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    20 views21 pages

    US20190256368A1

    Uploaded by

    rriondar

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    © All Rights Reserved
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    of 21
    cu») United States 2) Patent Application Publication co) Pub. No.: US 2019/0256368 A1 oy ow 2 an @ (63) (60) MARSTON et al. PROCESS FOR SELECTIVE ADSORPT AND RECOVERY OF LITHIUM FROM NATURAL AND SYNTHETIC BRINES SOURCE MINERALS Inventors: CHAR MIDL SOURCE MINERALS Assignee: ENER LLC, San Diego, CA (US Appl. No. 16/402,991 Filed: May 3, 2019 Related US. Application Data Continuation-in-par of application No, 161010.286, fled on Jun, 15, 2018. Provisional application No, 62(671,489, fled on May 15, 2018, provisional application No. 62/671,889, ‘US 2019025636841 (43) Pub. Date: Aug. 22, 2019 filed on May 15, 2018, provisional application No, 62/520,024, filed on Ju. 15, 2017 Publication Classification GI) Inc, CoiD 1508 (200601) COLD 1502 (2005.01), BOD 1502 (2006.01), BOLD 15/12 (2006.01), BOD 1318 (200601), 2) Co1D 18/08 (2013.01), COLD 15/2 (2013.01); Bou 22157023 (2013.01); BOLD 15/128 (2013.01), BOID 15/1807 (2013.01) BOLD 1542 (2013.01) on ABSTRACT Tie invention relates generally to a process for selective adsorption aod recovery of lithium from natural and syn thetic brines, and more particular to a process for recovering Jithium from a natural or synthetic brine solution by passing the brine solution through a lithium selective adsorbent in a continous countercurrent adsorption and desorption cic it Patent Application Publication Aug. 22,2019 Sheet 1 of 8 US 2019/0256368 Al \ 1000 Si S| T FIG. 4 PRIOR ART 1016 1024 1028 f 1022 Patent Application Publication Aug. 22,2019 Sheet 2 of 8 US 2019/0256368 Al ‘ono ‘STEAM FLASH tJ PRIMARY CLARFCATION is > 1098 }ECONDARY CLARIFICATION (Si, Fe} 30h ne TERTIARY CLARIFICATION at em 314 300 ‘ im see FINAL CLARFICATION Mn, Zn REMOVAL) 08 = 316 ‘AGDFICATION hog 00 CCAD ORCUTT a (600 gpm 10%) 42—“y = 320 IMPURITY REMOVAL (Cahig®) (5500 gom- 90%) 502 oo REVERSE OSHOSS ee 508 510 EVAPORATION (TRIPLE EFFECT) WATER ; 5 512—e{___ LITHIUM CARBONATE CRYSTALLIZATION oe a0 CENTRIU ud 318 LITHIUM REDISOLUTION a INPURITY REMOVAL me 5m THIN RE CRYSTALLZATION a wr Patent Application Publication Aug. 22,2019 Sheet 3 of 8 US 2019/0256368 Al $000 STEAM FLASH i PRIMARY CLARIFICATION ‘28 ~~ 1006 SECONDARY CLARIFICATION (SF 1000 REACTORS i TERTARY CLARFICATION _ am 3h = 0 eae REACTORS 06 FINAL CLARIFICATION (vn, 2n REMOVAL) - 36 ACIDIFICATION 36 CCAD CRCUT eof 5 5 =~ 20 (500 gpm 108) 42 . TNPURITY REMOVAL cag) aad sa SHELEVATION a SOLVENT EXTRACTION m SCRUBBING. me 5 706 STRIPPING 708 ELECTROLYSIS LITHIUM HYDROXIDE CRYSTALLIZATION a DRYING / PACKAGING m FIG. 3 US 2019/0256368 AI Aug. 22, 2019 Sheet 4 of 8 Patent Application Publication Ve ols , Aug. 22,2019 Sheet 5 of 8 US 2019/0256368 AI Patent Application Publication ap ‘Old Patent Application Publication Aug. 22,2019 Sheet 6 of 8 US 2019/0256368 AI | Ie oF mo 3 g y = + = | | fd | | | tt sy . o =z | | 2 7 | g S| * 2 5 = + | | | | fa is ig i US 2019/0256368 AI Aug. 22,2019 Sheet 7 of 8 Patent Application Publication 9°Old 24 a8 eo ‘ONIddLS +9 7A vl ‘ONIBENYOS 29 bw 89: Os pot NOILOWULYG SSSNVONYN trYVIN COW HSSMS 209: 008 ge ‘ONiddhuls: 89 oNrgenuos oa 429 9g NOLLOWEIXS ONZ St HOWST COVE ‘OH HO FOSCH NYLdINGTY WALSAS NOLLWLIciO3Ud §Z/ UN WO8d BVO BSL Td US 2019/0256368 AI Aug. 22, 2019 Sheet 8 of 8 Patent Application Publication L°Old oe oe aaquiny; uumnyo in st yu wine dq te pent, US 2019/0256368 Al PROCESS FOR SELECTIVE ADSORPTION AND RECOVERY OF LITHIUM FROM. NATURAL AND SYNTHETIC BRINES CROSS REFERENCE TO RELATED 'APPLICATIONS| [0001] This application claims the benefit of U.S. Pro sional Patent Application No, 62/671,489 filed on May 15, 2018, This application is also a coatinuation-in-part of US. Patent Application No. 16i010.286 filed on Jun. 15, 2018, which claims the benefit of US. Provisional Patent Appi ‘ation No. 62/520,024 filed on fun. 15, 2017 and the benefit, ‘of US, Provisional Patent Application No. 62/671,489 filed ‘on May 15, 2018. This application incorporates each ofthe Toregoing applications by reference ino this document as i fully set out at this point BACKGROUND OF THE INVENTION 1, Field of the Inveation [0002] ‘This invention relates generally to a process for Selective adsorption and recovery of lithium from natural and synthetic brines, and more particular