US3860504A - Process for the production of elemental fluorine by electrolysis - Google Patents
Process for the production of elemental fluorine by electrolysis Download PDFInfo
- Publication number
- US3860504A US3860504A US450487A US45048774A US3860504A US 3860504 A US3860504 A US 3860504A US 450487 A US450487 A US 450487A US 45048774 A US45048774 A US 45048774A US 3860504 A US3860504 A US 3860504A
- Authority
- US
- United States
- Prior art keywords
- electrolyte
- barium
- skirts
- cell
- electrolysis
- 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
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 14
- 239000011737 fluorine Substances 0.000 title abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 16
- 229910001427 strontium ion Inorganic materials 0.000 claims abstract description 16
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 229910001515 alkali metal fluoride Inorganic materials 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000004880 explosion Methods 0.000 description 4
- 229910000792 Monel Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001632 barium fluoride Inorganic materials 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
Definitions
- potassium bifluoride or a similar electrically conductive salt is generally added to the electrolyte.
- electrically conductive salts such as fluorides of sodium, lithium, and ammonium are sometimes used for such purposes.
- the hydrogen fluoride and salt of which the electrolyte is composed must have high degrees of purity. They must be, for example, substantially free of water, compounds of sulfur, silicon, and heavy metals. As a general rule, however, an electrolyte containing a maximum of 0,1 percent by weight of water, for example, is considered to be acceptable.
- the walls of the tanks of which such cells are constructed are generally formed of welded sheet steel or Monel Metal, or of steel sheets lined with Monel Metal. These walls generally serve as cathodes of the cell.
- the anodes are generally fastened to but electrically insulated from the lid or cell cover and the cell cover is generally cast and machined and is provided with skirts or partitions on its underside to separate the gas streams evolved at the anodes and cathodes from each other.
- These skirts or partitions are usually formed of nickel or nickel alloys such as Monel Metal or of a magnesium alloy, as they are enumerated in Kirk-Othmer-Encyclopedia of Chemical Technology,
- Corrosion of the cell cover is a serious problem affecting the operation of such electrolytic cells and occurs especially at the gas separation skirt as a result of which the material of which the skirts are formed dissolves in and consequently contaminates the electrolyte.
- the corrosion of the skirt proceeds to such an extent that the skirt is pierced or perforated, the hydrogen in a cathode chamber can then mix with the fluorine in an adjacent anode chamber.
- An explosion can result from the reaction of the two gases in such a mixture.
- Frequent inspection of such skirts for evidences of corrosion is accordingly required to prevent the occurrences of explosions. For such inspections, the operation of the cell must be discontinued and the cell must be dismantled so that its cover can be removed and examined.
- the process of the present invention for the production of elemental fluorine by electrolysis of a mixture of hydrogen fluoride and potassium bifluoride or similar fluoride salt in such electrolytic cells provided with gas separation skirts and covers accordingly comprises adding a barium or strontium salt or mixture thereof that is capable of supplying barium or strontium ions to the said electrolyte.
- the rate of corrosion of the skirts can be reduced to from onetenth to one-hundredth of its original rate by the presence of the barium or strontium ions in the electrolyte, when the salt is present in an amount that is equivalent to at least 0.05 and at most 0.9 percent, and preferably at least 0.10 and at most 0.35 percent by weight of the electrolyte, these percentages pertaining to the equivalent content of barium or strontium ions or both ions in the salt.
- the barium or strontium ions are added as barium or strontium fluoride.
- EXAMPLE 1 A new electrolytic fluorine generator cell of the type referred to as the Allied Chemical Corporation fluorine generator cell which is illustrated on page 513 of the Kirk-Othmer Encyclopedia of Chemical Technology Second Edition, Vol. 9, published in 1966 by Interscience Publishers, a division of John Wiley and Sons, Inc., New York, was used in this example.
- the shell or walls of the cell were formed of steel plates.
- the lid or cell cover was a machined casting formed of a magnesium alloy containing more than percent by weight magnesium on the underside of which two gas separation skirts of the same material were arranged longitudinally and located appropriately with respect to the side of the shell and its longitudinal to produce elemental fluorine and hydrogen was continously replaced by fresh quantities.
