EP3315634A1 - A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof - Google Patents
A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof Download PDFInfo
- Publication number
- EP3315634A1 EP3315634A1 EP16196270.9A EP16196270A EP3315634A1 EP 3315634 A1 EP3315634 A1 EP 3315634A1 EP 16196270 A EP16196270 A EP 16196270A EP 3315634 A1 EP3315634 A1 EP 3315634A1
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- Prior art keywords
- rare earth
- anode
- carbon
- oxide
- compounds
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 21
- 239000000956 alloy Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229910052751 metal Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 title description 3
- 150000002739 metals Chemical class 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- -1 rare earth compound Chemical class 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000001722 carbon compounds Chemical class 0.000 claims description 7
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 229910021387 carbon allotrope Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000003487 electrochemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000691 Re alloy Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- 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
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
Definitions
- a method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof.
- the present invention is related to a method and an electrochemical cell thereof providing electrochemical production of rare earth (RE) alloys and metals and especially to a method wherein raw material used in the process is supplied through a rare-earth-oxide-carbon composite anode.
- RE rare earth
- Rare earth (RE) materials are a strategic commodity today, and rare earth elements are important ingredients in most electronic circuitry used in our daily life.
- China is today the most prominent supplier of rare earth elements, rare earth alloys and rare earth metals.
- a common method when producing rare earth metals like Nd, Pr, La, Ce as well as some alloys with Fe, for example Dy-Fe, can be produced by electrolysis from molten fluoride based electrolytes using raw materials comprising rare earth oxides. This is the dominant technology in China used in industrial level production of rare earth elements and alloys.
- An electrolytic process may be using a vertical set-up cell comprising graphite anodes, and molybdenum and iron as non-consumable or consumable cathode materials, respectively. Tungsten may also be used instead of molybdenum.
- the electrolyte may comprise an equimolar REF 3 -LiF mixture, and the raw material used in the electrolysis is RE 2 O 3 . The raw material can be placed as a batch in the electrolyte, or continuously or semi-continuously added at the top of the electrolyte.
- an object of the present invention to provide an electrochemical production method and an electrochemical cell thereof comprising a composite anode-supplying raw material for the production.
- a further aspect of the present invention comprises a composite anode comprising carbon compound(s) mixed with rare earth oxide(s) in amounts such that the molar ratio between carbon and rare earth oxide(s) yields stoichiometric amounts according to a specific electrochemical reaction at a specific operating temperature.
- a further aspect of the present invention comprises an electrochemical electrolysis cell comprising at least one composite anode according to the present invention.
- Figure 1 illustrates an example of embodiment of the present invention.
- production of rare earth elements or alloys containing one or more rare earth elements comprises using a molten salt electrochemical process, more specifically molten chlorides with known low solubility of oxide containing rare earth compounds are used.
- the problem of low oxide solution and sludge formation can be mitigated if the raw material (RE 2 O 3 ) can be supplied through a rare-earth-oxide-carbon composite electrode being a consumable anode.
- RE oxide is mixed with a carbon source, acting as a binder, and formed into a suitable bar or cylinder, and then heated or baked and used as an anode
- the expected anode reaction is that during polarisation carbon will react with the oxygen atoms from RE 2 O 3 forming carbon oxide or/and carbon dioxide, and RE ions.
- the RE ions are electrochemically released and will recombine with halide ions, thus dissolving in the electrolyte as a RE halide complex.
- the reactions can be noted stoichiometric in the following way when using a Nd 2 O 3 - composite. The same reaction scheme is valid for other rare earths, substituting Nd with another rare earth element(s).
- the theoretical standard potential for other rare earths varies only slightly from the potential of the reaction with Nd, as all RE elements have standard potential in the same range at given temperatures, as known to a person skilled in the art.
- Obtaining expected results in examples of embodiments of the present invention comprises manufacturing an anode in such a way that the rare earth metal ion(s) is (are) dissolved in a molten salt electrolyte while the oxygen in the oxide containing rare earth compound(s) is (are) released as oxygen containing gas species, most commonly CO or CO 2 , as a result of an electrochemical process.
- the dissolved rare earth element(s) is (are) deposited at the cathode, either in a pure form or as an alloy or as an alloy with the cathode material.
- the advantage of the present invention is that rare earth elements, or alloys containing rare earth elements, can be produced in an electrolyte with low solubility of the oxide.
