USOO874.1256B1 (12) United States Patent (10) Patent No.: US 8,741,256 B1 Harrison (45) Date of Patent: Jun. 3, 2014 (54) PREPARATION OF LITHIUM CARBONATE 4,036,713 A 7, 1977 Brown FROM LITHIUM CHILORIDE CONTAINING 4,142,950 A * 3/1979 Creamer et al. .............. 205,531 BRINES 4,209,369 A 6, 1980 Seko et al. 5,219,550 A 6/1993 Brown et al. 5,919.287 A * 7/1999 Moreau ........................... 95/130 (75) Inventor: Stephen Harrison, Benicia, CA (US) 5,951,843. A 9, 1999 Itoh et al. 5,993,759 A * 1 1/1999 Wilkomirsky ............. 423,179.5 (73) Assignee: Simbol Inc., Pleasanton, CA (US) 7,708,972 B2 5/2010 Coustry et al. 2005.0011753 A1 1/2005 Jackson et al. (*) Notice: Subject to any disclaimer, the term of this 2007/01 14134 A1* 5/2007 Legget al. .................... 205/.338 patent is extended or adjusted under 35 U.S.C. 154(b) by 409 days. FOREIGN PATENT DOCUMENTS EP 1900688 A1 * 3, 2008 ............... COD 707 (21) Appl. No.: 12/766,589 WO 2009131628 A1 10, 2009 (22) Filed: Apr. 23, 2010 OTHER PUBLICATIONS European Search Report and Written Opinion, Aug. 14, 2013. Related U.S. Application Data p p p 9. (60) Provisional application No. 61/172,540, filed on Apr. * cited by examiner 24, 2009. Primary Examiner — Stanley Silverman (51) Int. Cl. Assistant Examiner — Richard M. Rump COID 7700 (2006.01) (74) Attorney, Agent, or Firm — Bracewell & Giuliani LLP: (52) U.S. Cl. Michael R. Samardzija USPC ........................................... 423/421; 423/427 (57) ABSTRACT (58) USPCField of .................................................. Classification Search 423,421,427 This invention relates to a method for the preparation of lithium carbonate from lithium chloride containing brines. S ee appl1cauonlication fileIlle fIor completelet searcnh historv.n1Story The method can include a silica removal step, capturing (56) References Cited lithium chloride, recovering lithium chloride, supplying lithium chloride to an electrochemical cell and producing U.S. PATENT DOCUMENTS lithium hydroxide, contacting the lithium hydroxide with car bon dioxide to produce lithium carbonate. 3,523,751 A 8, 1970 Burkert et al. 4,016,075 A 4, 1977 Wilkins 27 Claims, 7 Drawing Sheets \ Silica Management Y- lithium Capture W i Concentration of Lithium Containing Solution 4. Electrochemical \ Prodiction of lithium Hydroxide \s Evaporation? m crystalization 6* Lithium hydroxide isolation and drying U.S. Patent Jun. 3, 2014 Sheet 1 of 7 US 8,741,256 B1 Silica Management Lithium Capture ? 3 Concentration of Lithium Containing Solution Electrochemical Production of lithium Hydroxide Evaporation? crystalization Lithium hydroxide isolation and drying Figure 1 U.S. Patent Jun. 3, 2014 Sheet 2 of 7 US 8,741,256 B1 Silica Management Lithium Capture ? 3 Electrochemical Production of Lithium Hydroxide Carbonation of Lithium Hydroxide Lithium Carbonate Isolation Figure 2 U.S. Patent US 8,741,256 B1 U.S. Patent Jun. 3, 2014 Sheet 4 of 7 US 8,741,256 B1 99 09 89 ~81, ŽA. U.S. Patent Jun. 3, 2014 Sheet 5 of 7 US 8,741,256 B1 08 Gaun61-I U.S. Patent Jun. 3, 2014 Sheet 6 of 7 US 8,741,256 B1 O rters - reas an as a resses arrier ruti ....... ------" " ... sess . as errrr"**** C.5 ------------------------------------------------------------------...----www.----------------- O.O ---------wro-or-morpo-r-----a-row-o-o-o-o-o-o-o-o-'go-oo-oorooo-o-o-o-wow-wow O 40 so 8O LOO 20 A) SO 18O 2CO time Elapsed/min anon 8-Jur a 10-Jun and 12-du sister 15 Jur Figure 6 2. s G era. 84 is was • *rocess......... carrrrrrries. .......... wiwirrkasawaw----------------------------------- 8O O Time Elapsed/min ass8-5 as 1-un in a 2-lar r r is Figure 7 U.S. Patent Jun. 3, 2014 Sheet 7 Of 7 US 8,741,256 B1 o . S. we s 2 LiOH Outlet Concentration, M Figure 8 . O 1. 15 2 2.5 LiOH Outlet Concentration, M Figure 9 US 8,741,256 B1 1. 2 PREPARATION OF LITHIUM CARBONATE In one aspect, a method for preparing lithium carbonate FROM LITHIUM CHILORIDE CONTAINING from a lithium chloride containing solution is provided. The BRINES method includes the steps of Supplying a lithium chloride containing solution to a silica removal step to produce a RELATED APPLICATIONS silica-lean lithium chloride containing solution, wherein the silica removal step is operable to remove at least a portion of This application claims priority to U.S. Provisional Patent silica present in the lithium chloride containing stream. The Application Ser. No. 61/172,540, filed on Apr. 24, 2009, silica-leanlithium chloride containing solution is Supplied to which is incorporated herein by reference in its entirety. a lithium chloride capture step, wherein the lithium chloride 10 capture step is operable to selectively capture said lithium BACKGROUND OF THE INVENTION chloride from the silica-lean lithium chloride containing 1.Technical Field of the Invention stream. Lithium chloride is recovered from the lithium cap This invention generally relates to the field of recovering ture step to produce a lithium chloride rich stream. The lithium from lithium containing Solutions. More particularly, 15 lithium chloride-rich stream is supplied to an electrochemical the invention relates to the preparation of lithium carbonate cell, wherein the electrochemical cell is maintained at condi from lithium chloride containing brines. tions sufficient to produce a lithium hydroxide-rich solution. 