US3344049A - Method of producing lithium - Google Patents
Method of producing lithium Download PDFInfo
- Publication number
- US3344049A US3344049A US3344049DA US3344049A US 3344049 A US3344049 A US 3344049A US 3344049D A US3344049D A US 3344049DA US 3344049 A US3344049 A US 3344049A
- Authority
- US
- United States
- Prior art keywords
- lithium
- chlorine
- electrolysis
- licl
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052744 lithium Inorganic materials 0.000 title claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- 238000005868 electrolysis reaction Methods 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 22
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000000155 melt Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 239000011833 salt mixture Substances 0.000 claims description 14
- 150000002642 lithium compounds Chemical class 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910003002 lithium salt Inorganic materials 0.000 description 16
- 159000000002 lithium salts Chemical class 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 150000001447 alkali salts Chemical class 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
Definitions
- Oxygen-containing lithium salts such as Li CO may be made by the usual process for extracting lithium salts from lithium ores. Proceeding directly to the lithium electrolysis from such oxygen-containing lithium salts obviates the necessity for conversion of Li CO to LiCl as a separate process.
- a method has been discovered of producing lithium through molten salt electrolysis of salt mixtures such that the chlorine produced in the electrolysis cell reacts with oxygen-containing lithium salts, particularly Li CO and the salt melt is renewed by the LiCl produced.
- This process has the advantage that the continuous melt electrolysis of lithium-containing alkali salt mixtures can be carried out and maintained even with certain oxygen-containing lithium salts, which salts are made in the conventional processes for extracting lithium salts from ores, for example Li CO or LiOH.
- the anode is not attacked since the conversion of carbonate to chloride is completed before the molten mixture moves into the electrolysis zone.
- the problem as evidenced by the prior art has been the lack of a technically suitable and economic material which will withstand attack by chlorine at the required reaction temperatures of between 400-480" C.
- the process of this invention may be carried out in commonly used electrolytic cells operating with alkali salt mixtures at a temperature of 400480 C.
- the cell construction closely resembles that of sodium electrolysis in which the molten zone is separated by a diaphragm into an anode and cathode compartment, and the space above the molten salt is likewise separated into cathode and anode compartments which permits separation of the 3,344,049 Patented Sept. 26, 1967 "ice products of electrolysis, namely alkali metal and chlorine.
- well dried Li CO is put into th anodic collection compartment with the evolved chlorine which produces CO and 0 by the reaction:
- the Li CO should be evenly distributed over the surface of the molten salt in the anodic compartment, and in such amount as is required by the depletion of the LiCl in the melt through production of lithium and chlorine.
- the dried lithium carbonate reacts very quickly with the nascent chlorine due to the high temperature of the melt and of the chlorine gas itself. This results in only the newly formed lithium chloride being taken up by the melt. In this manner the disadvantages of the direct electrolytic conversion of Li CO are avoided. In addition, by maintaining an excess of lithium carbonate on the molten surface, practically all of the chlorine released by the electrolysis is used for conversion of the lithium carbonate.
- a continuous molten electrolytic process for obtaining lithium metal is provided which permits the required replenishment of the melt with LiCl continuously through use of an equivalent amount of Li CO which Li CO is converted by chlorine directly to LiCl in the collection space over the anode.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Description
United States Patent 3,344,049 METHOD OF PRODUCING LITHIUM Erich Thieler, Bad Homburg vor der Hohe, Germany, assignor to Foote Mineral Company, Exton, Pa., a corporation of Pennsylvania No Drawing. Filed Mar. 1, 1965, Ser. No. 436,263 Claims priority, application Germany, Mar. 6, 1964, M 60,174 3 Claims. (Cl. 20468) The present invention relates to a method for producing lithium through the electrolysis of molten salt mixtures.
It is well known how to produce metallic lithium through electrolysis of molten lithium salt mixtures, such as a mixture of LiCl and KCl. The prior art suggests the molten salt electrolysis of Li CO as well as a mixture of alkali chlorides with the addition of a small quantity of oxygen-containing alkali salts, for example Li CO Utilizing the methods suggested by the prior art has caused considerable technical difficulty in that the graphite anode is oxidized by the nascent oxygen produced in the electrolysis and is also mechanically destroyed, whereby undesirable foaming and contamination of the melt bath takes place and the electrolysis becomes inoperable.
