DE2312297B2 - METHOD FOR PRODUCING ELEMENTAL FLUORINE - Google Patents
METHOD FOR PRODUCING ELEMENTAL FLUORINEInfo
- Publication number
- DE2312297B2 DE2312297B2 DE19732312297 DE2312297A DE2312297B2 DE 2312297 B2 DE2312297 B2 DE 2312297B2 DE 19732312297 DE19732312297 DE 19732312297 DE 2312297 A DE2312297 A DE 2312297A DE 2312297 B2 DE2312297 B2 DE 2312297B2
- Authority
- DE
- Germany
- Prior art keywords
- electrolyte
- barium
- fluoride
- elemental fluorine
- corrosion
- 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052731 fluorine Inorganic materials 0.000 title claims description 5
- 239000011737 fluorine Substances 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 16
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001422 barium ion Inorganic materials 0.000 claims description 9
- 229910001427 strontium ion Inorganic materials 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910000792 Monel Inorganic materials 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000002994 raw material Substances 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
- 239000010959 steel Substances 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
Description
Fluor, dessen industrielle Bedeutung in der jüngsten Vergangenheit erheblich zugenommen hat, wird technisch durch Elektrolyse einer Lösung eines Fluorids in wasserfreiem Fluorwasserstoff dargestellt Der Zusatz von Fluoriden ist notwendig, um die Leitfähigkeit zu erhöhen, den Dampfdruck des Fluorwasserstoffs herabsetzen und das Auftreten von sogenannten Anodeneffekten weitgehend zu verhindern. Als Fluoride werden bevorzugt Kaliumfluorid, daneben unter anderem die des Lithiums, Natriums und Ammoniums eingesetzt An die Rohstoffe für den Elektrolyten werden hohe Reinheitsanforderungen gestellt beispielsweise bezüglich des Gehaltes an Wasser, Schwefel-, Silicium- und Schwermetallverbindungen. Als obere Grenze für den Wassergehalt wird in der Regel 0,1% für noch zulässig erachtetFluorine, its industrial importance in the recent Has increased significantly in the past becomes technical represented by electrolysis of a solution of a fluoride in anhydrous hydrogen fluoride The addition of fluorides is necessary to increase the conductivity, to lower the vapor pressure of the hydrogen fluoride and to largely prevent the occurrence of so-called anode effects. As fluoride are preferred potassium fluoride, among others those of lithium, sodium and ammonium used to the raw materials for the electrolyte high purity requirements are made, for example with regard to the content of water, sulfur, Silicon and heavy metal compounds. The upper limit for the water content is usually 0.1% for still considered permissible
Die Elektrolysezelle ist in verschiedenen Ausführungsformen bekannt Der Zellentrog besteht meistens aus Stahl oder Monel und dient als Kathode. Am Zellendeckel sind die Anoden elektrisch isoliert befestigt und außerdem in den Elektrolyten hineinragende Elemente zur Trennung des Kathodengasraumes vom Anodengasraum. Die Trennelemente (Schürzen) bestehen üblicherweise aus Monel oder einer Magnesiumlegierung. The electrolytic cell is known in various embodiments. The cell trough mostly exists made of steel or monel and serves as a cathode. The anodes are electrically isolated on the cell cover attached and also protruding into the electrolyte elements for separating the cathode gas space from the anode gas compartment. The separating elements (aprons) usually consist of Monel or a magnesium alloy.
Ein ernsthaftes Problem beim Betrieb der Zellen sind Korrosionserscheinungen, die besonders an den Schürzen auftreten und zur Verunreinigung des Elektrolyten durch gelöstes Schürzenmaterial führen. Wenn die Korrosion bis zur Perforation der Schürzen fortschreitet tritt der Wasserstoff im Kathodenraum mit dem Fluor im Anodenraum explosionsartig in Reaktion. Eine häufige Kontrolle der Schürzen ist daher erforderlich. Dazu muß die Zelle außer Betrieb gesetzt und demontiert werden.Corrosion, particularly on the aprons, is a serious problem with the operation of the cells occur and lead to contamination of the electrolyte by dissolved apron material. If the As corrosion progresses to the perforation of the aprons, the hydrogen enters the cathode compartment with the An explosive reaction of fluorine in the anode compartment. Frequent checks of the aprons are therefore necessary. To do this, the cell must be put out of operation and dismantled.
