WO2014078908A1 - Processus de récupération de lithium à partir de saumure avec régénération de réactif et processus peu coûteux de purification du lithium - Google Patents

Processus de récupération de lithium à partir de saumure avec régénération de réactif et processus peu coûteux de purification du lithium Download PDF

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WO2014078908A1
WO2014078908A1 PCT/AU2013/001357 AU2013001357W WO2014078908A1 WO 2014078908 A1 WO2014078908 A1 WO 2014078908A1 AU 2013001357 W AU2013001357 W AU 2013001357W WO 2014078908 A1 WO2014078908 A1 WO 2014078908A1
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brine
lithium
solution
process according
treated
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PCT/AU2013/001357
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English (en)
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Daniel Ernesto Galli
Carlos Daniel GALLI
Demetrio Humana
Daniel Jorge GALASTRO
Emanuel Arnaldo CASTILLO
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Ady Resources Limited
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • 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
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • 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

Definitions

  • the present invention relates to a method for recovering metal compounds from brines. Particularly, the present invention relates to a method for recovering lithium salts from brines.
  • Li which chemical symbol is Li
  • Lithium batteries are rechargeable and are preferably used in portable computers, mobile telephones and digital cameras.
  • the first successful lithium batteries contained a metal lithium anode, but since lithium is a highly reactive metal its use raised serious safety concerns. Moreover, as the number of charge-discharge cycles that the battery might undergo was very low, the lifetime of the battery was short. This was due to the formation of dendrites in the anode during use, which modified the anode geometry and further incremented its reactivity.
  • Li-ion batteries with nanostructurated anode and based on lithium titanate nanoparticles provide a better performance than Li- ion batteries with graphite anode.
  • These new generation batteries allow to operate under high power conditions, are long-lasting, their recharge times are substantially shorter and have a great thermal stability, thus being safer.
  • Li-ion rechargeable batteries with graphite anode represented an important improvement as they are light, scarcely contaminant, have higher energy density and no memory effects in the charge-discharge cycles, they had some drawbacks, such as safety problems when the temperature exceeded 100°C, a limited battery lifetime, low charge rhythm and restricted power.
  • Lithium minerals and salts are used in the manufacture of glass and ceramics, the latter use being generalized to a greater scale. Also they are used in the manufacture of china, porcelains, sanitary appliances, glazing and enamels, and in the manufacture of glasses and containers. Particularly, the lithium mineral called spodumene is capable of supporting sudden temperature changes.
  • the most important commercial lithium minerals obtained from veins are: spodumene, lepidolite, ambligonite, trifilite, petalite, zinnwaldite and eucripte,
  • lithium carbonate which is mainly used in the manufacture of glasses, enamels for ceramics, and it is also a critical ingredient in the manufacture of television tubes.
  • Lithium hydroxide is used in the manufacture of lubricant greases of multiple uses, in obtaining metal lithium, as air purifier in ventilation systems by absorbing the CO 2 produced in closed environments such as space shuttles and submarines, as a component of the electrolyte of accumulators used in submarines and telephone installations, as well as in power supplies for trains and telephones, and as starting material to obtain the 6 Li sotope.
  • lithium halides have various applications; lithium bromide is used as a catalyst in the manufacture of oriented polymers useful in the rubber industry, in the photography field, and due to its high hygroscopicity in the control of gas moisture and air conditioning, and also it is used in heat absorption pumps; lithium iodide is used in the photography field; lithium chloride is also highly hygroscopic and is used as a drying agent for air conditioning, in special welding and other fluxes, and also for obtaining metal lithium by electrolysis; and lithium fluoride is used in special welding and aluminum metallurgy.
  • Lithium hypochlorite is used in the sterilization of water for swimming pools as its quick solubility makes it ideal for shock ch!orination. Since it does not contain calcium, it does not harden water, is not flammable and does not produce dust; it is stable as it loses only 0.1% of available chlorine per month and it dissolves without clouding the water.
  • Lithium peroxide is used for obtaining oxygen and lithium borohydride and lithium hydride are used for obtaining hydrogen.
  • Aluminum and lithium hydride is used in organic chemical synthesis as a reducing agent of organic compounds at room temperature in ethereal solutions.
  • lithium hydride is used to inflate life vests.
  • Lithium stearate is used as an additive in lubricant greases in the automobile and industrial fields. Perhaps the most significant commercial use of lithium compounds is the manufacture of greases capable of retaining their lubricant properties within a wide range of extreme temperatures, thus making them water and stain resistant .
  • Lithium niobate is an electrooptical material currently leading the manufacture of optical communication devices, where it has shown great applicability and capability.
  • ceramic materials made of lithium tantalate or lithium nitrate have been developed, which have become the most widely used piezoelectric materials. These materials show a piezoelectric character after an artificial polarization.
  • metal lithium As regards metal lithium, it can be mentioned that it is used together with hydrogen in the manufacture of tritium bombs, and also as an ingredient of space rocket fuels.
  • Lithium- aluminum alloys show great resistance under high temperature conditions, and extra-light lithium-magnesium alloys are used mainly in the space industry. It is also a common component of some cadmium, copper and manganese alloys used in aeronautical manufacturing.
  • lithium has become relevant in the steel industry, particularly in processes known as "continuous casting” in which liquid materials are solidified. Lithium steam prevents carbon dioxide and oxygen from forming a rust layer in the furnaces during the thermal treatment of steel.
  • the advantage of using lithium is that its chemical properties provide a quicker and effortless operation during the molding process. Also, it is used as a cleaner and degreaser of stainless ductile steels, and as a deoxidant and purifier by extracting undesirable gases in copper castings and during the production of iron, nickel and copper alloys.
  • the key to obtain high purity metal lithium is to minimize the level of impurities such as sodium, calcium and magnesium in the lithium salt used to feed the electrolytic cells.