- the composite anode can be made by multiple procedures: For example, the carbon compound(s) is (are) mixed with the rare earth oxide(s) in amounts such that the molar ratio between carbon and rare earth oxide(s) yields stoichiometric amounts according to the electrochemical reaction at the operating temperature.
- An example of method according to the present invention is mixing a carbon based binder, e.g. coal tar pitch, petroleum tar pitch or a synthetic binder, either in solid or liquid form, with the rare earth oxide(s) to yield the stoichiometric composition (equation (V) or (VI) above), when baked or heated to operating temperature.
- Some of the pitch may be substituted with another carbon source or another carbon containing source, e.g. graphite, carbon black, carbides or oxycarbides of the RE(s). It is advantageous that intimate mixing is achieved avoiding solid particles falling off the anode during use.
- Electrochemical characterisation, polarisation and gas evolution When the anode is polarised, e.g. at 150 mV vs an Ag/AgCl reference electrode, in the molten equimolar NaCl-KCl mixture at 860 °C, the Nd 2 O 3 and carbon reacts, evolving CO and/or CO 2 at the anode.
- the gas evolution that occur during the electrolysis can be visually observed. The gas bubbles observed were small and evenly distributed.
- baked anodes made from a mix of graphite powder, oxide and various amounts of pitch are proven to provide good results with respect to criteria like sufficient electrical conductivity, mechanical stability during electrolysis, even gas distribution, small gas bubbles and enough RE ions that is released during electrolysis.
- Consumable anodes according to the present invention may be manufactured externally and be placed inside an electrochemical cell according to the present invention when production starts. It is also within the scope of the present invention to arrange the step of baking an anode when the anode is placed inside the electrochemical cell, and baking the anode there before or during the production.
- An aspect of the present invention comprises manufacturing an anode which may comprise mixing a binder with the rare earth compounds of the anode, followed by forming the anode into a desired shape by pressing or vibro-forming and baking the anode, either in-situ in the cell or in a separate baking furnace forming a solid composite anode.
- Figure 1 illustrates the principle layout of an example of an electrochemical cell being able to support respective method steps of examples of embodiments of the present invention.
- a vessel 10 defines the outer walls of an electrochemical cell according to the present invention.
- two manufactured anodes 11, for example manufactured according to the example disclosed above is located inside the vessel 10 and are partly submerged into an electrolyte 13 comprising chloride compounds.
- a cathode 12 manufactured as known in prior art is located in between the two anodes 11.
- an electric power source (not illustrated) supplies current to the anodes 11 and the cathode 12.
- the electrochemical reaction dissolves RE and oxygen containing species 14 as disclosed above.
- Liquid RE/RE alloy products 15 are collected by the cathode, and below the cathode there is a compartment 16 receiving the liquid RE/RE alloy products 15.
- a tubing or channel 17 is removing collected liquid RE/RE alloy products from the inside of the compartment 15.
- An example of a method according to the present invention comprises steps of:
- the step of manufacturing the anode may comprise adding at least one or multiple reducing agents participating in the anode reaction when passing direct current through the electrolysis cell.
- the at least one or multiple reducing agents may comprise at least one or multiple carbon allotropes.
- the at least one or multiple reducing agents may comprise at least one or multiple carbon compounds.
- the at least one or multiple reducing agents may comprise a mixture of at least one or multiple carbon allotropes and at least one or multiple carbon compounds.
- the step of manufacturing the anode may comprise mixing a binder with the rare earth compounds of the anode, followed by forming the anode into a desired shape by pressing or vibro-forming and baking the anode, either in-situ in the cell or in a separate baking furnace forming a solid composite anode.
- the electrolyte may comprise a composition of molten halides with low or no solubility of the oxide containing rare earth compounds of the anode.
- oxygen containing gas species are carbon oxide or carbon dioxide unless other reducing agents in the anode participates in the reaction.
- the oxygen containing gas species may contain COS or SO 2 .
- the deposition of the rare earth elements on the cathode is either in pure form, or as an alloy, or as an alloy with the cathode material.
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- 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)
Abstract
Description
- A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof.
- The work leading to this invention has received funding from the European Union's Seventh Framework Programme (FP7/2007-2013) under grant agreement n° 603564.
- The present invention is related to a method and an electrochemical cell thereof providing electrochemical production of rare earth (RE) alloys and metals and especially to a method wherein raw material used in the process is supplied through a rare-earth-oxide-carbon composite anode.