Bei den Explosionen werden in der Regel die Anoden teilweise zerstört, so daß der Elektrolyt mit Kohlenstoff verunreinigt und dadurch unbrauchbar wird. Bei heftigen Explosionen kommt es vor, daß der Druckanstieg ein Abheben des Zellendeckels zur Folge hat dadurch tritt heißer Elektrolyt aus den Zellen und stellt eine ernsthafte Gefahr für das Bedienungspersonal dar. Außerdem kann es zu erheblichen Schädigungen der umliegenden Anlageteile kommen.In the explosions, the anodes are usually partially destroyed, leaving the electrolyte with carbon contaminated and thereby useless. With violent explosions it happens that the pressure increase Lifting the cell cover causes hot electrolyte to escape from the cells and replace it a serious danger for the operating personnel. It can also cause considerable damage to the surrounding parts of the system.
zellen beträgt zwischen 1 und 12 Monaten Betriebszeitcells is between 1 and 12 months of operation
(s. A. J. R u d g e in A. T. Kuhn Industr. Electrochemical(see A. J. R u d g e in A. T. Kuhn Industr. Electrochemical
Es wurde nun überraschenderweise gefunden, daß durch Zusatz von Barium- und/oder Strontiumionen zum Elektrolyten die Korrosion weitgehend eingeschränkt werden kann, so daß die Lebensdauer der Zelle ίο um ein Vielfaches erhöht wird.It has now surprisingly been found that by adding barium and / or strontium ions to the electrolyte the corrosion can be largely limited, so that the life of the cell ίο is increased many times over.
von elementarem Fluor durch Elektrolyse einesof elemental fluorine by electrolysis of a
dadurch gekennzeichnet, daß der Elektrolyt Barium-characterized in that the electrolyte is barium
is und/oder Strontiumionen enthältis and / or contains strontium ions
Es hat sich gezeigt daß bereits Mengen von 0,05 bis 03%, vorzugsweise 0,10 bis 035%, an Barium- und/oder Strontiumionen die Korrosionsrate um einen Faktor von 10 bis 100 verringern.It has been shown that amounts of 0.05 to 03%, preferably 0.10 to 035%, of barium and / or Strontium ions reduce the corrosion rate by a factor of 10 to 100.
Die Barium- oder Strontiumionen können in Form von Barium- oder Strontiumverbindungen, vorzugsweise als Fluorid, zugesetzt werden.The barium or strontium ions can be in the form of barium or strontium compounds, preferably as fluoride.
i$ In einer neuen Elektrolysezeile vom Typ der Allied Chem. Corp., wie sie beispielsweise in Kirk-Othm e r: Encyclopedia of Chemical Technology 2nd Ed., Vol. 9, S. 513, beschrieben ist wurde ein Elektrolyt der Zusammensetzung KF-2,0 HF und mit einem Bariumgehalt von 0,15% Bariumionen, die in Form von Bariumfluorid dem Elektrolyten zugesetzt wurden, unter kontinuierlicher Zuführung von Fluorwasserstoff mit einem durchschnittlichen Gehalt an HF von 99,90% und einem durchschnittlichen Wassergehalt von 0,02% unter den, in der oben zitierten Literaturstelle auf S. 514 beschriebenen Betriebsbedingungen über einen Zeitraum entsprechend 26 Betriebsmonaten elektrolysiert Nach dieser Zeit ergab eine Untersuchung der Elektrolytzusammensetzung einen Gehalt an Magnesium von 0,008%. Auch das Aussehen der Schürzen und der Deckelunterseite ließ darauf schließen, daß praktisch keine Korrosion eingetreten war. i. $ In a new electrolysis line type of Allied Chem Corp., as described for example in Kirk-Othm he:.. is described Encyclopedia of Chemical Technology 2nd Ed, Vol 9, p 513, an electrolyte composition KF-2 , 0 HF and with a barium content of 0.15% barium ions, which were added to the electrolyte in the form of barium fluoride, with continuous supply of hydrogen fluoride with an average content of HF of 99.90% and an average water content of 0.02% below The operating conditions described in the above-cited reference on p. 514 were electrolyzed over a period corresponding to 26 operating months. After this time, an examination of the electrolyte composition showed a magnesium content of 0.008%. The appearance of the aprons and the underside of the lid also indicated that practically no corrosion had occurred.
Werden anstelle von 0,15% Bariumionen 0,12% Strontiumionen in Form von Strontiumfluorid dem Elektrolyten zugesetzt so konnte ebenfalls nach der angegebenen Betriebszeit praktisch keine Korrosion festgestellt werden.If 0.12% strontium ions in the form of strontium fluoride are used instead of 0.15% barium ions Electrolytes were added so there was also practically no corrosion after the specified operating time to be established.
Der Versuch wurde unter den gleichen Bedingungen, ebenfalls in einer neuen Elektrolysezelle wiederholt nur mit der Ausnahme, daß der Elektrolyt keine Bariumoder Strontiumionen enthielt Nach 2 Monaten Betriebszeit betrug der Magnesiumgehalt des Elektrolyten bereits 0.81% und die Schürzen zeigten sehr starke Korrosionserscheinungen.The experiment was only repeated under the same conditions, also in a new electrolysis cell with the exception that the electrolyte did not contain any barium or strontium ions. After 2 months of operation the magnesium content of the electrolyte was already 0.81% and the aprons were very strong Signs of corrosion.
