WO2011138389A1 - Verfahren zur abreicherung von magnesium und anreicherung von lithium in chloridisch geprägten salzlösungen - Google Patents
Verfahren zur abreicherung von magnesium und anreicherung von lithium in chloridisch geprägten salzlösungen Download PDFInfo
- Publication number
- WO2011138389A1 WO2011138389A1 PCT/EP2011/057194 EP2011057194W WO2011138389A1 WO 2011138389 A1 WO2011138389 A1 WO 2011138389A1 EP 2011057194 W EP2011057194 W EP 2011057194W WO 2011138389 A1 WO2011138389 A1 WO 2011138389A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- kcl
- carnallite
- solution
- lithium
- separation
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/1081—Preparation by working up other natural sources, e.g. seawater
-
- 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
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
Definitions
- the present invention relates to a process for the enrichment of lithium with simultaneous depletion of magnesium from solutions of chloridic nature, which have high magnesium contents in relation to the lithium content.
- the currently known, largest resources of lithium are in the form of aqueous solutions (brines) in dried or partially dried salt lakes in South America, Asia and Africa.
- the solutions are mostly saturated NaCl solutions with varying concentrations of the ions K + , Mg ++ , Li + and SO 4 ⁇ as well as borate.
- the concentration for Li + is usually in a range between 200-4000 ppm.
- K + , Mg ++ and SO 4 ⁇ the concentrations reach into the tens of gram range.
- the solutions are z.
- evaporation basins or other technical equipment for fermentation (as in DE 10 2009 006 668.3).
- most of the salts are usually separated in the approximate sequence NaCl, KCl and, depending on the specific composition of the brine, various sulfates of the alkali metal magnesium sulfates.
- the most soluble salts LiCl and MgCl 2 continue to accumulate in the solution.
- the last parts of K + are crystallized on further evaporation as carnallite until finally bischofite, MgCl2 * 6H 2 O is deposited.
- magnesium hydroxide Mg (OH) 2
- Mg (OH) 2 these magnesium hydroxide precipitates occurring both partially in the evaporation basins and in the processing tanks. could be done in the factory.
- the solution for precipitating the magnesium hydroxide may also contain sodium carbonate.
- Li + is tried directly from the solutions by specific adsorption or ion exchange on granules or tablets based on (Al (OH) 3 (US Pat. No. 5,389,349, US Pat. No. 6,280,693 B1), certain types of manganese oxides, such as ⁇ type [Sagara, F., Ning, WB, Yoshida, I., Ueno, K., Separately See Technol. 24 (1989), 1227-1243; Chitrakar, R., Kanoh, H., Miyai, Eng. Chem. Res. 40 (2001), 2054-2058] or titanic acids [Yawata, K., Res. Rep.
- ⁇ type Sagara, F., Ning, WB, Yoshida, I., Ueno, K., Separately See Technol. 24 (1989), 1227-1243; Chitrakar, R., Kanoh, H., Miyai, Eng. Chem. Res. 40 (2001
- Ion exchange resins for Li separation have also been proposed instead of the inorganic sorbents [Bauman, WC, "Structure and Operation of DOW's New Lithium Selective Ion-Exchange Resin", in “Lithium - Current Applications in Science, Medicine and Technology”, J. Wiley and Sons, 1985].
- ion exchange resins can be better cut with respect to lithium ion selectivity, they are often more expensive than the abovementioned sorbents.
- the object of the invention is therefore a method that allows the accumulation of lithium and the separation of companion salts without lithium loss.
- the object is achieved by a process for the depletion of magnesium and enrichment of lithium in chloride salt solutions, in which the further evaporated solution is added with minimum contents of 4 g / L Li + and 60 g / L Mg 2+ KCl, which with the MgC of the solution is at least partially converted to carnallite (Kaliunncarnallit) and deposited in the form of Kaliunncarnallit, wherein the added KCI amount is such that the composition of the mother solution in the vicinity of the saturation of carnallite (Kaliunncarnallit) and KCl is adjusted and thus the formation of lithium carnallite is avoided.
- composition of the mother solution sets in the vicinity of the saturation of Kaliunncarnallit and KCl, means that the mother solution has taken according to their temperature, the maximum amount of KCL and thus the preferred deposit Kaliunncarnallit is secured against lithium carnallite.
- the solution in the presence of KCl, the solution can be further evaporated until a sufficiently high Li: Mg mass ratio is achieved.
- Li: Mg mass ratios of up to 7: 1 can be achieved in this way.