- Rare earth (RE) materials are a strategic commodity today, and rare earth elements are important ingredients in most electronic circuitry used in our daily life. China is today the most prominent supplier of rare earth elements, rare earth alloys and rare earth metals. A common method when producing rare earth metals like Nd, Pr, La, Ce as well as some alloys with Fe, for example Dy-Fe, can be produced by electrolysis from molten fluoride based electrolytes using raw materials comprising rare earth oxides. This is the dominant technology in China used in industrial level production of rare earth elements and alloys.
- The report by D. K. Dysinger and J. E. Murphy, "Electrowinning of Neodymium From a Molten Oxide-Fluoride Electrolyte," United States Department of the Interior, Report of Investigations 9504, disclose some of these techniques.
- An electrolytic process may be using a vertical set-up cell comprising graphite anodes, and molybdenum and iron as non-consumable or consumable cathode materials, respectively. Tungsten may also be used instead of molybdenum. The electrolyte may comprise an equimolar REF3-LiF mixture, and the raw material used in the electrolysis is RE2O3. The raw material can be placed as a batch in the electrolyte, or continuously or semi-continuously added at the top of the electrolyte.
- There are some technical challenges operating such a cell. It is necessary to have a good balance between the feeding rate of raw material and oxide consumption. It is necessary that the amount of dissolved oxides match the supply of electrolytic current. For example, if the oxide concentration becomes too low the fluoride electrolyte itself will start to decompose. On the other hand, if the oxide concentration is too high, some of the oxides will settle at the bottom of the cell as sludge instead.
- Therefore, it is a need of an improved electrochemical process when producing rare earth elements, rare earth alloys and rare earth metals.
- In particular, it may be seen as an object of the present invention to provide an electrochemical production method and an electrochemical cell thereof comprising a composite anode-supplying raw material for the production.
- It is a further object of the present invention to provide an alternative to the prior art.
- Thus, the above described object and several other objects are intended to be obtained in a first aspect of the invention by providing a method of producing rare earth elements or rare earth alloys in a molten salt electrochemical process, comprising:
- arranging an electrolysis cell with a solid composite anode and a cathode facilitating deposition of rare earth elements, wherein a molten salt electrolyte in the cell comprises chloride compounds,
- manufacturing the anode with one or multiple oxygen containing compounds of one or more rare earth elements,
- wherein the electrochemical process results in that the oxygen in the oxide containing rare earth compound(s) are released as oxygen containing gas species and the rare earth element(s) in the anode is(are) electrochemically dissolved as rare earth metal ion(s) in the electrolyte,
- collecting rare earth element(s) or rare earth alloy(s) from the cathode.
- A further aspect of the present invention comprises a composite anode comprising carbon compound(s) mixed with rare earth oxide(s) in amounts such that the molar ratio between carbon and rare earth oxide(s) yields stoichiometric amounts according to a specific electrochemical reaction at a specific operating temperature.
- A further aspect of the present invention comprises an electrochemical electrolysis cell comprising at least one composite anode according to the present invention.
- The method according to the present invention will now be described in more detail with reference to the accompanying figure. The figure illustrates examples of embodiments of the present invention and is not to be construed as being limiting to other possible embodiments falling within the scope of the attached claim set. Further, respective examples of embodiments may each be combined with any of the other examples of embodiment.
-
Figure 1 illustrates an example of embodiment of the present invention. - Although the present invention has been described in connection with the specified embodiments, it should not be construed as being in any way limited to the present examples. The scope of the present invention is set out by the accompanying claim set. In the context of the claims, the terms "comprising" or "comprises" do not exclude other possible elements or steps. Also, the mentioning of references such as "a" or "an" etc. should not be construed as excluding a plurality. The use of reference sign in the claims with respect to elements indicated in the figures shall also not be construed as limiting to the scope of the invention. Furthermore, individual features mentioned in different claims, may possibly be advantageously combined, and the mentioning of these features in different claims does not exclude that a combination of features is not possible and advantageous.
- According to an aspect of the present invention, production of rare earth elements or alloys containing one or more rare earth elements comprises using a molten salt electrochemical process, more specifically molten chlorides with known low solubility of oxide containing rare earth compounds are used.
- According to an example of embodiment of the present invention, the problem of low oxide solution and sludge formation can be mitigated if the raw material (RE2O3) can be supplied through a rare-earth-oxide-carbon composite electrode being a consumable anode.
