minute.
• a pressure of 80 bar was applied under vacuum for one minute. Once the pressure was released, the vacuum was maintained for an additional minute.
• the lithium pellet thus formed was found between a stainless steel pellet and a UHMW-PE pellet.
• the pellet was then ejected from the die using an extraction ring and the hydraulic press. During extraction, the UHMW-PE pellet was peeled off using a cylindrical tool. The sample was then weighed on an analytical balance and the mass of the stainless steel pellet was subtracted.
• the lithium or lithium-based alloy pellet thus formed on a stainless steel pellet was inserted into a 25-mL graduated cylinder.
• the lithium pellet was placed upward to promote the release of hydrogen bubbles during dissolution (see Figure 1B).
• the dissolution was carried out in a cylinder in order to obtain a column of liquid which captures the residual lithium extracted.
• the hydrogen release is gradual in order to avoid reaching a high local concentration of flammable hydrogen and limiting the increase in temperature at the lithium surface, reducing thus the risk of fire or explosion.
• a volume of 5 mL of propylene glycol was added.
• 1 mL of ultrapure water was added every 15 minutes for a period of about 6 hours to obtain a total volume of water of about 25 mL.
• the sample was then allowed to react until complete dissolution and until there was no further formation of hydrogen bubbles.
• the resulting solution of dissolution was transferred to a 50 mL volumetric flask and acidified with 4.15 mL of concentrated hydrochloric acid. Solutions Concentrates of hydrochloric acid (2.50 mL) and nitric acid (2.50 mL) were then added (final concentrations of 5% v / v, respectively). The volume of the vial was supplemented by dipstick with ultrapure water. The solution was thus acidified to obtain the same matrix as the standards for the ICP-OES analysis.
• the solution is then analyzed by ICP-OES.
• This method makes it possible to quantify magnesium and lithium at a high concentration using a calibration curve. This analysis therefore makes it possible, among other things, to quantify the lithium or other content in a lithium-based alloy. It also makes it possible to quantify the impurities contained in metallic lithium or in a lithium-based alloy.
• the impurities may, for example, include calcium, chromium, iron, potassium, magnesium, manganese, sodium, nickel, silicon, strontium and / or zinc.
• blanks and standards are prepared with the same concentration of propylene glycol and lithium as the samples to be analyzed, in order to obtain the same matrix as the samples analyzed ("matrix matching").
• a lithium sample was prepared according to the method set forth in Example 1 (a). The sample was then dissolved in accordance with the method presented in Example 1 (b), replacing the propylene glycol with light mineral oil. Again, with this example, the lithium pellet was deposited in a graduated cylinder. Lithium was placed upward to promote the release of hydrogen bubbles. Light mineral oil was then added to to completely immerse the lithium pellet. Gradually, ultrapure water or an emulsion of ultrapure water and mineral oil was added to control the oxidation reaction of the lithium metal and the evolution of hydrogen. Subsequently, the solution was left to settle and was decanted. ICP-OES analysis is then performed.
• the reaction inhibitor may be employed to safely destroy and stabilize residues of alkali metals, alkaline earth metals and alloys comprising at least one of them adhering or not to a piece of equipment.
• the reaction inhibitor may be employed to inactivate the lithium or lithium-based alloy contained in a primary or secondary battery to recover commercially valuable materials and / or recycle them.
• a recycling process comprises shredding the cells by grinding in the presence of an aqueous solution containing the organic inhibitor. When using this process lithium oxidizes in the aqueous solution to form LiOH. Once the lithium is completely dissolved in this form, the shredded (and non-reactive) materials are rinsed with water to remove traces of LiOH. The lithium can then be recycled from the aqueous solution of LiOH as UOH H 2 O or converted to form U 2 CO 3 or another lithium salt. These compounds can then be reused for the production of electrochemically active materials such as, for example, LiFePO 4 , LUTi 5 O 12, or lithium metal, or for the production of lithium salts used in the manufacture of liquid, solid electrolytes. or gels.
• electrochemically active materials such as, for example, LiFePO 4 , LUTi 5 O 12, or lithium metal, or for
• Example 5 Controlled solution of lithium metal in lithium hydroxide solution
• the reaction inhibitor can also be a concentrated solution of lithium hydroxide.
• the dissolution of lithium metal in a concentrated aqueous solution of LiOH occurs very slowly, it can therefore be used to solubilize lithium metal safely.
• the solution resulting from this controlled dissolution can then be used to recover the lithium in a form having a significant commercial value (such as anhydrous LiOH, LiOH H20 or L12CO3).
• This inhibitor can also be used for the destruction of metallic lithium residues, for the recycling of lithium metal batteries or for quantitative chemical analysis of the impurities contained in lithium.
• the controlled solution of a lithium metal sample as prepared in Example 1 (a) was carried out by adding, initially, 5 ml of a saturated solution of lithium hydroxide (12.8 % w / v). Then, water was added gradually in portions at regular intervals (about 1 mL per 15 minutes for 0.350 g of metal) to control the dissolution rate of the metal. To complete the dissolution reaction, a total of 18 mL of water was added, corresponding to a final concentration of 8.03% w / v.
• Figure 3 shows an image of the controlled solution of lithium metal in a solution of saturated lithium hydroxide (12.8% w / v LiOH) as described in this example.
• the lithium metal was held at the bottom of the solution by a stainless steel pellet on which the metal was pressed, as described in Example 1 (a).
• the evolution of hydrogen takes place slowly and the lithium does not heat up.
• (b) Dissolving in a solution of unsaturated lithium hydroxide (6.4
• Example 1 The controlled solution of a lithium metal sample, as prepared in Example 1 (a), was carried out according to the method described in Example 5 (a), except that the saturated solution of LiOH is replaced by 5 mL of a solution containing 6.4% w / v LiOH (64 g / L). Using the method of this example, the reaction is more violent and faster. The solution warms up slightly and the release of hydrogen is more pronounced. In order to complete the lithium dissolution reaction, a total quantity of water of 14 ml was added per portion at regular intervals (ie about 1 ml of water per 15 minutes for 0.350 g of metal). The final concentration obtained was 8.04% weight / volume.

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