2. Description of the Prior Art The lithium hydroxide-rich solution is contacted with carbon It is known that geothermal brines can include various dioxide to produce lithium carbonate. metal ions, particularly alkali and alkaline earth metals, in In certain embodiments, the method can further include a varying concentrations, depending upon the source of the purification step for decreasing the concentration of at least brine. Recovery of these metals is important to the chemical one of calcium, magnesium, manganese or Zinc ions present and pharmaceutical industries. in the lithium chloride rich stream after the lithium chloride Geothermal brines are of particular interest for a variety of recovery step. The purification step can include the steps of reasons. First, geothermal brines provide a source of power 25 contacting the lithium chloride rich stream with a base; add due to the fact that hot geothermal pools are stored at high ing a carbonate such that at least a portion of calcium, mag pressure underground, which when released to atmospheric nesium, manganese or Zinc present precipitates as a Solid; and pressure, can provide a flash-steam. The flash-stream can be separating the precipitate from the lithium chloride rich used, for example, to run a power plant. Additionally, geo stream to produce a solid waste precipitate and a purified thermal brines typically contain various useful metals. Such 30 lithium chloride rich stream, said purified lithium chloride as, lithium, lead, silver and Zinc, each of which can be recov rich stream having a lower concentration of at least one of ered from the brine for further use. calcium, magnesium, manganese or Zinc. Lithium may be recovered from ores, as the ore may be baked with sulfuric acid, and the product leached with water. In another aspect, a method for the preparation of lithium The resulting lithium sulfate solution is treated with lime and 35 carbonate from a lithium chloride containing brine solution is Soda ash to remove calcium and magnesium, and lithium is provided. The method includes the steps of providing a then precipitated as a carbonate. Other known methods for lithium chloride containing brine Solution. At least a portion recovering lithium from ores include alkaline methods and of silica present in said lithium chloride containing solution is ion-exchange methods, each of which can yield solutions of removed to produce a silica-lean lithium chloride containing lithium as hydroxide, chloride or sulfate. These methods may 40 solution. Lithium chloride is isolated from said silica-lean also include the removal of calcium and magnesium by treat lithium chloride containing solution. Isolated lithium chlo ment with lime and Soda ash. ride is recovered to produce a lithium chloride-rich solution. Typically, the economic recovery of lithium from natural, The lithium chloride-rich solution is supplied to an electro predominantly chloride, brines (which may vary widely in chemical cell, which is operated at conditions Sufficient to composition), depends not only on the overall lithium con 45 produce a lithium hydroxide solution. Lithium hydroxide tent, but also upon the concentrations of interfering ions, solution from said electrochemical cell. Lithium hydroxide particularly calcium and magnesium, which can greatly effect Solution is then contacted with carbon dioxide to produce a the performance and economics of the lithium recovery. Mag slurry that can include lithium carbonate. Lithium carbonate nesium can be difficult to remove because it is chemically is then recovered from the slurry. similar to lithium in Solution. Generally, at low concentra 50 In another embodiment, a method for preparing lithium tions, magnesium may be removed by precipitation with lime carbonate from a lithium chloride containing brine solution is as magnesium carbonate. At higher magnesium concentra provided. The method can include the steps of Supplying a tions, removal with lime is not feasible and various ion exchange and liquid-liquid extraction methods have been substantially silica-free lithium chloride solution to a lithium proposed. 55 chloride capture step, wherein the lithium chloride capture Although conventional processing of ores and brines step is operable to capture a Substantial portion of the lithium makes it possible to eliminate major portions of interfering chloride present in the silica-leanlithium chloride containing ions, there remains a need for the simplified removal of inter stream; recovering lithium chloride from the lithium capture fering ions from brines for the production of lithium carbon step to produce a concentrated lithium chloride rich stream; ate.