US3753876A - Process for electrochemical fluorination - Google Patents

Process for electrochemical fluorination Download PDF

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Publication number
US3753876A
US3753876A US00225075A US3753876DA US3753876A US 3753876 A US3753876 A US 3753876A US 00225075 A US00225075 A US 00225075A US 3753876D A US3753876D A US 3753876DA US 3753876 A US3753876 A US 3753876A
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United States
Prior art keywords
electrolyte
hydrofluoric acid
cell
electrolytic cell
fluorinated
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Expired - Lifetime
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US00225075A
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English (en)
Inventor
G Kaule
R Trupp
P Voss
H Niederprum
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Bayer AG
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Bayer AG
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Priority claimed from DE19712106870 external-priority patent/DE2106870C3/de
Application filed by Bayer AG filed Critical Bayer AG
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    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination

Definitions

  • PROCESS FOR ELECTROCHEMICAL FLUORINATION Filed Feb. 10, 1972 United States Patent "ice 3,753,876 PROCESS FOR ELECTROCHEMICAL FLUORINATION Peter Voss, Leverkusen, Hans Niederprum, Monheim, Rhineland; Gustav Kaule, Cologne, and Rudiger Trupp, Leverkusen, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany Filed Feb. 10, 1972, Ser. No. 225,075 Claims priority, application Germany, Feb. 13,1971, P 21 06 870.2 Int. Cl. B01k 3/00; C22d 1/02; (1231) 5 68 U.S. Cl.
  • the invention relates to a process and apparatus for electrochemical fluorination of organic and inorganic substances in anhydrous hydrofluoric acid.
  • the whole concept of the invention and the apparatus used difler radically from any previously described electrofluorination cells (J. Burdon, J. C. Tallow: Advances in Fluorine Chemistry, vol. 1, p.p. 129-165, London, 1960; Forche, Houbeu- Weyl: Methoden der Qrganischen Chemie, vol. V/3, pp. 38-53, Stuttgart, 1962; S. Nagase, Fluorine Chemistry Reviews 1 (1), 77-106, 1967; N. Watanabe, Denki Kagaku 36 [1968], pp. 172-186 and 264-269.
  • the process according to this invention for electrochemical fluorination has distinct advantages over all the processes previously known and described in the literature. It is distinguished by the fact that the electrolyte is continuously pumped from a large storage vessel through an electrode block in such a manner that the resulting perfiuorinated product which is insoluble in hydrofluoric acid is separated, e.g. by interposing tranquillizing zones which are either arranged separately or situated in the storage vessel, so that this insoluble product only passes once through the electrolytic cell.
  • the capacity of the storage vessel should be at least the volume of electrolyte said cell may contain and is preferably from 4 to 6 timeslarger, but without any limitation of the upper value.
  • electrolytic cell unit consisting of more than one individual cell.
  • the individual cells of such an electrolytic unit may be connected either parallel or in series.
  • a preferred method of carrying out the process is de- (1) container for anhydrous hydrofluoric acid; (2) storage vessel for electrolyte;
  • Hydrofluoric acid is forced from a container 1 into the storage vessel 2 together with nitrogen.
  • Inorganic or or ganic solid, liquid or gaseous materials which are to be fluorinated are fed continuously or intermittently into the storage vessel through suitable devices in its cover.
  • An immersion pump 3 forces the electrolyte through a cooling system via a flow rate regulator 4, and from there into an electrolytic cell 6 arranged above the cooling system, the flow of electrolyte into the electrolytic cell being preferably so arranged that the whole quantity of electrolyte must flow through the electrode block 7 from below.
  • the electrolyte level in the cell is controlled by an overflow dam.
  • the fluorinated compounds produced by electrolysis are fed into the storage vessel 2 together with circulated electrolyte.
  • Liquid and solid perfluorinated reaction products may be removed continuously or intermittently from the bottom of the storage vessel.
  • Gaseous products, especially hydrogen and hydrofluoric acid, are passed through a condenser 8 in known manner and from there to a KOH gas scrubber.
  • the condensate obtained is returned to the storage vessel 2.
  • the rates of circulation and cooling are preferably so regulated that a temperature of to 15 C. is maintained in the electrolytic cell.
  • Electrolyte was pumped from a storage vessel containing 24.0 kg. of butadiene sulphone dissolved in 120 litres of anhydrous hydrofluoric acid into the electrolytic vessel proper via a throughflow cooler at an average flow rate of 400 l./hr.
  • the electrolytic cell had a capacity of 27.5 1.
  • the electrode block consisted of 15 anodes and 16 cathodes.
  • the eflective anode surface area was 12,390 cm. corresponding to a current density of 0.008 a./cm. when the current supply was 100 amps.
  • a total quantity of 100.0 kg. of butadiene sulphone was employed at an average concentration of about 10%.
  • the current consumption after 5014.40 hours was 459,774 ampere hours, i.e. the average load was 91.8 amps.
  • the average cell temperature was +5 C.
  • the voltage varied during the whole experiment between 6.7 and 7.0 volt.
  • the total amount of product removed was 163.5 kg. which according to gas chromatographic analysis contained 85.5% of perfluorobutyl sulphonyl fluoride. This corresponds to a yield of 139.8 kg. of pure C F SO F.
  • the material yield was 54.6% of the theoretical.
  • the current yield was 42.9% of the theoretical.
  • the electrolytic cell in the operative state contained 27.5 i. of hydrofluoric acid.
  • the electrode block consisted of 31 nickel plates (15 anodes and 16 cathodes).
  • the effective anode surface was 12,390 cm. corresponding to a current density of 0.008 a./cm. at a load of amps.
  • the cell was charged with 5.500 kg. of butadiene sulphone and filled up with hydrofluoric acid. This corresponded to an electrolyte concentration of 20%.
  • Electrolysis was carried out at an average temperature of 0 C. Hydrofluoric acid and butadiene sulphone were added as required so that the average electrolyte concentration was about 10%.
  • the conductivity of butadiene sulphone in HF was so high that no other electrolyte needed to be added.
  • the material yield was 38.5% of the theoretical.
  • the current yield was 30.1% of the theoretical.
  • composition to be fluorinated is butadiene sulphone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00225075A 1971-02-13 1972-02-10 Process for electrochemical fluorination Expired - Lifetime US3753876A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712106870 DE2106870C3 (de) 1971-02-13 Verfahren zur elektrochemischen Fluorierung von organischen Verbindungen

Publications (1)

Publication Number Publication Date
US3753876A true US3753876A (en) 1973-08-21

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ID=5798679

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US00225075A Expired - Lifetime US3753876A (en) 1971-02-13 1972-02-10 Process for electrochemical fluorination

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US (1) US3753876A (it)
FR (1) FR2125409B1 (it)
GB (1) GB1382511A (it)
IT (1) IT951057B (it)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322597A (en) * 1992-07-30 1994-06-21 Minnesota Mining And Manufacturing Company Bipolar flow cell and process for electrochemical fluorination

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB740723A (en) * 1952-08-05 1955-11-16 Bayer Ag Production of saturated carbon compounds containing fluorine and the same or another halogen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322597A (en) * 1992-07-30 1994-06-21 Minnesota Mining And Manufacturing Company Bipolar flow cell and process for electrochemical fluorination

Also Published As

Publication number Publication date
GB1382511A (en) 1975-02-05
DE2106870A1 (de) 1972-08-24
IT951057B (it) 1973-06-30
FR2125409B1 (it) 1976-10-29
FR2125409A1 (it) 1972-09-29
DE2106870B2 (de) 1976-07-08

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