  • impurities such as sodium, calcium and magnesium
  • other impurities such as carbonate, sulfate and borate which, while not significantly affecting the purity of the obtained metal lithium, impair the performance of the electrochemical cell, thus increasing the carbon electrode consumption due to the oxidation of these species in the anode, resulting in the production of carbon dioxide and decreasing the efficiency of the metal production.
  • Li + ion is used in the form of its salts as a drug. It is believed that its action is based on its agonist effects on the serotoninergic function. Lithium salts stabilize altered states of mind, especially bipolar disorder, and are efficiently useful in the treatment of unipolar depression and mania. Particularly in cases of depression, lithium can be used to enhance the effect of other antidepressants. While lithium carbonate is the most prescribed salt, there are some alternatives such as citrate salt, lithium sulfate, lithium aspartate and orotic acid lithium salt.
  • Table 1 Composition of natural brines expressed by weight percent.
  • Brine sources of lithium include the salars in the Andes Mountains of South America which have been discovered to contain significant deposits of lithium salts; these comprise the Salar de Atacama, Chile, Salar de Uyuni, Cambodia, and Salar de Rincon, Republic of Salta, Argentina.
  • the impurities of the matrix such as magnesium, calcium, sodium, sulfate and boron, must be minimized in order to obtain a lithium saline product suitable for the intended use.
  • Alkali metals such as sodium, and alkali-earth metals, such as calcium and especially magnesium, must be substantially removed.
  • the simple technical means to remove them from lithium alkali metal are not profitable.
  • the individual applications require that these ionic impurities be reduced to maximum specific levels and a number of processes have been described to eliminate such impurities.
  • United States Patent No. 4,207,297 describes an integrated continuous process for producing lithium hydroxide monohydrate and high purity lithium carbonate with a high average particle size, that comprises: converting technical grade impure lithium carbonate into lithium hydroxide by a basification step with a suspension of calcium hydroxide; separating the precipitated calcium carbonate of the resulting lithium hydroxide solution; dividing the resulting lithium hydroxide solution in two: a major portion and a minor portion at a volume of said major portion to said minor portion ratio from about 10:1 to about 2:1; precipitating the lithium hydroxide monohydrate from the major portion of the lithium hydroxide solution and recovering the same; introducing carbon dioxide or lithium carbonate to the minor portion of the lithium hydroxide solution for further precipitation of calcium as calcium carbonate; separating the calcium carbonate from the lithium hydroxide solution; introducing carbon dioxide to the hydroxide lithium solution to precipitate high purity lithium carbonate with high average particle size; separating said lithium carbonate from the resulting solution of diluted lithium carbonate and recycling said diluted solution of lithium carbon
  • US 4.980.136 discloses a process for producing lithium chloride substantially free from boron having a purity higher than 99% from a natural or waste brine of other processes that contains a sufficient amount of lithium substantially free from sulfate, comprising the steps of: contacting said brine containing lithium chloride that comprises from 2% to 7% by weight of lithium obtained by solar evaporation, by heating or any other conventional means, saturated in hydrated metal salts present in the brine and substantially devoid of free water, with an organic solution comprising from 5% to 40% by volume of a fatty alcohol that contains from 6 to 16 carbon atoms in kerosene in a volume ratio of organic solution to brine that ranges from about 1 :1 to 5:1 to extract the boron from the brine to the organic solution phase; separating said organic solution phase from said brine; evaporating the aqueous phase at a temperature higher than about 100,5°C under vacuum of about 590 mm Hg to about 760 mm Hg to crystallize lithium chlor
  • this process is followed by washing and/or extraction with a low molecular weight alcohol of the resulting lithium chloride to remove the residual boron together with other contaminants present below 1% in the lithium chloride thus solubilizing the same.
  • the alcohol solution containing lithium chloride is then filtered and evaporated to form lithium chloride crystals with a high degree of purity greater than 99.9%.
  • the obtained anhydrous lithium chloride is particularly useful for producing lithium metal by electrolysis.
  • This process comprises the steps of extracting with a mixture of alcohol-kerosene solvents that are potentially economically unviable at the requested industry scales, let alone the negative impact on the environment because of the use of alcohol-kerosene as solvents.
  • US 5.219.550 describes a process for producing lithium carbonate having a low content of boron from a lithium containing natural brine, comprising essentially the steps of: contacting a lithium chloride containing brine substantially free from sulfate, that has a lithium content from about 2% to about 7% by weight obtained by solar evaporation or other conventional means, said brine saturated in hydrated metal salts present in the same and substantially devoid of free water, having a pH that ranges from about 1 - 2 measured when diluted with 10 volumes of water, with an organic solution comprising from about 5% to about 50% by volume of a fatty alcohol containing from 6 to 16 carbon atoms in kerosene in a volume ratio of organic solution to brine ranging from about 1:1 to 5:1 , to extract the boron present in the brine to the organic phase; separating said organic solution phase from said brine; removing magnesium and calcium from said brine by conventional means; adding sodium carbonate to precipitate lithium carbonate from said brine; and separating the
  • Table 2 shows in detail the lithium, potassium and magnesium contents and the content ratios for the main saline bodies in the Argentine Puna and the Atacama Salt Deposit.
  • step (a) treating a feed brine containing lithium with Na 2 C0 3 (sodium carbonate) solution in order to precipitate magnesium and separate the precipitated MgC0 3 (magnesium carbonate); (b) adjusting the feed brine pH treated in step (a) with NaOH (sodium hydroxide) solution up to a value not lower than 11.3 and separating the precipitated solid waste.
  • Na 2 C0 3 sodium carbonate
  • MgC0 3 magnesium carbonate
  • the process comprises the previous step (a.0) pre- concentrating the feed brine thus increasing the Li + ion concentration up to a maximum value wherein no lithium salt crystallization occurs.
  • the process comprises pre-concentration of the feed brine up to a value not lower than approximately 2,500 mg of Li + /liter.