SS Allein schon anhand des Vergleichs der aus den Schürzen und der Deckelinnenseite stammenden Magnesiumverunreinigungen in den beiden Versuchen läßt sich die beachtliche Verringerung der Korrosion durch die Anwesenheit von Barium- bzw. Strontiumionen im Elektrolyten meßbar feststellen.SS Alone based on the comparison of those from the aprons and the inside of the lid Magnesium impurities in the two experiments can significantly reduce corrosion detectable by the presence of barium or strontium ions in the electrolyte.
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732312297 DE2312297C3 (en) | 1973-03-13 | Process for the production of elemental fluorine | |
| GB938974A GB1407579A (en) | 1973-03-13 | 1974-03-01 | Method of electrolytically producing elemental fluorine |
| JP2672974A JPS5644152B2 (en) | 1973-03-13 | 1974-03-07 | |
| FR7408406A FR2221400B1 (en) | 1973-03-13 | 1974-03-12 | |
| US450487A US3860504A (en) | 1973-03-13 | 1974-03-12 | Process for the production of elemental fluorine by electrolysis |
| IT20687/74A IT1007448B (en) | 1973-03-13 | 1974-04-08 | PROCEDURE FOR PREPARING ELEMENTARY FLUORIDE |
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 (3)
| Publication Number | Publication Date |
|---|---|
| DE2312297A1 DE2312297A1 (en) | 1974-09-26 |
| DE2312297B2 true DE2312297B2 (en) | 1977-03-03 |
| DE2312297C3 DE2312297C3 (en) | 1977-10-20 |
Family
ID=
Also Published As
| Publication number | Publication date |
|---|---|
| DE2312297A1 (en) | 1974-09-26 |
| FR2221400B1 (en) | 1976-12-17 |
| JPS5025494A (en) | 1975-03-18 |
| IT1007448B (en) | 1976-10-30 |
| FR2221400A1 (en) | 1974-10-11 |
| GB1407579A (en) | 1975-09-24 |
| US3860504A (en) | 1975-01-14 |
| JPS5644152B2 (en) | 1981-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2251262C2 (en) | Process for the continuous production of aluminum by the electrolysis of aluminum chloride | |
| DE1184967B (en) | Process for the recovery of fluorine from solid residues by aluminum fused-salt electrolysis | |
| DE334475C (en) | Process for the extraction of metals and alloys by molten electrolysis | |
| DE2312297C3 (en) | Process for the production of elemental fluorine | |
| DE2312297B2 (en) | METHOD FOR PRODUCING ELEMENTAL FLUORINE | |
| EP0305910B1 (en) | Process for the production of alkali metal nitrates | |
| EP2877614A1 (en) | Method for producing an alkali metal | |
| DE2434819A1 (en) | PROCESS FOR EXTRACTION OF GALLIUM FROM ALUMINATE LYES | |
| DE1210426C2 (en) | Process for the electrolytic production of phosphine | |
| DE1567586A1 (en) | Process for the production of alkali metal chlorates by electrolytic means and equipment for carrying out the process | |
| CH493637A (en) | Process for the production of aluminum or aluminum alloys | |
| CH261436A (en) | Process for the production of metals. | |
| EP0283785B1 (en) | Process for recovering mercury by electrolysis | |
| DE1147761B (en) | Method and device for the production of titanium by reducing titanium tetrachloride with liquid magnesium produced by means of fused-salt electrolysis | |
| DE1956554A1 (en) | Electrolytic production of magnesium | |
| DE1204834B (en) | Process for the electrolytic deposition of metals that form sulfo salts, in particular antimony, arsenic, mercury or tin | |
| DE619475C (en) | Process for the extraction of metallic lead | |
| DE4303836C1 (en) | Anhydrous technical hydrofluoric acid purificn. by electrolysis - in presence of small amt. of water to minimise electrode corrosion | |
| AT117439B (en) | Process for the electrolytic extraction of pure aluminum from raw aluminum, alloys and the like like | |
| DE964676C (en) | Process for the production of pure aqueous lithium hydroxide solutions using the amalgam process | |
| DE477500C (en) | Process for the electrolytic extraction of pure aluminum from raw aluminum, alloys and the like like | |
| DE3109654A1 (en) | Process for recovering heavy metals from sulphide ore concentrates | |
| DD148523A5 (en) | METHOD FOR THE ELECTROLYTIC MANUFACTURE OF SODIUM CHLORATE | |
| DE746215C (en) | Metal electrolysis process | |
| DE488667C (en) | Production of hydrogen peroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 |