EP0053567A1 - Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen - Google Patents
Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen Download PDFInfo
- Publication number
- EP0053567A1 EP0053567A1 EP81420175A EP81420175A EP0053567A1 EP 0053567 A1 EP0053567 A1 EP 0053567A1 EP 81420175 A EP81420175 A EP 81420175A EP 81420175 A EP81420175 A EP 81420175A EP 0053567 A1 EP0053567 A1 EP 0053567A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- metal
- cell
- diaphragm
- wall
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 22
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims 2
- 150000002739 metals Chemical class 0.000 title 1
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010935 stainless steel 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
- 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
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
Definitions
- the new electrolysis cell which is the subject of the invention relates to the preparation by electrolysis of Zr or Hf.
- FIG. 1 represents an electrolysis cell for the preparation of zirconium, which is described in the report RI8125 of the USBM: "Investigation of a cell design for electrowinning zirconium metal from zirconium tetrachloride", G.M. Martinez et al, (1976).
- a graphite anode (3) is connected to the positive pole of a current source not shown and an annular cathode (4) of nickel surrounds the anode and is connected to the negative pole of the current source.
- a graphite collector (5) collects the chlorine which is released at the anode and directs it towards the gas evacuation pipe (6).
- the lower part of the collector penetrates a little below the surface of the electrolyte so as to form a hydraulic seal.
- a connecting pipe (7) with a container (8) on the left of the figure, also made of 316 stainless steel, allows the cell to be emptied by transferring the electrolyte into the container (8). Such an operation is carried out, for example, after electrolytic deposition on the cathode (4) of the zirconium initially contained in the electrolyte, in order to recover it.
- the new electrolysis cell which is the subject of the invention, makes it possible to resolve these difficulties. It comprises above the electrolyte an anode space delimited by a graphite collector or coated with graphite; the lower end of which penetrates a little below the surface of the electrolyte to form a hydraulic seal. This end is extended in the electrolyte by a solid metal wall, or a perforated or porous wall, made of metal to be deposited or coated with the metal to be deposited.
- This wall can advantageously be produced in the form of a diaphragm and a fraction of the anode current is diverted through it.
- the intensity of this derivative current can be compared to a potential difference reference.
- a first embodiment in accordance with the invention, consists, as shown in FIG. 3, of placing in a cell similar to that described in FIG. 1, a collector (15) of graphite or of metal unassailable by the electrolyte coated with graphite on the anode side.
- the coating of graphite can be carried out for example by means of a felt based on expanded graphite.
- the end of this collector only enters the electrolyte over a shallow depth; it is extended into the electrolyte by an annular wall (16) of polyvalent metal to be deposited (zirconium or hafnium). This wall (16) of limited height may or may not be perforated.
- the chlorine ions produced in the electrolyte by the dissolution of anodic chlorine in contact with the collector dissolve, in the chloride state, the polyvalent metal from the wall, thus eliminating any release of chlorine gas on the cathode face. of the collector and it is sufficient simply to periodically replace the polyvalent metal wall which acts as a sacrificial anode.
- Such a device which eliminates the release of chlorine from the cathode side, makes it possible to avoid any corrosion phenomenon in this area of the cell and also makes it possible to very significantly increase the yields of the amps as well as regards the return. in chlorine as the yield in Zr or Hf.
- the use in the cell of only metallic materials, and of graphite makes it possible to obtain deposits of Zr or Hf of high purity, the oxygen contents of which are particularly low.
- a second embodiment also in accordance with the invention consists in making the wall of polyvalent metal in the form of a diaphragm of suitable porosity completely surrounding the anode, made of a metal which cannot be attacked by the electrolyte such as nickel, cobalt or stainless steels.
- this diaphragm is kept slightly cathodic with respect to the anode by deriving a current I 1 , fraction of the current I, through this diaphragm.
- the diaphragm is covered with polyvalent metal and, provided that the current I 1 is sufficient, it is this constantly renewed deposit which serves as a sacrificial anode.
- the diaphragm behaves with respect to the electrolyte like a zirconium electrode in equilibrium of potential with respect to this electrolyte. Cathodic side, this potential is defined by the formula:
- e o Zr4 + / Zr o represents the normal potential of the zirconium electrode: "Zr o ⁇ Zr 4+ + 4e", "a Zr4 + cathodic” representing the activity of Zr 4+ ions in the catolyte.
- the potential of the diaphragm with respect to the electrolyte is defined in the formula:
- This resistance R D depends not only on the initial porosity of the diaphragm but also on the quantity of zirconium deposited which itself results from the intensity of the current I 1 which tends to increase it and of the corrosion current which tends to decrease it . It is therefore enough, to cancel the effects of the latter, to adjust I 1 , in such a way that R D remains constant, that is to say, for a constant intensity I, to subject I 1 to the variations of IR D , so as to keep the latter constant.
