
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2014/078908 Al 30 May 2014 (30.05.2014) P O P C T (51) International Patent Classification: (74) Agent: SPRUSON & FERGUSON; GPO Box 3898, COW 15/08 (2006.01) C22B 26/12 (2006.01) Sydney, New South Wales 2001 (AU). COW 15/04 (2006.01) (81) Designated States (unless otherwise indicated, for every (21) International Application Number: kind of national protection available): AE, AG, AL, AM, PCT/AU20 13/001 357 AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (22) International Filing Date: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, 25 November 2013 (25.1 1.2013) HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (25) Filing Language: English KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (26) Publication Language: English OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, (30) Priority Data: SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, 61/729,439 23 November 2012 (23. 11.2012) US TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (71) Applicant: ADY RESOURCES LIMITED [AU/AU]; Level 44 Grosvenor Place, 225 George Street, Sydney, (84) Designated States (unless otherwise indicated, for every NSW 2000 (AU). kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, (72) Inventors: GALLI, Daniel, Ernesto; Ruta Nacional 66, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, sobre Colectora, No 152 esq. Pto Argentino, Antartida Ar TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, gentina, Palpala, 4612, Jujuy (AR). GALLI, Carlos, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, Daniel; Ruta Nacional 66, sobre Colectora, No 152 esq. MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Pto Argentino, Antartida Argentina, Palpala, 4612, Jujuy TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, (AR). HUMANA, Demetrio; Ruta Nacional 66, sobre KM, ML, MR, NE, SN, TD, TG). Colectora, No 152 esq. Pto Argentino, Antartida Argen tina, Palpala, 4612, Jujuy (AR). GALASTRO, Daniel, Published: Jorge; Ruta Nacional 66, sobre Colectora, No 152 esq. Pto — with international search report (Art. 21(3)) Argentino, Antartida Argentina, Palpala, 4612, Jujuy (AR). CASTILLO, Emanuel, Arnaldo; Ruta Nacional 66, sobre Colectora, No 152 esq. Pto Argentino, Antartida Argen tina, Palpala, 46 12, Jujuy (AR). (54) Title: PROCESS FOR RECOVERING LITHIUM FROM A BRINE WITH REAGENT REGENERATION AND LOW COST PROCESS FOR PURIFYING LITHIUM (57) Abstract: A process for the recovery of lithium from a natural or industrial impure brine comprising: (a) treating a feed brine 0 o0 containing lithium with a Na2C0 solution in order to precipitate magnesium and separate the precipitated MgC0 ; and (b) adjusting the feed brine pH treated in step (a) with a NaOH solution up to a value not lower than 11.3 and separating the precipitated solid 00 waste. Additionally, the process comprises the previous step (a.O) pre- concentrating the feed brine thus increasing the Li+ ion con o centration up to a maximum value wherein no lithium salt crystallization occurs. The Na2C03 used in step (a) is regenerated by means of a modified Solvay process; the NaOH is regenerated by means of a causticising process with Ca(OH) 2 obtained by calcina tion of precipitated and hydration of the CaO produced in said calcination; the Na 2C0 used in the causticising process is obtained by o means of a modified Solvay process comprising release of NH by means of a neutralization process of the NH CI produced when obtaining NaHC0 from carbonation of an ammoniacal brine, wherein neutralization is conducted using Mg(OH as the base, which is obtained by precipitation with NaOH, or by calcination of MgC0 and subsequent hydration of the MgO formed in said calcina tion process. A processed brine solution, lithium carbonate solution, or lithium chloride solution prepared by the above described process. PROCESS FOR RECOVERING LITHIUM FROM A BRINE WITH REAGENT REGENERATION AND LOW COST PROCESS FOR PURIFYING LITHIUM CARBONATE FIELD OF THE INVENTION 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. BACKGROUND OF THE INVENTION A significant number of commercial applications for lithium, minerals thereof and salts thereof are known at present, being used in various industries such as electronic, pharmaceutical, ceramic and lubricant industries, among others. First, lithium, which chemical symbol is Li, was used in accumulation batteries due to its high electrochemical potential and because it is the lightest solid. 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. These problems were solved with the appearance of Li-ion batteries, wherein the metal lithium anode was substituted by a carbon anode capable of intercalating lithium ions inside, thus becoming reversible. In this way lithium ions go back and forth between the carbon anode and a cathode formed by a cobalt-lithium double oxide. However, Li-ion batteries with nanostructurated anode and based on lithium titanate nanoparticles (Li Ti 0i2) 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. Although 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. But the massive use of Lithium developed from military uses, mainly in lubricant greases, and a wide variety of industrial applications, among others the use as catalyst in the manufacture of synthetic rubber. 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, Among the industrial grade lithium chemical compounds, we can mention 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 CO2 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 Li sotope. On the other hand, 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. In turn, 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. On the other hand, ceramic materials made of lithium tantalate or lithium nitrate have been developed, which have become the most widely used piezoelectric materials.
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