- the cell was operated in this manner for a period corresponding to 26 months, after which the magnesium content of the electrolyte was determined and found to be 0.008 percent by weight. Inspection of the gas separation skirts on the underside of the cell cover revealed that no substantial amount of corrosion of the magnesium alloy of which the cell cover and skirts was composed had occurred during this period.
- EXAMPLE 2 A similar result as was described in Example 1 was observed when strontium fluoride instead of barium fluoride was added to the electrolyte in an amount corresponding to 0.12 percent by weight (calculated as strontium ion) of the total weight of the electrolyte. At the end of the 26-month operating period, the electrolyte contained a negligible proportion of magnesium and no substantial amount of corrosion of the cell cover and skirt was found.
Abstract
A process for the production of elemental fluorine by electrolysis of an electrolyte consisting essentially of hydrogen fluoride and an alkali metal fluoride in an electrolytic cell the cover of which is provided with gas separation skirts in which corrosion of the skirts is prevented by the addition to the electrolyte of a small proportion of an electrically conductive salt of barium or strontium that is capable of supplying barium or strontium ions to the said electrolyte.
Description
United States Patent [191 Kaudewitz et al.
[4 1 Jan. 14, 1975 PROCESS FOR THE PRODUCTION OF ELEMENTAL FLUORINE BY ELECTROLYSIS [75] Inventors: Peter Kaudewitz; Hubert Friedrich,
both of Bad Wimpfen, Germany [73] Assignee: Kali-Chemie Fluor GmbH, Bad
Wimpfen,-Germany 22 Filed: Mar. 12, 1974 21 Appl. No.: 450,487
[30] Foreign Application Priority Data Mar. 13, 1973 Germany 2312297 [52] U.S. Cl. 204/59 R, 204/60 [51] Int. Cl 301k l/00 [58] Field of Search 204/59 R, 60
[56] References Cited UNITED STATES PATENTS 2,034,458 3/1936 Calcott et al7 204/59 R Howell et a1 204/60 Grubb 204/60 Primary ExaminerF. Edmundson Attorney, Agent, or Firm-Michael S. Striker [57] ABSTRACT 4 Claims, N0 Drawings PROCESS FOR THE PRODUCTION OF ELEMENTAL FLUORINE BY ELECTROLYSIS BACKGROUND OF THE INVENTION Elemental fluorine which has recently attained considerable industrial importance is produced commercially by electrolysis of anhydrous hydrofluoric acid (HF) which is also known as hydrogen fluoride. In order to increase the conductivity of the hydrogen fluoride and decrease its vapor pressure and inhibit polarization at the electrode and similarvundesirable effects that occur at the anode, potassium bifluoride or a similar electrically conductive salt is generally added to the electrolyte. However other electrically conductive salts such as fluorides of sodium, lithium, and ammonium are sometimes used for such purposes. The hydrogen fluoride and salt of which the electrolyte is composed must have high degrees of purity. They must be, for example, substantially free of water, compounds of sulfur, silicon, and heavy metals. As a general rule, however, an electrolyte containing a maximum of 0,1 percent by weight of water, for example, is considered to be acceptable.
Various electrolytic cells for generating fluorine are known which differ from each other generally only in structural details. The walls of the tanks of which such cells are constructed are generally formed of welded sheet steel or Monel Metal, or of steel sheets lined with Monel Metal. These walls generally serve as cathodes of the cell. The anodes are generally fastened to but electrically insulated from the lid or cell cover and the cell cover is generally cast and machined and is provided with skirts or partitions on its underside to separate the gas streams evolved at the anodes and cathodes from each other. These skirts or partitions are usually formed of nickel or nickel alloys such as Monel Metal or of a magnesium alloy, as they are enumerated in Kirk-Othmer-Encyclopedia of Chemical Technology,
2" Edition Vol. 12 pages 688 and 689 or in Ullmanns Encyklopadie der techn. Chemie, 3" Edition, Vol. 12
pages 109 and 111.