to @ process for recovering lithium from a natural or synhetie brine solution by contacting the brine solution with a lithium selective continvons countercurrent adsorption and AD") process 2. Description of the Related Art Seawater contains about 0.17 mgrk. and subsur- 0003) ace brines may contain up to 4,000 mg/kg, more than four orders of magnitude greater than sea Water. Typical com- mercial lithium concentrations are between 200 and 1.400 mg/kg. In 2015, subsurface brines yieKded about half of the ‘world's lithium production, 10004) The Salton Sea Known Geothermal Resource Area (CSSKGRA") has the most geothermal eapucty potential in the United States. Geothermal energy the hamesting of heat radiating from the beneath the Earth's erst, is a renewable resource that is capable of cost-effectively generating lange nounts of power. In addition, the SSKGRA has the poten tial w bocome North America's prime sources of alkali metals, alkaline eath meals nx! wansition metals, such as lithium, potassium, rubidium, iron, zinc andl manganese 0005] Brines from the Salton Sea Known Geothermal Resource Area are unusually hot (up to atleast 390° C. at 2 km dept, hypersaline (up to 26 wt. "), and metaliferous (ron (Fe), zine (Zn), lead (PB), copper (Cu) The brnes are primarily sodium (Na), potassium (5), calcium (Ca) chlo- Fides with up to 25 percent of total dissolved solids. While the chemist and high temperature ofthe Salton Sea brines have led to the principal challenges to the development of the SSKGA, lithium and other brine elements typically ‘maintain high commodity value and are used in a range of industrial and techaological applications. 10006} The “tithium ‘wiangle™ of Chile, Argentina and Bolivia s where approximately 75% ofthe world’s Tithinm ‘comes from, Chile is curently the second largest producer ‘of lithium carbonate and lithium hydroxide, which are key raw materials for producing lithium-ion batteries, bohind ‘only Australia. Salar de Atacama is one of the hottest driest, ‘windiest and most inhospitable places on Farth, and the largest operations are in the shallow brine beneath the Salar Aug. 22, 2019 {de Atacama dry lakebed in Chile, whieh as of 2015, yielded fhout a third ofthe world's supply. The Atacama in Chile is ideal for lithium mining because the lithium-containing brine ponds evaporate quickly, and the solution is concen- trated into high-grade lithium peodvets ike lithium earbon- tte and lithium hydroxide. Mining lithium in the salars of Chile and Argentina is much more cost-effective than hard rock mining. where the lithium is blasted from granite pezamite orebodies contsining spodumene, apatite, lepido- Iie, tourmaline and amblygonite. The shallow brine beneath the Salar de Uyuni in Bolivia is thought to contain the world's langest lithium deposit often estimated to be hall oF more of the world's resource; however, as of 2015, no commercial extraction hus taken place, other than a pilot plant, The mining of lithium from brine resourees in the “‘ithiun triangle” historically depends upon easy access to Jarge amounts of fresh water and very high evaporation rates. With declining availability of fresh water and climate ‘change, the economic advantage of conventional processing techniques is disappearing. [0007] Fixed-bod and continuous countereurrent ion exchange (*CCIX") systems have been used 10 recover ‘etal, such as nickel (Ni) and cobalt (Co), fram ore Teach solutions. While fixed-bed systems are generally used in recovery projects, they are known to require relatively lange ‘amounts of Water and chemicals and the perfomance is generally weaker than CCIX systems. [0008] Utilizing CCIX-type equipment in the adsorption ‘of lithium from brines wth ithium selective adsorbents in a CCAD circuit will bring increased process ellicieney versus classical fixed-bed processing. The water and reagent ef ciency of a CCAD eireuit/process shoud be a. preferred replacement for evaporation ponds in the brine ‘operations inthe salars of “lium triangle”, saving m fof acre fect of water Irom evaporative loss, [0009] It is therefore desitable to provide aa improved process for selective adsorption and recovery of Hithinm from natural and symtberie Brines, [0010] It is funher desirable to provide a continuous ‘countercurrent adsoeption and desorption process for the Selective recovery of lithium from natural andor synthetic brine, whieh are normally considered economically non- viable using conventional membranes, solvent