  • the process comprises pre-concentration of the feed brine up to a value ranging from approximately 2,500 mg of Li + /liter to approximately 3,000 mg of LiVliter.
  • the process comprises pre-concentration of the feed brine up to a value not greater than approximately 5,000 mg of LiVliter.
  • the process comprises pre-concentration of the feed brine up to a value ranging from approximately 10,000 mg of Li + /liter to approximately 15,000 mg of Li + /liter.
  • step (a) of the process comprises adding a flocculant solution to the feed brine in order to facilitate the separation of precipitated solids from the pre-treated brine solution; and separating the precipitated solids from the pre-treated brine to make a solution of pre-treated brine and precipitated MgCO 3 .
  • step (b) of the process comprises adding a flocculant solution to the brine pre-treated in step (a) in order to facilitate the separation of the precipitated solids from the treated brine solution; and separating the precipitated solids from the treated brine to make a solution of treated brine and a precipitated waste sludge.
  • the process comprises the previous step (b.0) concentrating the feed brine pre-treated in step (a) thus increasing the Li + ion concentration up to a maximum value wherein no lithium salt crystallization occurs.
  • the process comprises concentration of the feed brine pre- treated in step (a) up to a value not greater than approximately 80,000 mg of Li + /liter. Additionally, and if necessary, the process further comprises adjustment of Ca 2+ (calcium ions) concentration in the feed brine prior to treatment of step (a).
  • the process comprises precipitation of Ca 2+ by adding a Na 2 S0 4 (sodium sulfate) solution or any other reagent at low temperature containing an anion to form a calcium salt that is insoluble in the brine, and does not alter the final product quality.
  • a Na 2 S0 4 sodium sulfate
  • the Na 2 C0 3 used in step (a) is regenerated by means of a modified Solvay process.
  • the NaOH is regenerated by means of a causticising process of Na 2 CC>3 with Ca(HO) 2 (calcium hydroxide) obtained by calcination of precipitated CaC0 3 (calcium carbonate) and hydration of CaO (calcium oxide) formed in said calcination.
  • Ca(HO) 2 calcium hydroxide
  • CaC0 3 precipitated CaC0 3
  • CaO calcium oxide
  • the Na 2 C0 3 used in the causticising process is obtained by means of a modified Solvay process.
  • the modified Solvay process comprises release of NH 3 (ammonia) by means of a neutralization process of the NH 4 Cl (ammonium chloride) formed in the production of NaHC0 3 (sodium bicarbonate) from carbonation of an ammoniacal brine, wherein the neutralization is conducted by using Mg(HO) 2 (magnesium hydroxide) as a base obtained by precipitation with NaOH, or by calcination of MgC0 3 and subsequent hydration of the MgO (magnesium oxide) formed in said calcination process.
  • Mg(HO) 2 magnesium hydroxide
  • the Mg 2+ (magnesium ions) content of the feed brine to be treated in step (a) by precipitation with Na2C0 3 ranges from approximately 0% w/w to 80% w/w of the magnesium contained in the brine.
  • step (c) precipitating borates and sulfates present in the brine treated in step (b) by adding a CaCI 2 (calcium chloride) solution.
  • the CaCl 2 comes from the mother liquor of the NH 3 recovery process used in a conventional Solvay process applied for obtaining Na 2 C0 3 .
  • the Mg 2+ concentration present in the brine treated after step (b) decreases to a value lower than 3 mg/l.
  • the process comprises the steps of: (d) obtaining crude Li 2 C0 3 (lithium carbonate) from the treated brine precipitating Li 2 C0 3 by adding a soluble carbonate solution and separating the solid product; and
  • step (e) re-dissolving crude Li 2 C0 3 obtained in step (d) and re-precipitating highly pure U2CO3 and separating the solid product from the mother liquor.
  • the soluble carbonate used in step (d) is Na 2 C0 3 obtained by means of a conventional Solvay process.
  • the crude Li 2 C0 3 obtained in step (d) is re-dissolved in cold water at a temperature lower than 25°C, wherein the cold water is distilled water, demineralized water, or water permeated by reverse osmosis.
  • re-precipitation of highly pure Li 2 C0 3 from step (e) is conducted by heating the solution or by jointly heating and evaporating the solution.
  • re-precipitation of highly pure Li 2 C0 3 from step (e) is conducted by at least one of the following sub-steps: i) crystallization in a multiple effect evaporative crystallizer, ii) crystallization in a multiple effect evaporative crystallizer with thermo-compression, iii) crystallization in an evaporative crystallizer by mechanical compression and thermo-compression, iv) crystallization by heating using only heat exchangers, v) crystallization by heating and evaporating processes using heat exchangers and any of the evaporative crystallizers indicated in i), ii), and iii).
  • the mother liquor of the purification process of Li 2 C0 3 is treated using ion exchange to minimize the purge and recycle the maximum amount of mother liquor into the re-crystallization process.
  • step (f) preparing a LiCI (lithium chloride) solution from the U2CO3 obtained in step (e).
  • the present invention refers to a processed brine solution, lithium carbonate solution, or lithium chloride solution prepared by the above described process.
  • Figure 1 shows a graph providing the dispersion of the potassium/magnesium (K/Mg) ratio as a function of the main saline bodies of the Argentine Puna and the Salar de Atacama.
  • Figure 2 shows a diagram of alternative I for pre-concentration and treatment of a natural brine with reagent regeneration according to the present invention; wherein, PN stands for Natural Pond, PN 800 stands for Natural Pond of brine with a Li + concentration of 800 mg/l, Pl-halite stands for Impermeabilized Pond of halite, SNP 800-900 stands for Preconcentrated Natural Brine with a Li + concentration of 800-900 mg/l, and SNP 2.500-3.000 stands for Preconcentrated Natural Brine with a Li + concentration of 2.500- 3.000 mg/l.