- FIG. 4 is a. diagram similar to that of the right part of FIG. 3 showing a zirconium electrolysis cell operating according to this second improved variant.
- the diaphragm (17) in nickel canvas is connected via the collector (18) also in nickel, covered on its face opposite the anode by a felt of expanded graphite, to the negative pole of a current source not shown, the positive pole of which is connected to the anode (19).
- the collector is isolated from the anode (19) and from the cell cover by the insulating passage (20) (21). It is thus possible to derive in the diaphragm a current of intensity I 1 which is a fraction of the electrolysis current of intensity I which passes through the anolyte. Thanks to this current I 1 , metallic zirconium is deposited on the diaphragm and can thus compensate for that which is dissolved by the corrosion current resulting from there redissolution of chlorine in ionic form in contact with the anode face of the collector.
- I 1 As a function of this corrosion current. For this, we compare the drop in potential IR D through the diaphragm or a voltage depending on this drop in potential, to a reference voltage. When IR D or the function voltage of IR D becomes lower than the reference voltage, a current I 1 is derived in the diaphragm which is all the more intense as the difference between IP D or the function voltage of IR D and the reference voltage is bigger. The intensity of the current flowing through the catolyte is of course I - I 1 .
- IR D An approximate measurement of IR D can be carried out by measuring the potential difference between two reference electrodes such as electrodes sensitive to chlorine ions, placed on either side of the diaphragm without contact therewith.
- the porosity of the diaphragm is not critical. It only needs to be sufficient so as not to hinder the equalization of the pressures between the cathode and anode compartments and, however, low enough to give rise to a fall in easily measurable potential.
- Such a device has the advantage over the previous one of not requiring any intervention on the cell to replace the sacrificial wall which is, in this case, self-healing.
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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81420175T ATE20608T1 (de) | 1980-11-27 | 1981-11-25 | Zelle zur herstellung mehrwertiger metalle, z.b. zr oder hf, durch elektrolyse geschmolzener halogenide und verfahren, um diese zelle in betrieb zu setzen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8025507 | 1980-11-27 | ||
| FR8025507A FR2494727A1 (fr) | 1980-11-27 | 1980-11-27 | Cellule pour la preparation de metaux polyvalents tels que zr ou hf par electrolyse d'halogenures fondus et procede de mise en oeuvre de cette cellule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0053567A1 true EP0053567A1 (de) | 1982-06-09 |
| EP0053567B1 EP0053567B1 (de) | 1986-07-02 |
Family
ID=9248547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81420175A Expired EP0053567B1 (de) | 1980-11-27 | 1981-11-25 | Zelle zur Herstellung mehrwertiger Metalle, z.B. Zr oder Hf, durch Elektrolyse geschmolzener Halogenide und Verfahren, um diese Zelle in Betrieb zu setzen |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4443306A (de) |
| EP (1) | EP0053567B1 (de) |
| JP (1) | JPS5834553B2 (de) |
| AT (1) | ATE20608T1 (de) |
| DE (1) | DE3174903D1 (de) |
| FR (1) | FR2494727A1 (de) |
| NO (1) | NO157025C (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2560896A1 (fr) * | 1984-03-12 | 1985-09-13 | Pechiney | Procede d'obtention d'un metal par electrolyse d'halogenures en bain de sels fondus comportant un double depot simultane et continu et dispositifs d'application |
| WO1989010437A1 (en) * | 1988-04-19 | 1989-11-02 | Ginatta Torino Titanium S.P.A. | A method for the electrolytic production of a polyvalent metal and equipment for carrying out the method |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0633476B2 (ja) * | 1987-05-27 | 1994-05-02 | 三菱原子燃料株式会社 | 融解塩電解によるジルコニユウムとハフニユウムの分離方法 |
| JPH0624982B2 (ja) * | 1988-01-12 | 1994-04-06 | 三菱原子燃料株式会社 | 四塩化ジルコニュウムと四塩化ハフニユウムを分離する方法 |
| US4865694A (en) * | 1988-09-12 | 1989-09-12 | Westinghouse Electric Corp. | Electrochemical decomposition of complexes of zirconium or hafnium |
| US4874475A (en) * | 1988-09-12 | 1989-10-17 | Westinghouse Electric Corp. | Molten salt extractive distillation process for zirconium-hafnium separation |