- If for example RE oxide is mixed with a carbon source, acting as a binder, and formed into a suitable bar or cylinder, and then heated or baked and used as an anode, the expected anode reaction is that during polarisation carbon will react with the oxygen atoms from RE2O3 forming carbon oxide or/and carbon dioxide, and RE ions.
- Then the RE ions are electrochemically released and will recombine with halide ions, thus dissolving in the electrolyte as a RE halide complex. For neodymium in a chloride melt, the reactions can be noted stoichiometric in the following way when using a Nd2O3 - composite. The same reaction scheme is valid for other rare earths, substituting Nd with another rare earth element(s).
-
Nd2O3 + 3 C = 2 Nd3+ (dissolved) + 3 CO (g) + 6 e- (I)
or
Nd2O3 + 3/2 C = 2 Nd3+ (dissolved) + 3/2 CO2 (g) + 6 e- (II)
-
Nd3+ (dissolved) + 3 Cl- = NdCl6 3- (III)
-
NdCl6 3- + 3 e- = Nd + 6 Cl- (IV)
with an overall cell reaction:
Nd2O3 + 3 C = 2 Nd + 3 CO (g) (V)
or
Nd2O3 + 3/2 C = 2 Nd + 3/2 CO2 (g) (VI)
with a theoretical standard potential E° = -1.48 and -1.55 volt for reaction (V) and (VI), respectively at 850 °C. The theoretical standard potential for other rare earths varies only slightly from the potential of the reaction with Nd, as all RE elements have standard potential in the same range at given temperatures, as known to a person skilled in the art. - Obtaining expected results in examples of embodiments of the present invention comprises manufacturing an anode in such a way that the rare earth metal ion(s) is (are) dissolved in a molten salt electrolyte while the oxygen in the oxide containing rare earth compound(s) is (are) released as oxygen containing gas species, most commonly CO or CO2, as a result of an electrochemical process. The dissolved rare earth element(s) is (are) deposited at the cathode, either in a pure form or as an alloy or as an alloy with the cathode material.
- The advantage of the present invention is that rare earth elements, or alloys containing rare earth elements, can be produced in an electrolyte with low solubility of the oxide.
- The composite anode can be made by multiple procedures: For example, the carbon compound(s) is (are) mixed with the rare earth oxide(s) in amounts such that the molar ratio between carbon and rare earth oxide(s) yields stoichiometric amounts according to the electrochemical reaction at the operating temperature. An example of method according to the present invention is mixing a carbon based binder, e.g. coal tar pitch, petroleum tar pitch or a synthetic binder, either in solid or liquid form, with the rare earth oxide(s) to yield the stoichiometric composition (equation (V) or (VI) above), when baked or heated to operating temperature. Some of the pitch may be substituted with another carbon source or another carbon containing source, e.g. graphite, carbon black, carbides or oxycarbides of the RE(s). It is advantageous that intimate mixing is achieved avoiding solid particles falling off the anode during use.
- Electrochemical characterisation, polarisation and gas evolution: When the anode is polarised, e.g. at 150 mV vs an Ag/AgCl reference electrode, in the molten equimolar NaCl-KCl mixture at 860 °C, the Nd2O3 and carbon reacts, evolving CO and/or CO2 at the anode. Using a gold coated see-through furnace and a quartz container for the electrolysis cell, the gas evolution that occur during the electrolysis can be visually observed. The gas bubbles observed were small and evenly distributed.
- Any other methods of manufacturing the anode providing same operational characteristics as disclosed above is within the scope of the present invention.
- Especially, baked anodes (REO-C anodes) made from a mix of graphite powder, oxide and various amounts of pitch are proven to provide good results with respect to criteria like sufficient electrical conductivity, mechanical stability during electrolysis, even gas distribution, small gas bubbles and enough RE ions that is released during electrolysis.
- Consumable anodes according to the present invention may be manufactured externally and be placed inside an electrochemical cell according to the present invention when production starts. It is also within the scope of the present invention to arrange the step of baking an anode when the anode is placed inside the electrochemical cell, and baking the anode there before or during the production.
- An aspect of the present invention comprises manufacturing an anode which may comprise mixing a binder with the rare earth compounds of the anode, followed by forming the anode into a desired shape by pressing or vibro-forming and baking the anode, either in-situ in the cell or in a separate baking furnace forming a solid composite anode.