  • Figure 3 shows a diagram of alternative II for pre-concentration and treatment of a natural brine with reagent regeneration according to the present invention
  • PN stands for Natural Pond
  • PN 800 stands for Natural Pond of brine with a Li+ concentration of 800 mg/l
  • Pl-halite stands for Impermeabilized Pond of halite
  • SNP 800-900 stands for Preconcentrated Natural Brine with a Li + concentration of 800-900 mg/l
  • SNP 2.500-3.000 stands for Preconcentrated Natural Brine with a Li + concentration of 2.500- 3.000 mg/l
  • Pl-K salts stands for Impermeabilized Pond with K salts
  • Pl- sylvinite stands for Impermeabilized Pond of sylvinite
  • SNP 9.000 stands for Preconcentrated Natural Brine with a Li + concentration of 9.000 mg/l
  • Pl- g salts (or Mg salts I, or Mg salts II) stands for Impermeabilized Pond with Mg salts (or Mg salts I, or Mg salts II)
  • Figure 4 shows a diagram describing the procedure for the production of crude IkCO ⁇ according to the present invention.
  • Figure 5 shows a diagram describing the procedure for the purification of U2CO3 by re-crystallization according to the present invention
  • the references used have the following meanings: M-401-402, Mixer (s/l); F- 401/402, Polishing filter; P401 A/B, Pump for Li 2 C0 3 solution; P402 A/B, Pump for polished solution; TK401 , Buffer Tank of solution; IE401 , Ion- exchange unit; TK402, Condensate tank; P406 A/B, Condensate pump; C401 A/B, Steam compressor; P403 A/B, Magma pump; E401 , Solution pre-heater; E402, Solution heater; CR-401 , Evaporative crystallizer; Tk403, Mother liquor tank; P404 A/B, Crystallizer discharge pump; CE401 , Centrifuge; P405 A/B, Mother liquor pump; and E403, Water cooler.
  • M-401-402 Mixer (s/l); F- 401/402
  • Figure 6 shows a scheme for the production of sodium carbonate from brine and sludges.
  • Figure 7 shows the scheme of the ammonia recovery system ith MgO according to Test 1 of Example 1.
  • Figure 8 shows the scheme of the ammonia recovery system with sludge according to Test 2 of Example 1.
  • Figure 9 shows the evolution of the Mg concentration in Test 2-1 of Example 1.
  • Figure 10 shows the progress of the reaction using MgO in Test 2-1 of Example 1.
  • Figure shows the evolution of the Mg and Ca concentration in Test 2-2 of Example 1.
  • Figure 12 shows the progress of the reaction using sludge in Test 2-2 of Example 1.
  • Figure 13 shows the evolution of the conversion for Test 2-1 and Test 2-2 of Example .
  • Figure 14 shows a conceptual scheme of the purification process of crude lithium carbonate by dissolution and crystallization of Example 4.
  • Figure 15 shows a scheme of the steps of the purification process of crude lithium carbonate by dissolution and crystallization as tested at the laboratory in Example 4.
  • Figure 16 shows a flow chart for the purification process of crude lithium carbonate by dissolution and crystallization as tested in a pilot plant in Example 4.
  • Brines as used in this description means waters strongly impregnated with salts. Waters containing a high concentration of dissolved solids constitute at present an important source of mineral salts. Brines are an important source of common salt, potassium, bromine, boron, lithium, iodine, magnesium and sodium carbonate.
  • salar as used in this description is understood as an evaporite that is essentially a centripetal area that accumulated and accumulates salts of hydrothermal and/or volcanic origin, and that in past geological eras was salt lakes with a high content of salts.
  • the term "substantially” means that the form, circumstance, magnitude, measurement or any other described characteristic but syntactically associated to it, resemble as desired to said form, circumstance, magnitude, measurement or any other characteristic as unequivocally or definitively known. Specifically, this term means that the described matter is practically equivalent for the purposes of the invention or resembles to the concrete reference used for the description, without necessarily becoming identical.
  • the terms "about”, “of about”, or similar, used in this description and the claims mean that the numerical values affected are close to the limit value specifically mentioned and within a specific range of values and comprised within 20 % of said numerical value, preferably within 10 % of said value and, more preferably within 5 % of said value. Ranges are determined by the measuring method used and the thresholds established in the corresponding determinations.
  • the procedure object of the present invention comprises separation of the magnesium contained in the brine by means of a treatment comprising the following steps:
  • Step I) Addition of a sodium carbonate aqueous solution, preferably having a concentration of about 290 g/l of water, in an amount sufficient to separate approximately 80% of the magnesium contained in the brine.
  • a sodium carbonate aqueous solution preferably having a concentration of about 290 g/l of water, in an amount sufficient to separate approximately 80% of the magnesium contained in the brine.
  • the sludge obtained post-treatment following separation, washing and drying of the solid phase contains more than 95% magnesium carbonate, expressed as w/w on a dry basis.
  • this solid is calcined at 900°C, it decomposes into magnesium oxide and carbon dioxide.
  • Magnesium oxide is hydrated with permeated water and the obtained magnesium hydroxide is used for neutralizing an ammonium chloride solution produced in the reactor where sodium bicarbonate is obtained, as described below, giving off ammonia, which is recycled to the sodium bicarbonate process in order to obtain ammoniacal brine.
  • the ammonium chloride neutralization reaction also generates a magnesium chloride aqueous solution, the only liquid effluent produced in the treatment process.
  • Step II Addition of a sodium hydroxide aqueous solution, having a concentration of approximately 400 g/l of water, in an amount sufficient to separate the remaining magnesium contained in the brine after treatment with sodium hydroxide.
  • a sodium hydroxide aqueous solution having a concentration of approximately 400 g/l of water, in an amount sufficient to separate the remaining magnesium contained in the brine after treatment with sodium hydroxide.
  • the sludge obtained post- treatment following separation and washing of the solid phase contains more than about 97% magnesium carbonate, expressed as w/w on a dry basis.
  • this sludge is also used directly in the neutralization reaction of ammonium chloride. The neutralization reaction is similar to reaction (5).