Corrosion of the cell cover is a serious problem affecting the operation of such electrolytic cells and occurs especially at the gas separation skirt as a result of which the material of which the skirts are formed dissolves in and consequently contaminates the electrolyte. When the corrosion of the skirt proceeds to such an extent that the skirt is pierced or perforated, the hydrogen in a cathode chamber can then mix with the fluorine in an adjacent anode chamber. An explosion can result from the reaction of the two gases in such a mixture. Frequent inspection of such skirts for evidences of corrosion is accordingly required to prevent the occurrences of explosions. For such inspections, the operation of the cell must be discontinued and the cell must be dismantled so that its cover can be removed and examined. In such explosions, carbon anodes are also generally ruined and the electrolyte is thereby contaminated with carbon particles and as a result cannot as such be reused. In a violent explosion such a rise in pressure may also be produced that the cover of the cell is blown off and the hot electrolyte is blown out of the cell, thereby causing serious injury to the operating personnel and considerable damage to the surrounding areas of the plant.
As reported by A. J. Rudge on page 55 of chapter 1 entitled Production of Elemental Fluorine by Electrolysis in the book Industrial Electrochemical Processes, edited by A. T. Kuhn and published in 1971 by Elsevier Publishing Co., Amsterdam, Netherlands, the normal life of a cell with a cover formed of a machined magnesium alloy casting is estimated, depending upon an assumed cell capacity of 2O 10 Ah, to be between 20 and 30 weeks.
SUMMARY OF THE INVENTION We have discovered that, by adding barium or strontium ions or mixture of both ions to the electrolyte in a fluorine-generator cell provided with a lid or cover with gas separator skirts on its underside the corrosion of the cells as well as the gas separating skirts thereon can be considerably inhibited as a result of which the lives of such cells is increased manyfold.
The process of the present invention for the production of elemental fluorine by electrolysis of a mixture of hydrogen fluoride and potassium bifluoride or similar fluoride salt in such electrolytic cells provided with gas separation skirts and covers accordingly comprises adding a barium or strontium salt or mixture thereof that is capable of supplying barium or strontium ions to the said electrolyte. It has been found that the rate of corrosion of the skirts can be reduced to from onetenth to one-hundredth of its original rate by the presence of the barium or strontium ions in the electrolyte, when the salt is present in an amount that is equivalent to at least 0.05 and at most 0.9 percent, and preferably at least 0.10 and at most 0.35 percent by weight of the electrolyte, these percentages pertaining to the equivalent content of barium or strontium ions or both ions in the salt. Preferably the barium or strontium ions are added as barium or strontium fluoride.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION The present invention is further described in connection with the following examples which are preferred embodiments thereof and which were selected solely for purposes of illustration and are accordingly not to be construed as limiting the invention.
. EXAMPLE 1 A new electrolytic fluorine generator cell of the type referred to as the Allied Chemical Corporation fluorine generator cell which is illustrated on page 513 of the Kirk-Othmer Encyclopedia of Chemical Technology Second Edition, Vol. 9, published in 1966 by Interscience Publishers, a division of John Wiley and Sons, Inc., New York, was used in this example.
The shell or walls of the cell were formed of steel plates. The lid or cell cover was a machined casting formed of a magnesium alloy containing more than percent by weight magnesium on the underside of which two gas separation skirts of the same material were arranged longitudinally and located appropriately with respect to the side of the shell and its longitudinal to produce elemental fluorine and hydrogen was continously replaced by fresh quantities.
The electrolyte that was maintained in this cell con sisted of potassium acid fluoride having the formula KF-2HF which contained barium ions in an amount equivalent to 0,15 percent by weight, which had been added as barium fluoride in hydrogen fluoride, which electrolyte had a hydrogen fluoride content between 40 and 42 percent by weight. The hydrogen fluoride had an average purity of 99.90 percent HF by weight and its average water content was less than 0.02 percent by weight.