- the KCl is fed gradually or continuously to the evaporator.
- the addition of the KCl can be carried out periodically or continuously, just as the carnallite can be separated off in one or more stages or can also be made continuous.
- the actual design depends essentially on the mass ratio of potassium carnallite to be formed and the remaining volume of mother solution resulting for a desired Li: Mg ratio.
- the KCl is added in solid form, as an aqueous suspension with optionally further dissolved salts such as NaCl or MgC or as a homogeneous saturated solution.
- the KCl may be in solid form, preferably fine-grained, metered or in a thick aqueous suspension, which may contain besides water also other for LiCI separation less disturbing components such as NaCl, MgC or some sulfate.
- a homogeneous saturated or nearly saturated aqueous solution of KCl is also applicable.
- the time of KCI addition in the process can be chosen differently, but should be at least shortly before reaching saturation of lithium carnallite in the mother liquor.
- KCl is added after the evaporation of the desired amount of water.
- the evaporation can be carried out according to this variant, first at elevated temperature to the desired degree of concentration and then added KCl and cooled after a certain period of time for the Liereretress and as described above potassium carnallite are separated.
- the potassium carnallite which forms is discharged stepwise or continuously from the solution to the evaporator by means of solid-liquid separation.
- solid-liquid separation filtration with vacuum or overpressure or centrifugation or a combination of methods is used.
- the potassium carnallite separation takes place at temperatures of 15 to 60 ° C, preferably at 15 to 40 ° C.
- the suitable temperature for carnallite separation is preferably the ambient temperature.
- the deposition of magnesium chloride in the form of potassium carnallite has the further advantage that the morphology of the carnallite crystals for a solid-liquid separation is more favorable than that of bishopite and less mother solution sticks to the solid-liquid separation.
- solutions close to the compositions of simultaneous saturation of potassium carnallite and KCl, at a given LiCl concentration have higher vapor pressures and lower viscosities than solutions at higher MgC.sub.x concentrations necessary for bischofite deposition.
- the precipitated and discharged potassium carnallite can be broken down into KCl and a concentrated MgC ⁇ solution by using water or a relatively dilute MgCl solution by known methods.
- this carnallite decomposition will be carried out at ambient temperature.
- the KCl used for MgC ⁇ enrichment recovered back and can be used again for the inventive method.
- potassium carnallite precipitates on the basis of corresponding potassium contents of the starting solutions in upstream process steps, it can be included in the decomposition process of the KCI recovery and the excess KCl can be discharged from the process and further processed into a salable product.
- KCl is recovered in the process step of Carnallitzermaschine on the recovery of the KCl by incurred from other process steps potassium carnallite and / or KCI-containing fractions are included.
- the inventive method for depletion of magnesium and enrichment of lithium is an essential step in the production of concentrated lithium solutions of solutions of natural Li-containing salt deposits (Brines).
- the solutions are mostly saturated NaCl solutions with varying concentrations of the ions K + , Mg ++ , Li + and SO 4 ⁇ as well as borate.
- the concentration for Li + is usually in a range between 200-4000 ppm.
- K + , Mg ++ and SO 4 ⁇ the concentrations reach into the tens of gram range.
- Concentrated lithium solutions are prepared by the process according to the invention from such solutions with the following steps: a) separation of NaCl and KCl by evaporation,
- a concentration is carried out by evaporation.
- KCl can then be added in several stages, further evaporated and the crystallizing carnallite separated from the mother liquor by a suitable solid-liquid separation method (filtration, centrifugation).
- the Li: Mg ratio has then typically increased to about 3: 1, with Li + concentrations in the range of 20-60 g / L.
- the carnallite is washed with a small amount of water or a suitable process solution in order to remove most of the LiCI adhering to the mother liquor. before being sent to KCI recovery for decomposition. The washing solution is recycled in the process stages located further up.
- the highly concentrated LiCl solution is then subjected to a fine cleaning, in particular to the remaining magnesium removal by adding NaOH, if appropriate also containing Na 2 CO 3, in order then to precipitate with soda U 2 CO 3.