  • a sodium chloride aqueous solution is prepared which is similar to that used in the Solvay process for the production of sodium carbonate.
  • This brine is the other stream coming into the ammonia absorber to obtain an ammoniacal brine that gets carbonated with carbon dioxide resulting from calcination of the magnesium obtained in the treatment reactor, from calcination of calcium carbonate obtained from the basification reaction of sodium carbonate and from the calcination of sodium bicarbonate obtained in the carbonation process of the ammoniacal brine.
  • equations (6) and (7) are summarized in equation (8).
  • equations (1) and (2) are summarized in equation (9).
  • approximately 80% of the magnesium contained in the brine is separated using sodium carbonate and approximately 20% is separated using sodium hydroxide. This is so because about 80% is the amount that can be separated if only sodium carbonate is used, according to experimentation performed and the solubility of magnesium carbonate in the brine. It is important to note that all of the magnesium contained in the treated brine can be separated almost thoroughly by using only sodium hydroxide.
  • the degree of pre-concentration of the brine to be treated has also been specified. It is important to note that, for the process of the present invention, the brine entering the treatment process can range from a natural brine without any degree of pre-concentration up to a pre-concentrated brine (with or without pre-treatment) with a lithium concentration higher than 80 g/L.
  • This flexibility for the application of the procedure is important because the following factors depend on the degree of pre-concentration of the brine to be treated: i) the technology to be used for completion of the concentration of the treated brine before entering the lithium carbonate plant; ii) the specific consumption of reagents for the treatment; iii) the consumption of thermal energy, mechanical energy and water; iv) the time necessary to reach the steady state; v) the degree of lithium and potassium recovery; and vi) the environmental impact arising from performance of the procedure.
  • the calcium content in the brine to be treated is high, it must first be treated with sodium sulfate in order to avoid crystallization and precipitation of calcium carbonate.
  • the process according to the present invention for the separation of magnesium has a friendly logistics since the necessary reagents, namely H 2 0, CI 2 Na, CO 2 , CaCC>3, NH 3 , indicated with a bold circle in Figures (1) and (2), are available near the salar, except for the ammonia replacement which is about 0.6% of the stoichiometrically total required amount.
  • the magnesium separated from the brine remains in the form of magnesium chloride, thus minimizing the environmental impact of its application.
  • the treatment described for separating magnesium does not regulate the sulfate and borate contents.
  • the process for obtaining sodium carbonate from calcium hydroxide is described in the schemes of Figures 1 and 2.
  • this process produces a calcium chloride solution that is used in the treatment reactor for sulfates and borates.
  • the reactions involving this treatment are as follows:
  • the pre-concentrated, treated brine can be concentrated in ponds up to a lithium concentration of about 14g/l, without any crystallization of lithium salts.
  • Patent Application “A PROCESS FOR RECOVERING LITHIUM FROM A BRINE” (International publication number WO 2010/006366 A1)
  • potassium salts are harvested in the ponds which increase lithium concentration from 2.5 - 3 g/l up to 9 g/l. These salts are washed and delivered to a plant in order to obtain potassium chloride. The washing water is recycled to the potassium salts crystallization and precipitation ponds.
  • Figure 3 it is shown that the treated and pre-concentrated brine can be concentrated in evaporative crystallizers.
  • the present invention comprises a low cost purification process that reduces the level of soluble and insoluble impurities to values that are lower than those indicated in the specifications of battery grade lithium carbonate.
  • the scheme in Figure 4 indicates that only the rinsing water of the salts precipitated in the concentration pond of the mother liquor of the crude lithium carbonate reactor is recycled into the cold treatment reactor.
  • the purification procedure which is also an object of the present invention, comprises dissolution of the crude lithium carbonate, stream 1 , in distilled water, stream 4 which is part of stream 3 obtained by mixing stream 2 [replacement lower than 3% of stream 3] and stream 35 [condensate recycle]).
  • the amount of lithium carbonate entering mixer -401 is about 5% greater than the amount necessary to saturate stream 4 at a temperature close to room temperature, for example, about 20°C.
  • the obtained mixture, stream 7, is pumped by means of pump P-401 A/B to polishing filter F-401 thus obtaining a saturated lithium carbonate solution in water free from water- insoluble impurities, stream 8, and a mixture of solids, stream 9, containing the excess lithium carbonate, which entered mixer M-401 , and water-insoluble impurities.
  • Stream 9 enters mixer M-402 where it admixes with an amount of distilled water, stream 5, enough to assure complete dissolution of the lithium carbonate contained therein.
  • the mixture obtained in mixer M-402 is pumped by means of pump P-407 A/B to polishing filter F-402 A/B, thus obtaining stream 11 which consists of the water-insoluble impurities contained in crude lithium carbonate (waste) and stream 6 which is recycled into reactor M-401.
  • Stream 8 enters accumulation tank TK-401 from which it is pumped by means of pump P-402 A/B, thus obtaining stream 12.
  • This stream can totally or partly enter the ion-exchange unit IE-401 A/B as stream 13 and then enter solution pre-heater E-401 as stream 15, admixing with stream 14, a fraction of stream 12 not entering the ion-exchange unit.
  • the stream 13 to stream 14 ratio will depend on the target product quality.
  • Stream 15 is pre-heated with part of the condensate, stream 30, generated in solution pre-heater E-402, stream 28.
  • Stream 31 the condensate output of pre-heater E-401 , accumulates in tank TK-402 from which it is pumped by means of pump P- 406 A B as stream 34 to cooler E-403 in order to obtain cold distilled water stream 35. When necessary, part of the condensate is purged as stream 33.
  • the pre-heated solution, stream 16 enters the evaporative crystallizer as stream 17.
  • Stream 17 is the mixture of stream 16 with stream 18, which is the mother liquor from stream 24 exiting the evaporative crystallizer, and the rinsing water from stream 29 which is part of the condensate which is employed in washing the obtained lithium carbonate).