-
Figure 1 illustrates the principle layout of an example of an electrochemical cell being able to support respective method steps of examples of embodiments of the present invention. - A
vessel 10 defines the outer walls of an electrochemical cell according to the present invention. In the example illustrated inFigure 1 , two manufacturedanodes 11, for example manufactured according to the example disclosed above, is located inside thevessel 10 and are partly submerged into anelectrolyte 13 comprising chloride compounds. Acathode 12 manufactured as known in prior art is located in between the twoanodes 11. During operation of the cell an electric power source (not illustrated) supplies current to theanodes 11 and thecathode 12. The electrochemical reaction dissolves RE andoxygen containing species 14 as disclosed above. Liquid RE/RE alloy products 15 are collected by the cathode, and below the cathode there is acompartment 16 receiving the liquid RE/RE alloy products 15. A tubing orchannel 17 is removing collected liquid RE/RE alloy products from the inside of thecompartment 15. - An example of a method according to the present invention comprises steps of:
- arranging an electrolysis cell with a solid composite anode and a cathode facilitating deposition of rare earth elements, wherein a molten salt electrolyte in the cell comprises chloride compounds,
- manufacturing the anode with one or multiple oxygen containing compounds of one or more rare earth elements,
- wherein the electrochemical process results in that the oxygen in the oxide containing rare earth compound(s) are released as oxygen containing gas species and the rare earth element(s) in the anode is(are) electrochemically dissolved as rare earth metal ion(s) in the electrolyte,
- collecting rare earth element(s) or rare earth alloy(s) from the cathode.
- Further, the step of manufacturing the anode may comprise adding at least one or multiple reducing agents participating in the anode reaction when passing direct current through the electrolysis cell.
- Further, the at least one or multiple reducing agents may comprise at least one or multiple carbon allotropes.
- Further, the at least one or multiple reducing agents may comprise at least one or multiple carbon compounds.
- Further, the at least one or multiple reducing agents may comprise a mixture of at least one or multiple carbon allotropes and at least one or multiple carbon compounds.
- Further, the step of manufacturing the anode may comprise mixing a binder with the rare earth compounds of the anode, followed by forming the anode into a desired shape by pressing or vibro-forming and baking the anode, either in-situ in the cell or in a separate baking furnace forming a solid composite anode.
- Further, the electrolyte may comprise a composition of molten halides with low or no solubility of the oxide containing rare earth compounds of the anode.
- Further, the oxygen containing gas species are carbon oxide or carbon dioxide unless other reducing agents in the anode participates in the reaction.
- Further, if sulfur or a sulfur compound is present in the anode and participating in the reaction, the oxygen containing gas species may contain COS or SO2.
- Further, the deposition of the rare earth elements on the cathode is either in pure form, or as an alloy, or as an alloy with the cathode material.
Claims (12)
- A method of producing rare earth elements or rare earth alloys in a molten salt electrochemical process, comprising:- arranging an electrolysis cell with a solid composite anode and a cathode facilitating deposition of rare earth elements, wherein a molten salt electrolyte in the cell comprises chloride compounds,- manufacturing the anode with one or multiple oxygen containing compounds of one or more rare earth elements,- wherein the electrochemical process results in that the oxygen in the oxide containing rare earth compound(s) are released as oxygen containing gas species and the rare earth element(s) in the anode is(are) electrochemically dissolved as rare earth metal ion(s) in the electrolyte,- collecting rare earth element(s) or rare earth alloy(s) from the cathode.
- The method according to claim 1, wherein the step of manufacturing the anode comprises adding at least one or multiple reducing agents participating in the anode reaction when passing direct current through the electrolysis cell.
- The method according to claim 2, wherein the at least one or multiple reducing agents comprises at least one or multiple carbon allotropes.
- The method according to claim 2, wherein the at least one or multiple reducing agents comprises at least one or multiple carbon compounds.
- The method according to claim 2, wherein the at least one or multiple reducing agents comprises a mixture of at least one or multiple carbon allotropes and at least one or multiple carbon compounds.
- The method according to any claim 1-5, wherein the step of manufacturing the anode comprises mixing a binder with the rare earth compounds of the anode, followed by forming the anode into a desired shape by pressing or vibro-forming and baking the anode, either in-situ in the cell or in a separate baking furnace forming a solid composite anode.
