US3486994A - Process for preparing chlorine by electrolysis of aqueous hydrochloric acid - Google Patents

Process for preparing chlorine by electrolysis of aqueous hydrochloric acid Download PDF

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Publication number
US3486994A
US3486994A US603143A US3486994DA US3486994A US 3486994 A US3486994 A US 3486994A US 603143 A US603143 A US 603143A US 3486994D A US3486994D A US 3486994DA US 3486994 A US3486994 A US 3486994A
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US
United States
Prior art keywords
electrolysis
hydrochloric acid
current
aqueous hydrochloric
chlorine
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
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US603143A
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English (en)
Inventor
Ernst Donges
Hans Georg Janson
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Hoechst AG
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Hoechst AG
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Filing date
Publication date
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof

Definitions

  • the present invention relates to a process for preparing chlorine by electrolysis of aqueous hydrochloric acid in which compounds of metals occuring in several oxidation stages that are easy to convert into one another are added to the electrolyte to cut down the cell voltage.
  • the present invention provides a process for the preparation of chlorine by electrolysis of aqueous hydrochloric acid in the presence of metal compounds occuring in several oxidation stages that are easy to convert into one another, wherein with considerable gain in voltage the current efliciency is over and no additional and complicated process steps or installations are required.
  • the electrolysis of aqueous hydrochloric acid is carried out in cells with vertical electrode arrangement, the anode and cathode spaces of which are separated by diaphragms.
  • anolyte and as catholyte solutions are used that are 4 to 8 times molar with respect to the hydrochloric acid and contain 0.5 to 2 mols of copper chloride or iron chloride per liter of solution.
  • hydrogen chloride is introduced into the anolyte in the same measure as it is consumed and an oxidizing gas is introduced into the catholyte and the differential pressure between the anode space and the cathode space is maintained at zero.
  • the limiting current density is determined by the speed of the re-oxidation of the metal compound reduced at the cathode. As soon as the cathodic reduction is more rapid than the reoxidation due to too high a current density, the cell voltage gradually rises to the separation voltage of hydrogen.
  • nonionic, nonfoaming wetting agents Especially suitable are butyl diglycol (butyl ether of diethylene glycol) and particularly dibutyl diglycol (dibutyl ether of diethylene glycol).
  • the wetting agent is added to the electrolyte in an amount of up to about 1 gram per liter.
  • Air can be used as oxidizing gas.
  • the re-oxidation can be considerably accelerated when oxygen is used as oxidizing gas.
  • oxygen used as oxidizing gas
  • an addition of about 1 g./l. of dibutyl diglycol to the electrolyte an addition of about 1 g./l. of dibutyl diglycol to the electrolyte, current densities are obtained as reached in a conventional mode of operation while simultaneously current efiiciencies of over 90% are possible with about one-half of the hitherto required cell voltage.
  • the oxidizing gas is introduced into the catholyte in an amount such that at least about 40% of the metal ions present are in the higher valence stage and that the water formed in the oxidation is blown out of the cell with the gas current.
  • the elec- 20 EXAMPLE 2 trode spaces can be closed for the liquid and only provided with installations for the supply of hydrogen chloride and oxygen or air and for the removal of chlorine, air or oxygen and steam.
  • Table 2 indicates the results of a test carried out under the conditions of test 2 of Example 1 but without the use of a wetting agent.
  • the lectrolyte EXAMPLE 3 can be circulated by means of a pump in the cathode space or in the anode space or in both electrode spaces or it can be cycled through external coolers.
  • Table 5 shows the results of a test in which iron chloride 7 was used intsead of a copper salt.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Road Paving Machines (AREA)
US603143A 1966-01-03 1966-12-20 Process for preparing chlorine by electrolysis of aqueous hydrochloric acid Expired - Lifetime US3486994A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF48078A DE1277216B (de) 1966-01-03 1966-01-03 Verfahren zur Foerderung der Rueckoxydation von kathodisch reduzierten Metallverbindungen bei der Elektrolyse von waessriger Salzsaeure

Publications (1)