  • Stream 17 entering the evaporative crystallizer admixes with stream 19, which together with streams 20, 21 and 22 show recirculation of the solution in the evaporation equipment.
  • the crystallization equipment is a mechanical compression evaporative crystallizer and comprises evaporative crystallizer CR-401 , solution heater E-402 and steam compressor C-401. This is only an embodiment example intended to explain the procedure scheme.
  • the purification process can also be accomplished using: i) multiple-effect evaporative crystallizers; ii) multiple-effect evaporative crystallizers with thermal compression; iii) mechanical compression evaporative crystallizers and thermal compression; iv) heat crystallization using only heat exchangers; v) heating and evaporation crystallization using heat exchangers and any of the evaporative crystallizers indicated in i), ii) and iii).
  • the purified lithium carbonate obtained with this procedure is of higher quality than the battery grade lithium carbonate obtained with the procedure disclosed in the Patent Application PCT published under N° WO20107006366A1.
  • the present procedure has lower cost and permits purification of the crude lithium carbonate obtained with the procedure described in the first part of the present invention.
  • Example 1 Examples referred to release of NH3 from an ammonium chloride solution using magnesium hydroxide.
  • Example 2 Example referred to the separation of g using sodium carbonate and sodium hydroxide.
  • Example 3 Example referred to the precipitation of sulfates and borates with calcium chloride after Mg precipitation treatment.
  • Example 4 Example referred to the purification of crude lithium carbonate.
  • EXAMPLE 1 Ammonia recovery trials by neutralization with magnesium hydroxide Conventional Solvay process utilizes industrial lime to recover ammonia.
  • Trial 1 qualitative trial to evaluate feasibility of ammonia recovery from ammonium chloride solution utilizing magnesium oxide as the reagent.
  • Trial 2 quantitative trial to determine the reaction yield for ammonia recovery.
  • the reagents to be used are magnesium oxide and sludge.
  • the object of this trial is to prove the feasibility of the reaction between magnesium oxide, one of the components of sludge, and ammonium chloride.
  • the reagents were: ammonium chloride, one of the components of the mother liquor obtained in the solid-liquid separation step; and magnesium oxide, a component which converts into magnesium hydroxide and replaces the lime slurry.
  • ammonium chloride one of the components of the mother liquor obtained in the solid-liquid separation step
  • magnesium oxide a component which converts into magnesium hydroxide and replaces the lime slurry.
  • the next test aims to determine the conversion of ammonium chloride into ammonia, using sludge, and make a comparative analysis with the previous test.
  • the progress of the reaction was monitored as a function of the amount of magnesium ions entering the solution during the reaction time. This variable is considered to be directly related to the amount of ammonia produced.
  • Ammonium chloride and sludge from a filter press of a lithium carbonate plant were used in an aqueous medium.
  • the chemical composition of the sludge is shown in Table 3.
  • the moisture content of the sludge is 24% (wet basis).
  • All the magnesium in the sludge is part of the magnesium hydroxide.
  • Remaining calcium is part of the calcium hydroxide.
  • ammonium chloride reacts ith magnesium hydroxide and calcium hydroxide, both from the sludge.
  • Another component of the sludge is calcium sulfate, which does not react in the recovery of ammonia.
  • the dosage of sludge is calculated based on the stoichiometric necessary hydroxyl groups for the transformation of all the ammonium chloride into ammonia, with a 5% excess.
  • the proportions of reagents used are:
  • Ammonia recovery was conducted at 100°C and atmospheric pressure, with stirring of the reaction mixture.
  • the reaction was monitored based on the amount of magnesium and calcium ions that react and enter into solution. For such monitoring, periodic samples are taken to be analyzed for calcium and magnesium. The evolution of the concentration of these ions corresponds to the transformation of ammonium chloride into ammonia.
  • M Mg Molar mass of magnesium.
  • n° tii a Initial quantity of moles of ammonium chloride.
  • the conversion is calculated assuming that maximum conversion is when 2.24 moles of magnesium enter the liquid phase which is equal to 55.65 g of Mg ..
  • the limiting reagent is ammonium chloride.
  • Figure 10 shows the progress of the reaction.
  • the magnesium and calcium concentrations are determined to quantify the amount of ammonia released and the conversion.
  • Figure 1 1 the evolution of the concentration of magnesium and calcium ions is presented.
  • Ammonia can be recovered with sludge.
  • the trial time can be reduced by increasing the reaction temperature in the process of ammonia recovery.
  • the conversion results of the tests obtained are valid for comparative purposes and for the conditions in which they were carried out.
  • the test that utilizes magnesium oxide (MgO) has the goal of knowing a limit value in relation to the sludge and at the same time to evaluate alternatives to produce a sludge with a better magnesium hydroxide content.
  • This chemical treatment stage aims at precipitating the magnesium contained in the brine as magnesium carbonate using a sodium carbonate solution.
  • the amount of magnesium that precipitates as magnesium carbonate is based on its solubility in the reaction medium.
  • the test was conducted in 70 m 3 tank reactor with a stirrer. The reactor was loaded with 50 m 3 of brine with a density of 1.256 kg/l and a total dissolved solids (TDS) of 0.372 kg/l.
  • TDS Total dissolved solids.
  • the solid contained a mixture of magnesium carbonate and calcium carbonate. Since the moisture content was high, the washing process was conducted with water so as to minimize lithium losses. The amount of washing water depended on the amount of solids. The amount used was equivalent to a cake volume whose typical density is 1.45 kg/m 3 . The wetting water was sent to the ponds for concentration and lithium recovery. / Treatment with NaOH
  • This chemical treatment stage is aimed at precipitating the remaining magnesium contained in the brine treated with sodium carbonate solution.
  • the test was conducted in a 70 m 3 tank reactor with a stirrer.