- The method according to claim 1, wherein the electrolyte comprises a composition of molten halides with low or no solubility of the oxide containing rare earth compounds of the anode.
- The method according to claim 1, wherein the oxygen containing gas species released at the anode are carbon oxide or carbon dioxide.
- The method according to claim 8, wherein the oxygen containing gas species released at the anode are carbon oxide or carbon dioxide and other oxygen containing species from other reducing agents that participates in the anode reaction, e.g. sulfur forming COS and/or SO2 oxygen containing gas species.
- The method according to claim 1, wherein the deposition of the rare earth elements on the cathode is either in pure form, or as an alloy, or as an alloy with the cathode material.
- A composite anode to be used in a method according to any claim 1-10, wherein the composite anode comprises carbon compound(s) mixed with rare earth oxide(s) in amounts such that the molar ratio between carbon and rare earth oxide(s) yields stoichiometric amounts according to a specific electrochemical reaction at specific operating temperature.
- An electrochemical electrolysis cell comprising at least one anode according to claim 11.
Priority Applications (3)
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EP16196270.9A EP3315634B1 (en) | 2016-10-28 | 2016-10-28 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode |
PCT/EP2017/077408 WO2018077999A1 (en) | 2016-10-28 | 2017-10-26 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof |
EP17788249.5A EP3532656A1 (en) | 2016-10-28 | 2017-10-26 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof |
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EP16196270.9A EP3315634B1 (en) | 2016-10-28 | 2016-10-28 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode |
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EP3315634A1 true EP3315634A1 (en) | 2018-05-02 |
EP3315634B1 EP3315634B1 (en) | 2020-02-19 |
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EP16196270.9A Active EP3315634B1 (en) | 2016-10-28 | 2016-10-28 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode |
EP17788249.5A Withdrawn EP3532656A1 (en) | 2016-10-28 | 2017-10-26 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof |
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EP17788249.5A Withdrawn EP3532656A1 (en) | 2016-10-28 | 2017-10-26 | A method of electrochemical production of rare earth alloys and metals comprising a composite anode, and a system thereof |
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WO (1) | WO2018077999A1 (en) |
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CN112921361A (en) * | 2019-12-05 | 2021-06-08 | 有研稀土新材料股份有限公司 | Yttrium aluminum intermediate alloy and preparation method thereof |
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CN113416984A (en) * | 2021-06-09 | 2021-09-21 | 华北理工大学 | Method for preparing metallic iron by utilizing soluble anode electrolysis |
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US20050166706A1 (en) * | 2003-08-20 | 2005-08-04 | Withers James C. | Thermal and electrochemical process for metal production |
US20160102411A1 (en) * | 2013-06-24 | 2016-04-14 | Siemens Aktiengesellschaft | Device for reducing a metal ion from a salt melt |
-
2016
- 2016-10-28 EP EP16196270.9A patent/EP3315634B1/en active Active
-
2017
- 2017-10-26 EP EP17788249.5A patent/EP3532656A1/en not_active Withdrawn
- 2017-10-26 WO PCT/EP2017/077408 patent/WO2018077999A1/en unknown
Patent Citations (2)
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US20050166706A1 (en) * | 2003-08-20 | 2005-08-04 | Withers James C. | Thermal and electrochemical process for metal production |
US20160102411A1 (en) * | 2013-06-24 | 2016-04-14 | Siemens Aktiengesellschaft | Device for reducing a metal ion from a salt melt |
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\L S BUR6AU ET AL: "RI 9391 REPORT OF INVESTIGATIONS/1991 Electrolytic Production of Neodymium Metal From a Molten Chloride Electrolyte", 31 December 1991 (1991-12-31), XP055362234, Retrieved from the Internet <URL:https://stacks.cdc.gov/view/cdc/10115/cdc_10115_DS1.pdf> [retrieved on 20170405] * |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112921361A (en) * | 2019-12-05 | 2021-06-08 | 有研稀土新材料股份有限公司 | Yttrium aluminum intermediate alloy and preparation method thereof |
CN112921361B (en) * | 2019-12-05 | 2022-02-22 | 有研稀土新材料股份有限公司 | Yttrium aluminum intermediate alloy and preparation method thereof |
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EP3532656A1 (en) | 2019-09-04 |
WO2018077999A1 (en) | 2018-05-03 |
EP3315634B1 (en) | 2020-02-19 |
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