extraction, oF fixed-bed arrangement of lithium selective adsorbent tech- nologies. [0011] Its stil farther desirable to provide a process for recovering lithium from a natural or synthetic brine solution by treating the rine solution with a lithium selective adsor- bent in a CCTX-type system wsing a CCAD process. [0012] Before proceeding toa detailed description of the invention, however, it should be noted und remembered that the deseription ofthe invention which follows, together with the accompanying drawings, should not be construed as Timiting the invention to the examples (or embodiments) shown and described. Those skilled in the rt to which the invention perains will be able to devise other forms of this invention within the ambit of the appended claims. SUMMARY OF THE INVENTION [0013] tn genera, ina first aspect, the invention relates 10 ‘process for selective recovery of lithium from feed brine ‘olution, The process includes concentrating the lithium ia the brine solution by eyclially and sequentially owing the brine solution through a continuous countercurrent adsorp- US 2019/0256368 Al Gon and desorption circuit 19 form am enhanced Fithiom product seam, and recovering thelium from the ‘enhanced thm produet steam, {0014} The process can als include the steps of removing Snaps from the brine solution to farm poise brine solution, and then coneenttating the liu inthe polished brine solution by eyelieally and sequentially Howing the polished brie solution through a continuovs eountereurrent ‘sorption aad desorption eicit form an enhanced Tih pret stem, Lithium is then recovered fom the ‘enhanced thom produet steam, [0013], “The process ean aso include the step of obsining the brine solution having lithium chloride. The Tibia chloride inthe brine solution ean he concentrated! using the ‘continuous countercurrent adsorption aad desorption cect form the enhanced lium product stream, and then the thium chloride can be scleetively convered to lihium ‘rbonate thium hydroxide, oF both {0016} The continuous countercurrent adsorption desorp- tion circuit can have a plurality of process zones, with each ‘of the process zones having an adsorbent bed or eaimn ‘containing a ithium soloctive adsorbent. The lim sloc- tive absorbent can hea thom slmina intercalate prepared from hydrated alumina, thio aluminum layered double hydroxide chloride a layered double hydroxide modified activate alumina, layered double hydroxide imbibed ion ‘exchange resin or copolymer oF molecule sive oF zeolite layered aluminate polymer blends, a ithium manganese ‘ids, Glasium oxide, an imobiied erown ether, ora ‘combination thereof. The process zones can inclde a bine Aisplacement zone positioned upstream with respect oad flow ofa brine lading zone, whichis positioned upsteam ‘with respet to the uid flow of and in fid communication With an entrainment rejection zone, which is positioned Upsicum with respect fo fd ow of and in fat comm- nestion with an elation zone, which isin Bid commun ‘ation with the brine displacement ase, The brine solution is passed through the loading zone for @ predetermined ‘amount of ean ine 10017], The process can also include dewatering the ‘ehancod ihm product steam using @ spembrine ta ration, suchas reverse osmosis o nane-feation, in oer to produce a high lithium concention, enhanced Tihium ruet stream and areeyele elvan solution. The enhanced fhium product steam, the high lithium concentration, ‘enhanced lithium product steam or bth ean then be passed ‘or provided to ihm solvent extraction and clestowine hing process, solvent extraction and membrane electolysis proces, ora recovery process for podoction ol high purty Tithium hydroxide and thom carbonate fr batery prods 10018], The brine soloion can be a natural brine, a syne thetic bine, ora combination threo, soch us centnetal brine, a geothermal brine, an of fed brine bein fom hardrock this mining. oF combination thereof 10019} In general, ina seco aspect, the invention relates to continuous countereuerent adsorption desompion circuit configured forthe seevtive adsorption and recovery of Jithium from a lithiumrich brine station. The ert has a pray of process zones, with each ofthe process zones ‘comprising pray of adsorbent beds or cokumns having fa Tium selective odsrbent. The process zones include 9 brine lsplacement sone positioned upstream with respect fluid ow of a brine loading. Zone, which is positioned Aug. 22, 2019 upstream with respect 0 the uid low