| RU2140465C1 (ru) * | 1997-03-20 | 1999-10-27 | Открытое акционерное общество "Чепецкий механический завод" | Способ утилизации хлора, фтора из анодного газа и отработанного электролита, образующихся в процессе электролитического получения циркония |
| GB9812169D0 (en) * | 1998-06-05 | 1998-08-05 | Univ Cambridge Tech | Purification method |
| RU2257426C1 (ru) * | 2003-11-06 | 2005-07-27 | Открытое акционерное общество "Чепецкий механический завод" (ОАО ЧМЗ) | Способ получения циркония |
| RU2400568C2 (ru) * | 2008-08-08 | 2010-09-27 | Открытое акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А.Бочвара" | Способ получения циркония электролизом расплавленного электролита (варианты) |
| RU2654397C2 (ru) * | 2016-09-06 | 2018-05-17 | Акционерное общество "Высокотехнологический научно-исследовательский институт неорганических материалов имени академика А.А. Бочвара" | Способ получения циркония электролизом расплавленного электролита (варианты) |
| CN115896875A (zh) * | 2022-11-22 | 2023-04-04 | 南京佑天金属科技有限公司 | 海绵锆、铪在电子束熔炼过程中挥发物的回收装置及方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1201567B (de) * | 1953-11-06 | 1965-09-23 | Titanium Metals Corp | Verfahren und Vorrichtung zur elektrolytischen Herstellung von reinem Titan oder Zirkonium |
| US3622491A (en) * | 1969-04-23 | 1971-11-23 | Us Interior | Electrolytic apparatus for molten salt electrolysis |
| US4167468A (en) * | 1974-10-24 | 1979-09-11 | The Dow Chemical Company | Apparatus for electrowinning multivalent metals |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2760930A (en) * | 1952-01-31 | 1956-08-28 | Nat Lead Co | Electrolytic cell of the diaphragm type |
| US2789943A (en) * | 1955-05-05 | 1957-04-23 | New Jersey Zinc Co | Production of titanium |
| US3345278A (en) * | 1963-03-25 | 1967-10-03 | Hooker Chemical Corp | Anodic passivation of metals |
| US4116801A (en) * | 1974-10-24 | 1978-09-26 | The Dow Chemical Company | Apparatus for electrowinning multivalent metals |
| FR2423555A1 (fr) * | 1978-04-21 | 1979-11-16 | Dow Chemical Co | Appareil et procede pour l'obtention par electrolyse de metaux polyvalents |
| JPS5914556B2 (ja) * | 1978-04-28 | 1984-04-05 | ザ ダウ ケミカル カンパニ− | チタン電解製造用金属性隔膜および該隔膜を使用する電解槽と該電解槽中でのチタン製造法 |
-
1980
- 1980-11-27 FR FR8025507A patent/FR2494727A1/fr active Granted
-
1981
- 1981-11-16 US US06/321,624 patent/US4443306A/en not_active Expired - Lifetime
- 1981-11-25 AT AT81420175T patent/ATE20608T1/de not_active IP Right Cessation
- 1981-11-25 DE DE8181420175T patent/DE3174903D1/de not_active Expired
- 1981-11-25 EP EP81420175A patent/EP0053567B1/de not_active Expired
- 1981-11-25 JP JP56189037A patent/JPS5834553B2/ja not_active Expired
- 1981-11-26 NO NO814031A patent/NO157025C/no unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1201567B (de) * | 1953-11-06 | 1965-09-23 | Titanium Metals Corp | Verfahren und Vorrichtung zur elektrolytischen Herstellung von reinem Titan oder Zirkonium |
| US3622491A (en) * | 1969-04-23 | 1971-11-23 | Us Interior | Electrolytic apparatus for molten salt electrolysis |
| US4167468A (en) * | 1974-10-24 | 1979-09-11 | The Dow Chemical Company | Apparatus for electrowinning multivalent metals |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2560896A1 (fr) * | 1984-03-12 | 1985-09-13 | Pechiney | Procede d'obtention d'un metal par electrolyse d'halogenures en bain de sels fondus comportant un double depot simultane et continu et dispositifs d'application |
| EP0156744A1 (de) * | 1984-03-12 | 1985-10-02 | Pechiney | Verfahren zur Gewinnung eines Metalls durch Elektrolyse von geschmolzenen Halogeniden mit gleichzeitigem und fortlaufendem Doppelniederschlag und Vorrichtung dafür |
| WO1989010437A1 (en) * | 1988-04-19 | 1989-11-02 | Ginatta Torino Titanium S.P.A. | A method for the electrolytic production of a polyvalent metal and equipment for carrying out the method |
| GR890100259A (el) * | 1988-04-19 | 1991-12-30 | Ginatta Torno Titanium Spa | Μέ?οδος ηλεκτρολυτικής παραγωγής πολυσ?ενούς μετάλλου και εξοπλισμός διεξαγωγής της με?όδου. |
Also Published As
| Publication number | Publication date |
|---|---|
| NO157025B (no) | 1987-09-28 |
| EP0053567B1 (de) | 1986-07-02 |
| NO814031L (no) | 1982-05-28 |
| NO157025C (no) | 1988-01-20 |
| DE3174903D1 (en) | 1986-08-07 |
| ATE20608T1 (de) | 1986-07-15 |
| FR2494727A1 (fr) | 1982-05-28 |
| JPS5834553B2 (ja) | 1983-07-27 |
| FR2494727B1 (de) | 1982-12-10 |
| JPS57116792A (en) | 1982-07-20 |
| US4443306A (en) | 1984-04-17 |
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