However, it has been discovered that it is preferable to proceed directly to the lithium electrolysis from such oxygen-containing lithium salts as, preferably Li CO Oxygen-containing lithium salts such as Li CO may be made by the usual process for extracting lithium salts from lithium ores. Proceeding directly to the lithium electrolysis from such oxygen-containing lithium salts obviates the necessity for conversion of Li CO to LiCl as a separate process.
A method has been discovered of producing lithium through molten salt electrolysis of salt mixtures such that the chlorine produced in the electrolysis cell reacts with oxygen-containing lithium salts, particularly Li CO and the salt melt is renewed by the LiCl produced.
This process has the advantage that the continuous melt electrolysis of lithium-containing alkali salt mixtures can be carried out and maintained even with certain oxygen-containing lithium salts, which salts are made in the conventional processes for extracting lithium salts from ores, for example Li CO or LiOH. In addition, the anode is not attacked since the conversion of carbonate to chloride is completed before the molten mixture moves into the electrolysis zone. Furthermore, it is necessary to carry out the known reaction for conversion of Li CO with chlorine in the electrolytic cell itself since this eliminates the diificulties that have prevented the practical accomplishment of the direct conversion of Li CO with chlorine. The problem as evidenced by the prior art has been the lack of a technically suitable and economic material which will withstand attack by chlorine at the required reaction temperatures of between 400-480" C.
The process of this invention may be carried out in commonly used electrolytic cells operating with alkali salt mixtures at a temperature of 400480 C. The cell construction closely resembles that of sodium electrolysis in which the molten zone is separated by a diaphragm into an anode and cathode compartment, and the space above the molten salt is likewise separated into cathode and anode compartments which permits separation of the 3,344,049 Patented Sept. 26, 1967 "ice products of electrolysis, namely alkali metal and chlorine. According to the invention, well dried Li CO is put into th anodic collection compartment with the evolved chlorine which produces CO and 0 by the reaction:
The Li CO should be evenly distributed over the surface of the molten salt in the anodic compartment, and in such amount as is required by the depletion of the LiCl in the melt through production of lithium and chlorine.
The dried lithium carbonate reacts very quickly with the nascent chlorine due to the high temperature of the melt and of the chlorine gas itself. This results in only the newly formed lithium chloride being taken up by the melt. In this manner the disadvantages of the direct electrolytic conversion of Li CO are avoided. In addition, by maintaining an excess of lithium carbonate on the molten surface, practically all of the chlorine released by the electrolysis is used for conversion of the lithium carbonate.
Utilizing the process of the present invention, a continuous molten electrolytic process for obtaining lithium metal is provided which permits the required replenishment of the melt with LiCl continuously through use of an equivalent amount of Li CO which Li CO is converted by chlorine directly to LiCl in the collection space over the anode. Thus the previously required conversion of Li CO to LiCl in a separate process and by separate equipment can now be avoided.
Although the invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and that numerous changes in the method may be made without departing from the spirit and the scope of the invention as hereinafter claimed.
What is claimed is:
1. In a process for producing lithium by electrolysis of a molten salt mixture containing LiCl in an electrolytic cell wherein the space above the molten salt is separated into chlorineand lithium-collecting spaces, the improvement comprising introducing an oxygen containing lithium compound selected from the group consisting of Li CO and LiOH onto the surface of the melt in the chlorine collecting space whereby the oxygen containing lithium compound is converted by the chlorine to LiCl which in turn replenishes the bath, and withdrawing lithium from the lithium collecting space.
2. Process of claim 1 characterized in that Li CO is converted in the anode collection space with chlorine to LiCl.
3. Process of 1 characterized in that the lithium chloride is formed on the surface of the melt.
References Cited UNITED STATES PATENTS 1,515,001 11/1924 Girsewald et a1. 20468 2,059,750 11/1936 Roder et al 20468 2,862,863 12/1958 Grifiith 20468 FOREIGN PATENTS 582,642 9/ 1959 Canada.
JOHN H. MACK, Primary Examiner.