Publication Number Publication Date
US3486994A true US3486994A (en) 1969-12-30

Family

ID=7102026

Family Applications (1)

Application Number Title Priority Date Filing Date
US603143A Expired - Lifetime US3486994A (en) 1966-01-03 1966-12-20 Process for preparing chlorine by electrolysis of aqueous hydrochloric acid

Country Status (10)

Country Link
US (1) US3486994A (fr)
BE (1) BE692089A (fr)
DE (1) DE1277216B (fr)
ES (1) ES335071A1 (fr)
FI (1) FI45852B (fr)
FR (1) FR1507413A (fr)
GB (1) GB1140481A (fr)
NL (1) NL6618274A (fr)
NO (1) NO116757B (fr)
SE (1) SE324353B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635804A (en) * 1969-07-24 1972-01-18 Dow Chemical Co Preparation of chlorine by electrolysis of hydrochloric acid and polyvalent metal chlorides
US4320179A (en) * 1978-04-03 1982-03-16 Energy Development Associates, Inc. Transference and purification of halogen and hydrohalic acid in an electrochemical system
EP0785294A1 (fr) * 1996-01-19 1997-07-23 De Nora S.P.A. Procédé d'électrolyse de solutions aqueuses d'acide chlorhydrique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1246099A (en) * 1916-09-15 1917-11-13 Paul Leon Hulin Process for the extraction of chlorin.
US2468766A (en) * 1944-04-07 1949-05-03 Fmc Corp Recovery of chlorine from hydrogen chloride
US2666024A (en) * 1949-04-22 1954-01-12 Fmc Corp Oxidation and chlorine recovery process
GB834640A (en) * 1957-06-17 1960-05-11 L Von Roll Ag Improvements in or relating to electrolytic processes
US3119757A (en) * 1960-06-13 1964-01-28 Loda W Rogers Process and apparatus for the conversion of hydrochloric acid to chlorine
US3291708A (en) * 1964-12-31 1966-12-13 Ionics Electrolytic process for producing a halogen from its respective acid and the apparatus therefor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1746542A (en) * 1928-10-25 1930-02-11 Westvaco Chlorine Products Inc Manufacture of chlorine
US3117066A (en) * 1960-11-01 1964-01-07 Ionics Electrolytic process for producing halogen gases and the apparatus therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1246099A (en) * 1916-09-15 1917-11-13 Paul Leon Hulin Process for the extraction of chlorin.
US2468766A (en) * 1944-04-07 1949-05-03 Fmc Corp Recovery of chlorine from hydrogen chloride
US2666024A (en) * 1949-04-22 1954-01-12 Fmc Corp Oxidation and chlorine recovery process
GB834640A (en) * 1957-06-17 1960-05-11 L Von Roll Ag Improvements in or relating to electrolytic processes
US3119757A (en) * 1960-06-13 1964-01-28 Loda W Rogers Process and apparatus for the conversion of hydrochloric acid to chlorine
US3291708A (en) * 1964-12-31 1966-12-13 Ionics Electrolytic process for producing a halogen from its respective acid and the apparatus therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635804A (en) * 1969-07-24 1972-01-18 Dow Chemical Co Preparation of chlorine by electrolysis of hydrochloric acid and polyvalent metal chlorides
US4320179A (en) * 1978-04-03 1982-03-16 Energy Development Associates, Inc. Transference and purification of halogen and hydrohalic acid in an electrochemical system
EP0785294A1 (fr) * 1996-01-19 1997-07-23 De Nora S.P.A. Procédé d'électrolyse de solutions aqueuses d'acide chlorhydrique
CN1084395C (zh) * 1996-01-19 2002-05-08 德·诺拉有限公司 盐酸水溶液电解的方法

Also Published As

Publication number Publication date
DE1277216B (de) 1968-09-12
FI45852B (fr) 1972-06-30
NL6618274A (fr) 1967-07-04
ES335071A1 (es) 1968-05-01
GB1140481A (en) 1969-01-22
SE324353B (fr) 1970-06-01
BE692089A (fr) 1967-08-03
FR1507413A (fr) 1967-12-29
NO116757B (fr) 1969-05-19

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