The cell was operated in this manner for a period corresponding to 26 months, after which the magnesium content of the electrolyte was determined and found to be 0.008 percent by weight. Inspection of the gas separation skirts on the underside of the cell cover revealed that no substantial amount of corrosion of the magnesium alloy of which the cell cover and skirts was composed had occurred during this period.
EXAMPLE 2 A similar result as was described in Example 1 was observed when strontium fluoride instead of barium fluoride was added to the electrolyte in an amount corresponding to 0.12 percent by weight (calculated as strontium ion) of the total weight of the electrolyte. At the end of the 26-month operating period, the electrolyte contained a negligible proportion of magnesium and no substantial amount of corrosion of the cell cover and skirt was found.
COMPARATIVE EXAMPLE When another new cell that was identical with that referred to in Example 1 was operated in the same manner as described therein, but an electrolyte was used whichcontained no barium or strontium ions, the magnesium content of the electrolyte after 2 months of operation was 0.81% and the gas separation skirts were very heavily corroded.
Theforegoing examples, which show the differences in the extent of contamination of the electrolyte with magnesium that originated from the corrosion of the magnesium alloy of which the cell cover and skirts was composed, demonstrates the effectiveness of the addition of barium and strontium ions to the electrolyte to reduce considerably the corrosion of the magnesium alloy during operation of such a process in such an apparatus for the production of elemental fluorine.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features which, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and rangeof equivalence of the following claims.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims:
1. A process for the production of elemental fluorine by electrolysis of an electrolyte consisting essentially of hydrogen fluoride and an alkali metal fluoride in which process the electrolyte contains barium or strontium ions or a mixture of both.
2. A process as defined in claim 1 in which the electrolyte contains the said barium or strontium ions in an amount between 0,05 and 0,9 percent by weight of the electrolyte.
3. A process as defined in claim 1 in which the electrolyte contains the said barium or strontium ions in an amount between 0,10 and 0,35 percent by weight of the electrolyte.
4. A process as defined in claim 1 in which the barium or strontium ions are present as a fluoride of barium or strontium.
Claims (3)
- 2. A process as defined in claim 1 in which the electrolyte contains the said barium or strontium ions in an amount between 0,05 and 0,9 percent by weight of the electrolyte.
- 3. A process as defined in claim 1 in which the electrolyte contains the said barium or strontium ions in an amount between 0,10 and 0,35 percent by weight of the electrolyte.
- 4. A process as defined in claim 1 in which the barium or strontium ions are present as a fluoride of barium or strontium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732312297 DE2312297C3 (en) | 1973-03-13 | Process for the production of elemental fluorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3860504A true US3860504A (en) | 1975-01-14 |
Family
ID=5874570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US450487A Expired - Lifetime US3860504A (en) | 1973-03-13 | 1974-03-12 | Process for the production of elemental fluorine by electrolysis |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3860504A (en) |
| JP (1) | JPS5644152B2 (en) |
| FR (1) | FR2221400B1 (en) |
| GB (1) | GB1407579A (en) |
| IT (1) | IT1007448B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139447A (en) * | 1975-03-21 | 1979-02-13 | Produits Chimiques Ugine Kuhlmann | Electrolyzer for industrial production of fluorine |
| US20030121796A1 (en) * | 2001-11-26 | 2003-07-03 | Siegele Stephen H | Generation and distribution of molecular fluorine within a fabrication facility |