D. R. VALENTINE, Assistant Examiner.
Claims (1)
1. IN A PROCESS FOR PRODUCING LITHIUM BY ELECTROLYSIS OF A MOLTEN SALT MIXTURE CONTAINING LICL IN AN ELECTROLYTIC CELL WHEREIN THE SPACE ABOVE THE MOLTEN SALT IS SEPARATED INTO CHLORINE- AND LITHIUM-COLLECTING SPACES, THE IMPROVEMENT COMPRISING INTRODUCING AN OXYGEN CONTAINING LITHIUM COMPOUND SELECTED FROM THE GROUP CONSISTING OF LI2CO3 AND LIOH ONTO THE SURFACE OF THE MELT IN THE CHLORINE COLLECTING SPACE WHEREBY THE OXYGEN CONTAINING LITHIUM COMPOUND IS CONVERTED BY THE CHLORINE TO LICL WHICH IN TURN REPLENISHES THE BATH, AND WITHDRAWING LITHIUM FROM THE LITHIUM COLLECTING SPACE.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3344049A true US3344049A (en) | 1967-09-26 |
Family
ID=3459370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3344049D Expired - Lifetime US3344049A (en) | Method of producing lithium |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3344049A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2532332A1 (en) * | 1982-08-31 | 1984-03-02 | Rhone Poulenc Spec Chim | PROCESS FOR THE CONTINUOUS PREPARATION OF LITHIUM BY ELECTROLYSIS OF LITHIUM CHLORIDE IN A MIXTURE OF MOLTEN SALTS AND APPARATUS FOR CARRYING OUT SAID PROCESS |
| US4455202A (en) * | 1982-08-02 | 1984-06-19 | Standard Oil Company (Indiana) | Electrolytic production of lithium metal |
| US4988417A (en) * | 1988-12-29 | 1991-01-29 | Aluminum Company Of America | Production of lithium by direct electrolysis of lithium carbonate |
| US5665220A (en) * | 1995-12-26 | 1997-09-09 | General Motors Corporation | Electrolytic magnesium production process |
| US20100051470A1 (en) * | 2006-11-02 | 2010-03-04 | Santoku Corporation | Process for producing metallic lithium |
| US11131028B2 (en) | 2012-07-26 | 2021-09-28 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1515001A (en) * | 1923-04-19 | 1924-11-11 | American Lurgi Corp | Process for obtaining lithium salts or metallic lithium |
| US2059750A (en) * | 1931-09-15 | 1936-11-03 | American Lurgi Corp | Process for the production of lithium salts and metallic lithium |
| US2862863A (en) * | 1957-09-23 | 1958-12-02 | Kenneth F Griffith | Apparatus for electrolytic production of a metal product from fused salts |
| CA582642A (en) * | 1959-09-01 | L. Slatin Harvey | Production of pure lithium |
-
0
- US US3344049D patent/US3344049A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA582642A (en) * | 1959-09-01 | L. Slatin Harvey | Production of pure lithium | |
| US1515001A (en) * | 1923-04-19 | 1924-11-11 | American Lurgi Corp | Process for obtaining lithium salts or metallic lithium |
| US2059750A (en) * | 1931-09-15 | 1936-11-03 | American Lurgi Corp | Process for the production of lithium salts and metallic lithium |
| US2862863A (en) * | 1957-09-23 | 1958-12-02 | Kenneth F Griffith | Apparatus for electrolytic production of a metal product from fused salts |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4455202A (en) * | 1982-08-02 | 1984-06-19 | Standard Oil Company (Indiana) | Electrolytic production of lithium metal |
| FR2532332A1 (en) * | 1982-08-31 | 1984-03-02 | Rhone Poulenc Spec Chim | PROCESS FOR THE CONTINUOUS PREPARATION OF LITHIUM BY ELECTROLYSIS OF LITHIUM CHLORIDE IN A MIXTURE OF MOLTEN SALTS AND APPARATUS FOR CARRYING OUT SAID PROCESS |
| EP0107521A1 (en) * | 1982-08-31 | 1984-05-02 | Rhone-Poulenc Chimie | Process for the continuous production of lithium by electrolysis of lithium chloride in a molten salt mixture, and apparatus for carrying out said process |
| US4988417A (en) * | 1988-12-29 | 1991-01-29 | Aluminum Company Of America | Production of lithium by direct electrolysis of lithium carbonate |
| US5665220A (en) * | 1995-12-26 | 1997-09-09 | General Motors Corporation | Electrolytic magnesium production process |
| US20100051470A1 (en) * | 2006-11-02 | 2010-03-04 | Santoku Corporation | Process for producing metallic lithium |
| US20130001097A1 (en) * | 2006-11-02 | 2013-01-03 | Santoku Corporation | Process for producing metallic lithium |
| US8911610B2 (en) * | 2006-11-02 | 2014-12-16 | Santoku Corporation | Process for producing metallic lithium |
| US11131028B2 (en) | 2012-07-26 | 2021-09-28 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
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