- the LiCl solution can be directly further evaporated to crystallize LiCl hydrate or LiCl.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180022561.6A CN103038170B (zh) | 2010-05-05 | 2011-05-05 | 在氯化物形成的盐溶液中贫化镁和富集锂的方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010019554.5 | 2010-05-05 | ||
DE201010019554 DE102010019554B4 (de) | 2010-05-05 | 2010-05-05 | Verfahren zur Abreicherung von Magnesium und Anreicherung von Lithium in chloridisch geprägten Salzlösungen |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011138389A1 true WO2011138389A1 (de) | 2011-11-10 |
WO2011138389A9 WO2011138389A9 (de) | 2012-01-05 |
Family
ID=44209945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/057194 WO2011138389A1 (de) | 2010-05-05 | 2011-05-05 | Verfahren zur abreicherung von magnesium und anreicherung von lithium in chloridisch geprägten salzlösungen |
Country Status (4)
Country | Link |
---|---|
CN (1) | CN103038170B (zh) |
CL (1) | CL2012003052A1 (zh) |
DE (1) | DE102010019554B4 (zh) |
WO (1) | WO2011138389A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2487136A1 (en) * | 2011-01-20 | 2012-08-15 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
Families Citing this family (4)
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---|---|---|---|---|
DE102015000872A1 (de) | 2015-01-23 | 2016-07-28 | K-Utec Ag Salt Technologies | Methode zur Gewinnung von Lithiumchlorid |
CN110342553B (zh) * | 2019-07-24 | 2022-04-29 | 武汉工程大学 | 一种辅助结晶晒盐降低盐湖中镁锂比的方法 |
CN110745838A (zh) * | 2019-10-25 | 2020-02-04 | 成都理工大学 | 一种CuB23纳米花的制备方法 |
CN113023751B (zh) * | 2021-05-06 | 2022-11-08 | 神华准能资源综合开发有限公司 | 一种从氯化盐水中回收锂、钠、钾、镁、钙的方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3099528A (en) * | 1962-01-10 | 1963-07-30 | Standard Magnesium Corp Inc | Recovery of values from natural lake and sea brines |
US3268289A (en) | 1962-12-11 | 1966-08-23 | Signal Oil & Gas Co | Recovery of lithium from brines |
US4271131A (en) * | 1979-04-11 | 1981-06-02 | Foote Mineral Company | Production of highly pure lithium chloride from impure brines |
US4274834A (en) | 1979-04-11 | 1981-06-23 | Foote Mineral Company | Process for purification of lithium chloride |
US4287163A (en) | 1979-05-29 | 1981-09-01 | Saline Processors, Inc. | Process for recovering lithium from brine by salting out lithium sulfate monohydrate |
US4723962A (en) | 1985-02-04 | 1988-02-09 | Lithium Corporation Of America | Process for recovering lithium from salt brines |
US5389349A (en) | 1993-05-24 | 1995-02-14 | Bauman; William C. | Recovery of lithium values from brines |
US6143260A (en) | 1998-07-16 | 2000-11-07 | Chemetall Foote Corporation | Method for removing magnesium from brine to yield lithium carbonate |
US6280693B1 (en) | 1993-05-24 | 2001-08-28 | Fmc Corporation | Composition for the recovery of lithium values from brine and process of making/using said composition |
US6547836B1 (en) | 1998-11-10 | 2003-04-15 | Sqm Salar S.A. | Process for obtaining monohydrated lithium sulfate from natural brines |
WO2003037794A1 (de) | 2001-10-25 | 2003-05-08 | Eurosina Technology Consulting & Project Development Gmbh | Verfahren zur gewinnung von lithiumchlorid aus salzlaugen und anlage zur durchführung des verfahrens |
US7157065B2 (en) | 1998-07-16 | 2007-01-02 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
DE102009006668A1 (de) | 2009-01-29 | 2010-08-05 | Technische Universität Bergakademie Freiberg | Verfahren und Vorrichtung zur solaren Eindampfung von Salzlösungen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536444A (en) * | 1969-06-13 | 1970-10-27 | Minera Bayovar Sa | Method for separating the components in brine |
KR100732066B1 (ko) * | 2006-07-25 | 2007-06-25 | (주)블루오션월드 | 해양심층수로부터 저온진공결정법을 이용한 고순도미네랄의 효율적 추출방법 |
CN101003382A (zh) * | 2006-10-19 | 2007-07-25 | 陈天强 | 盐湖废弃矿中氯化钾的回收方法 |
-
2010
- 2010-05-05 DE DE201010019554 patent/DE102010019554B4/de not_active Expired - Fee Related
-
2011