| US20040099537A1 (en) * | 2002-11-08 | 2004-05-27 | Toyo Tanso Co., Ltd. | Fluorine gas generator and method of electrolytic bath liquid level control |
| US20040108202A1 (en) * | 2002-10-04 | 2004-06-10 | Jacobson Craig P. | Fluorine separation and generation device |
| US20040109817A1 (en) * | 2002-12-06 | 2004-06-10 | Smith Donald K. | Method and apparatus for fluorine generation and recirculation |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5584580A (en) * | 1978-12-18 | 1980-06-25 | Eidai Co Ltd | Manufacture of decorated material |
| JPS5833256U (en) * | 1981-08-31 | 1983-03-04 | 東芝テック株式会社 | thermal printer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2034458A (en) * | 1932-10-31 | 1936-03-17 | Du Pont | Process and apparatus |
| US2592144A (en) * | 1948-05-14 | 1952-04-08 | Ici Ltd | Process for the electrolytic production of fluorine |
| US2716632A (en) * | 1952-02-21 | 1955-08-30 | Gen Electric | Electrolytic method of producing fluorine or fluorine oxide |
-
1974
- 1974-03-01 GB GB938974A patent/GB1407579A/en not_active Expired
- 1974-03-07 JP JP2672974A patent/JPS5644152B2/ja not_active Expired
- 1974-03-12 US US450487A patent/US3860504A/en not_active Expired - Lifetime
- 1974-03-12 FR FR7408406A patent/FR2221400B1/fr not_active Expired
- 1974-04-08 IT IT20687/74A patent/IT1007448B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2034458A (en) * | 1932-10-31 | 1936-03-17 | Du Pont | Process and apparatus |
| US2592144A (en) * | 1948-05-14 | 1952-04-08 | Ici Ltd | Process for the electrolytic production of fluorine |
| US2716632A (en) * | 1952-02-21 | 1955-08-30 | Gen Electric | Electrolytic method of producing fluorine or fluorine oxide |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139447A (en) * | 1975-03-21 | 1979-02-13 | Produits Chimiques Ugine Kuhlmann | Electrolyzer for industrial production of fluorine |
| US20030121796A1 (en) * | 2001-11-26 | 2003-07-03 | Siegele Stephen H | Generation and distribution of molecular fluorine within a fabrication facility |
| US20040108202A1 (en) * | 2002-10-04 | 2004-06-10 | Jacobson Craig P. | Fluorine separation and generation device |
| US7670475B2 (en) | 2002-10-04 | 2010-03-02 | The Regents Of The University Of California | Fluorine separation and generation device |
| US20090152125A1 (en) * | 2002-10-04 | 2009-06-18 | Jacobson Craig P | Fluorine separation and generation device |
| US20050263405A1 (en) * | 2002-10-04 | 2005-12-01 | Jacobson Craig P | Fluorine separation and generation device |
| US7090752B2 (en) | 2002-10-04 | 2006-08-15 | The Regents Of The University Of California | Fluorine separation and generation device |
| US7468120B2 (en) | 2002-10-04 | 2008-12-23 | The Regents Of The University Of California | Fluorine separation and generation device |
| US7351322B2 (en) * | 2002-11-08 | 2008-04-01 | Toyo Tanso Co., Ltd. | Fluorine gas generator and method of electrolytic bath liquid level control |
| US20040099537A1 (en) * | 2002-11-08 | 2004-05-27 | Toyo Tanso Co., Ltd. | Fluorine gas generator and method of electrolytic bath liquid level control |
| WO2004053198A3 (en) * | 2002-12-06 | 2005-03-31 | Mks Instr Inc | Method and apparatus for fluorine generation and recirculation |
| US7238266B2 (en) | 2002-12-06 | 2007-07-03 | Mks Instruments, Inc. | Method and apparatus for fluorine generation and recirculation |
| WO2004053198A2 (en) * | 2002-12-06 | 2004-06-24 | Mks Instruments, Inc. | Method and apparatus for fluorine generation and recirculation |
| US20040109817A1 (en) * | 2002-12-06 | 2004-06-10 | Smith Donald K. | Method and apparatus for fluorine generation and recirculation |
| KR100994298B1 (en) | 2002-12-06 | 2010-11-12 | 엠케이에스 인스트루먼츠, 인코포레이티드 | Method and apparatus for fluorine generation and recirculation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1407579A (en) | 1975-09-24 |
| JPS5025494A (en) | 1975-03-18 |
| DE2312297A1 (en) | 1974-09-26 |
| DE2312297B2 (en) | 1977-03-03 |
| FR2221400B1 (en) | 1976-12-17 |
| IT1007448B (en) | 1976-10-30 |
| JPS5644152B2 (en) | 1981-10-17 |
| FR2221400A1 (en) | 1974-10-11 |
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