of and in Mid communication with an entrainment rejection zone. The entrainment rijection zone is positioned upsteam with respect to fluid flow of and in Mud communication With an elution zone, and the elution zone in fid communication with the brine displacement zone. [0020] The lithium-rich brine solution can be a natural ‘rine, a symtbete brine, oF a combination thereof, such as a continental brine, a geothermal brine, an oil fl brie, a brine from hard’ rock lithium mining, or a combination thereof. The lithium selective absorbent may be a lium lumina interealate prepared from hytrated akimina, a tithium aluminum layered double hydroxide chloride, a layered douible hydroxide modified ativated alumina, a layered double hydroxide imbibed ion exchange resin oF copolymer or molecular sieve or zeolite, layered aluminate polymer blends, a lithium manganese oxide, titanium Oxide, an immobilized erown ether, or a combination thereof. [0021] genera, ina thind aspect, the invention relates 0 ‘continuous adsompion and desorption process for recovery of lithium from a brine solution. The process includes steps of: [0022] ) displacing lithium-contining feed brine solution from a freshly loaded adsorbent bet or column ‘using a Fithium product efuate and passing a displace- ment liguoe soliton toa brine feed inlet ofa fithium sxlsorption zone; [0023] _b) incorporating the displacement iquoe solution ino the feed brine solution to form a combined iguoo! feed brine solution; [0024] _) passing the combined liquorice brine sohi tion though a ihium loading zone where lithium is adsorbed on one oF more loading adsorbent beds oF columns and forming. lihium depleted brine rallinate; [0028] «displacing an eluate solution fom the loading ‘adsorbent beds with & portion ofthe lithium depleted brine rafinate from the Hihium loading zane and into an elution zone: [0026] ) owing a fesh eluant sofution through the lion zone siripping a portion of lithium adsorbed on the adsorbent beds oF cohumns; and [0027] collecting » portion of the eluant having high Fthium eoncenation as an enance Tithium product solution [0028]. fourth aspect, the invention relates to a contin ‘ous acsrption and desorption process for recovery of Tihium fom fed brine solution. An elsaat solution passes through an elation zone andl strips most of the lithium fom the lithium loaded adsorbent. portion of the lium product sofation i eaptred asthe purified lithium concen- trate, and a second portion is employed 1 displace lent brine rom fresh loaded adsorbent. portion a helium product solution along with the displaced brine is routed to the brine feed inlet and this recirculation of lithium via the Aisplacement stream increases te elective lium eoncen- tration in the brine feed stream. The brine feed solution, slong withthe recyeledprosuet and displaced brine, passes through a plurafity of adsorbent beds containing itium selective adsorbent snc that lithium is selectively Toad ‘nto the adsorbent and produces a lithiumedepleted brine raffisate. portion ofthe lithinm-depleted brine rffinate is introduced to the elution zone, displacing tatent eluant solution so its not lost to rafinate whea the fst adsorb US 2019/0256368 Al bed in the elution zone eventually transitions from the ‘lution zoe to the loading zone. In addition, the process ean include membrane dewatering of the lithium product eluate to concentrate the product lithium and replenish the low ‘concentration lithium eluant solution, 10029] The foregoing has outlined in broad terns some of the more important features ofthe invention disclosed hereia so thatthe detailed description that follows may be more ‘clearly understood, and so that the contribution ofthe instant wventors tothe art may be better appreciated, The instant invention is not to be limited in its aplication wo the details ‘of the constriction and to the arangemiens of the compo- nents set forth in the following description or illustrated i the dmwings. Rather, the invention is capable of other nbodiments and of being procticed and carried out is rious other ways not specifically enumerated herein Finally, it should be understood that the phraseology and terminology employed herein are for the purpose of deserip- tion and should not be regarded as limiting, unless the specification specifically so limits the invention, BRIEF DESCRIPTION OF THE DRAWINGS 10030] These and further aspects of the invention are

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