- 2011-05-05 CN CN201180022561.6A patent/CN103038170B/zh not_active Expired - Fee Related
- 2011-05-05 WO PCT/EP2011/057194 patent/WO2011138389A1/de active Application Filing
-
2012
- 2012-10-30 CL CL2012003052A patent/CL2012003052A1/es unknown
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3099528A (en) * | 1962-01-10 | 1963-07-30 | Standard Magnesium Corp Inc | Recovery of values from natural lake and sea brines |
US3268289A (en) | 1962-12-11 | 1966-08-23 | Signal Oil & Gas Co | Recovery of lithium from brines |
US4271131A (en) * | 1979-04-11 | 1981-06-02 | Foote Mineral Company | Production of highly pure lithium chloride from impure brines |
US4274834A (en) | 1979-04-11 | 1981-06-23 | Foote Mineral Company | Process for purification of lithium chloride |
US4287163A (en) | 1979-05-29 | 1981-09-01 | Saline Processors, Inc. | Process for recovering lithium from brine by salting out lithium sulfate monohydrate |
US4723962A (en) | 1985-02-04 | 1988-02-09 | Lithium Corporation Of America | Process for recovering lithium from salt brines |
US5389349A (en) | 1993-05-24 | 1995-02-14 | Bauman; William C. | Recovery of lithium values from brines |
US6280693B1 (en) | 1993-05-24 | 2001-08-28 | Fmc Corporation | Composition for the recovery of lithium values from brine and process of making/using said composition |
US6143260A (en) | 1998-07-16 | 2000-11-07 | Chemetall Foote Corporation | Method for removing magnesium from brine to yield lithium carbonate |
US7157065B2 (en) | 1998-07-16 | 2007-01-02 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
US6547836B1 (en) | 1998-11-10 | 2003-04-15 | Sqm Salar S.A. | Process for obtaining monohydrated lithium sulfate from natural brines |
WO2003037794A1 (de) | 2001-10-25 | 2003-05-08 | Eurosina Technology Consulting & Project Development Gmbh | Verfahren zur gewinnung von lithiumchlorid aus salzlaugen und anlage zur durchführung des verfahrens |
DE102009006668A1 (de) | 2009-01-29 | 2010-08-05 | Technische Universität Bergakademie Freiberg | Verfahren und Vorrichtung zur solaren Eindampfung von Salzlösungen |
Non-Patent Citations (10)
Title |
---|
BAUMAN, W.C.: "Lithium - Current Applications in Science, Medicine and Technology", 1985, J. WILEY AND SONS, article "Structure and Operation of DOW's new Lithium Selective Ion-Exchange Resin" |
BUKOWSKI, H., UHLEMANN, E., SEPAR. SCI. TECHNOL., vol. 28, 1993, pages 1357 - 1360 |
CHITRAKAR, R., KANOH, H., MIYAI, J., OOI, K., IND. ENG. CHEM. RES., vol. 40, 2001, pages 2054 - 2058 |
D.E. GARRETT: "Handbook of Lithium and Natural Calcium Chloride - their deposits, processing, uses and properties", 2004, ELSEVIER ACADEMIC PRESS |
HAM ZAOUI, A.H. M'NIF, A., HAMMI, H., ROKBANI, R., DESALINATION, vol. 158, 2003, pages 221 - 224 |
HAMZAOUI, A.H., JAMOUSSI, B., M'NIF, A., HYDROMETALLURGY, vol. 9, 2008, pages 1 - 7 |
MARCUS, Y., HYDROMETALLURGY, vol. 6, 1981, pages 269 - 275 |
RONA, M., SCHMUCKLER, G., TALANTA, vol. 20, 1973, pages 237 - 240 |
SAGARA, F, NING, W.B., YOSHIDA, 1., UENO, K., SEPAR. SCI. TECHNOL., vol. 24, 1989, pages 1227 - 1243 |
YAWATA, K., RES. REP. OF THE TSURUOKA TECHNICAL COLLEGE, vol. 41, 2006, pages 53 - 56 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2487136A1 (en) * | 2011-01-20 | 2012-08-15 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
AU2011236094B2 (en) * | 2011-01-20 | 2012-11-29 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
US9005557B2 (en) | 2011-01-20 | 2015-04-14 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
US9988280B2 (en) | 2011-01-20 | 2018-06-05 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
Also Published As
Publication number | Publication date |
---|---|
CN103038170B (zh) | 2015-01-21 |
DE102010019554A1 (de) | 2011-11-10 |
CL2012003052A1 (es) | 2013-05-31 |
WO2011138389A9 (de) | 2012-01-05 |
CN103038170A (zh) | 2013-04-10 |
DE102010019554B4 (de) | 2012-11-29 |
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