  • the reactor was loaded with 60 m 3 of brine with a density of 1.246 kg/I and a total dissolved solids (TDS) of 0.305 kg/I.
  • Table 5 shows the results of the chemical treatment.
  • TDS Total dissolved solids.
  • the solid contained magnesium hydroxide. Since the moisture content was high, the washing process was conducted with water so as to minimize lithium losses. The amount of washing water depended on the amount of solids. The amount used was equivalent to a cake volume. The wetting water was sent to the ponds for its concentration and lithium recovery.
  • This chemical treatment stage is aimed at precipitating the sulfates and borates contained in the brine.
  • a calcium chloride solution was dosed.
  • the amount of reagent was dosed so that the calcium concentration after the reaction was 2 g/L, 5.5 g/l of sulfate (S0 4 2' ) and 6.7 g/l of borates (B 4 0 7 2" )-
  • the test was conducted in a 70 m 3 tank reactor with a stirrer.
  • the reactor was loaded with about 60 m 3 of brine with a density of 1.249 kg/I and a STD of 0.302 kg/I.
  • Table 6 shows the results of the chemical treatment: Table 6: properties of the treatment system currents with CaCI 2 solution
  • TDS Total dissolved solids.
  • the solid-liquid separation was conducted. After the solid-liquid separation, 62 m 3 of brine were obtained with the concentration shown in 3, which were sent to concentration.
  • the solid mainly composed of dehydrated calcium sulfate (CaS0 4 .2H 2 0), contains wetting water with a moisture content of 45 % on a wet basis.
  • the solid contained dihydrated calcium sulfate. Since the moisture content was high, the washing process was conducted with water so as to minimize lithium losses. The amount of washing water depended on the amount of solids. The amount used was equivalent to a cake volume whose typical density is 1.45 kg/m 3 The wetting water was sent to the ponds for its concentration and lithium recovery.
  • the main stages of the proposed process are: Dissolution of crude lithium carbonate in water. A saturated lithium carbonate solution is obtained.
  • the transformation can be represented by the following equation.
  • Figure 14 shows a conceptual outline of the process.
  • the saturated solution of lithium carbonate in water has a lithium concentration of 1.41 % (w/w).
  • the solubility of lithium carbonate decreases with the increase of the temperature, to achieve a good recovery, it is necessary to raise the temperature up to 85-90°C; under these conditions the solubility is 0.78% (w/w).
  • Table 7 shows solubility for different temperatures.
  • the average composition of the product to be purified by dissolution in water is:
  • Table 8 Chemical composition of crude lithium carbonate.
  • Figure15 shows a diagram of the stages of the process.
  • Crude lithium carbonate is used for the test as specified in Table 8.
  • Osmosis water is used for dissolution having a conductivity lower than 4 pS/cm.
  • the solution is filtered to remove insolubles. Filtrate is concentrated by water evaporation.
  • samples are taken from the suspension, which separates the lithium carbonate, whose quality is presented in Table 9.
  • Mother liquor has a lithium concentration lower than 1.8 g Li/L, which represents an advantage over the purification process by transformation in lithium bicarbonate.
  • Table 9 Chemical composition (% w/w) of purified lithium carbonate by dissolution.
  • Table 10 Chemical composition (%w/w) of the lithium carbonate purified by dissolution.
  • one of the variables is the purge.
  • the purge In order to increase the performance of the process it is necessary to recycle, following an ion exchange treatment.
  • the present invention is applicable to the field of recovering metals from brines, particularly the invention relates to a high recovery process for the treatment of brines in an aqueous means to obtain high purity lithium carbonate, a solution of lithium chloride for producing electrolytic grade lithium chloride and derived products without the use of extraction solvents, which is easy to implement near salars, that will benefit mainly the mining industry related to exploitation of brines for obtaining lithium, as well as related industries, ail of which will be highly favored by having a procedure for obtaining high purity lithium carbonate, a solution of lithium chloride for producing electrolytic grade lithium chloride and derived products from brines in an aqueous means and with a low environmental impact, providing also an important economic benefit.

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Abstract

L'invention concerne un processus de récupération de lithium à partir d'une saumure naturelle ou industrielle impure, qui comprend : (a) le traitement de la saumure alimentée contenant du lithium avec une solution de Na2C03 afin d'amener le magnésium à précipiter et de séparer le MgC03 précipité ; et (b) l'ajustement du pH de la saumure alimentée traitée dans l'étape (a) avec une solution de NaOH jusqu'à une valeur non inférieure à 11,3 et la séparation des déchets solides précipités. En outre, le processus comprend l'étape précédente (a.O) de pré-concentration de la saumure alimentée, ce qui augmente la concentration en ions Li+ jusqu'à une valeur maximale à laquelle aucune cristallisation de sel de lithium n'a lieu. Le Na2C03 utilisé dans l'étape (a) est régénéré par le biais d'un processus de Solvay modifié ; le NaOH est régénéré par le biais d'un processus de caustification avec du Ca(OH)2 obtenu par calcination du précipité et hydratation du CaO produit pendant la calcination ; le Na2C03 utilisé dans le processus de caustification est obtenu au moyen d'un processus de Solvay modifié, comprenant la libération de NH3 par le biais d'un processus de neutralisation du NH4CI produit lors de l'obtention du NaHC03 à partir de la carbonation d'une saumure ammoniacale, la neutralisation étant réalisée avec Mg(OH)2 comme base, qui est obtenu par précipitation avec du NaOH ou par calcination de MgC03 et hydratation successive de MgO formé pendant le processus de calcination. L'invention concerne également une solution de saumure traitée, une solution de carbonate de lithium ou une solution de chlorure de lithium préparée par le processus susmentionné.
PCT/AU2013/001357 2012-11-23 2013-11-25 Processus de récupération de lithium à partir de saumure avec régénération de réactif et processus peu coûteux de purification du lithium WO2014078908A1 (fr)

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CN105036159A (zh) * 2015-07-23 2015-11-11 韦海棉 一种高锂盐湖卤水制备碳酸锂的方法
CN107311206A (zh) * 2017-07-21 2017-11-03 江苏万年长药业有限公司 一种阿托伐他汀中间体制备过程中碳酸锂的制备方法
CN108193058A (zh) * 2017-11-29 2018-06-22 潍坊学院 一种从盐湖中提取锂的离子液体萃取的方法
CN108428893A (zh) * 2017-09-21 2018-08-21 中国地质科学院矿产综合利用研究所 一种卤水电池级碳酸锂的制备方法
WO2019002653A1 (fr) 2017-06-26 2019-01-03 GRANDE VILLARINO, Alejandro María Procédé à impact environnemental minimum et à récupération maximum de lithium pour obtenir des saumures concentrées avec une teneur minimale en impuretés à partir de saumures qui imprègnent des salines et des mines de sel naturelles
CN109987615A (zh) * 2019-04-12 2019-07-09 中国科学院青海盐湖研究所 电池级碳酸锂生产中碳酸钠的纯化方法及其应用
CN112501455A (zh) * 2020-11-30 2021-03-16 五矿盐湖有限公司 一种从盐湖原卤卤水中分离锂的方法
WO2021053514A1 (fr) 2019-09-16 2021-03-25 InCoR Lithium Extraction sélective de lithium à partir de saumures
WO2021113948A1 (fr) * 2019-12-11 2021-06-17 The Unversity Of British Columbia Processus et procédé de raffinage de carbonate de lithium à partir d'une solution impure de chlorure de lithium
US20210207240A1 (en) * 2018-08-17 2021-07-08 Lithtech Industries Pty Ltd Method for lithium processing
WO2021228936A1 (fr) * 2020-05-13 2021-11-18 Katholieke Universiteit Leuven Méthode de production de monohydrate d'hydroxyde de lithium de qualité batterie
CN114735727A (zh) * 2022-06-13 2022-07-12 北京化工大学 一种碳酸锂的制备方法
RU2795224C1 (ru) * 2019-12-11 2023-05-02 Дзе Юниверсити Оф Бритиш Коламбиа Процесс и способ очистки карбоната лития, исходя из раствора хлорида лития с примесями

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US20120189516A1 (en) * 2011-01-20 2012-07-26 Andrew John Donaldson Production of high purity lithium compounds directly from lithium containing brines

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US20110300041A1 (en) * 2008-07-18 2011-12-08 Daniel Ernesto Galli process for recovering lithium from a brine
US20120189516A1 (en) * 2011-01-20 2012-07-26 Andrew John Donaldson Production of high purity lithium compounds directly from lithium containing brines

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* Cited by examiner, † Cited by third party
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CN105036159A (zh) * 2015-07-23 2015-11-11 韦海棉 一种高锂盐湖卤水制备碳酸锂的方法
WO2019002653A1 (fr) 2017-06-26 2019-01-03 GRANDE VILLARINO, Alejandro María Procédé à impact environnemental minimum et à récupération maximum de lithium pour obtenir des saumures concentrées avec une teneur minimale en impuretés à partir de saumures qui imprègnent des salines et des mines de sel naturelles
CN111448164A (zh) * 2017-06-26 2020-07-24 丹尼尔·恩内斯托·加利 从天然盐滩和盐沼中的盐水获得最低杂质含量的浓缩盐水的方法，所述方法具有最小环境影响和最大锂回收
US11920211B2 (en) 2017-06-26 2024-03-05 Daniel Ernesto Galli Method for obtaining concentrated brine of minimum impurity content from brine found in natural salt flats and salt marshes, said method having minimum environmental impact and maximum lithium recovery
CN107311206A (zh) * 2017-07-21 2017-11-03 江苏万年长药业有限公司 一种阿托伐他汀中间体制备过程中碳酸锂的制备方法
CN108428893A (zh) * 2017-09-21 2018-08-21 中国地质科学院矿产综合利用研究所 一种卤水电池级碳酸锂的制备方法
CN108193058A (zh) * 2017-11-29 2018-06-22 潍坊学院 一种从盐湖中提取锂的离子液体萃取的方法
US20210207240A1 (en) * 2018-08-17 2021-07-08 Lithtech Industries Pty Ltd Method for lithium processing
CN109987615A (zh) * 2019-04-12 2019-07-09 中国科学院青海盐湖研究所 电池级碳酸锂生产中碳酸钠的纯化方法及其应用
WO2021053514A1 (fr) 2019-09-16 2021-03-25 InCoR Lithium Extraction sélective de lithium à partir de saumures
US11634789B2 (en) 2019-09-16 2023-04-25 InCoR Lithium Selective lithium extraction from brines
WO2021113948A1 (fr) * 2019-12-11 2021-06-17 The Unversity Of British Columbia Processus et procédé de raffinage de carbonate de lithium à partir d'une solution impure de chlorure de lithium
CN115066395A (zh) * 2019-12-11 2022-09-16 不列颠哥伦比亚大学 从不纯的氯化锂溶液开始精炼碳酸锂的工艺和方法
RU2795224C1 (ru) * 2019-12-11 2023-05-02 Дзе Юниверсити Оф Бритиш Коламбиа Процесс и способ очистки карбоната лития, исходя из раствора хлорида лития с примесями
AU2020401568B2 (en) * 2019-12-11 2023-09-21 The University Of British Columbia Process and method for refining lithium carbonate starting from an impure lithium chloride solution
WO2021228936A1 (fr) * 2020-05-13 2021-11-18 Katholieke Universiteit Leuven Méthode de production de monohydrate d'hydroxyde de lithium de qualité batterie
CN112501455A (zh) * 2020-11-30 2021-03-16 五矿盐湖有限公司 一种从盐湖原卤卤水中分离锂的方法
CN114735727A (zh) * 2022-06-13 2022-07-12 北京化工大学 一种碳酸锂的制备方法

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