EP0382284A1 - Verfahren zur Herstellung von Alkalimetallsulfid - Google Patents

Verfahren zur Herstellung von Alkalimetallsulfid Download PDF

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Publication number
EP0382284A1
EP0382284A1 EP90200216A EP90200216A EP0382284A1 EP 0382284 A1 EP0382284 A1 EP 0382284A1 EP 90200216 A EP90200216 A EP 90200216A EP 90200216 A EP90200216 A EP 90200216A EP 0382284 A1 EP0382284 A1 EP 0382284A1
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EP
European Patent Office
Prior art keywords
alkali metal
cathode
sulfide
process according
anode
Prior art date
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Application number
EP90200216A
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English (en)
French (fr)
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EP0382284B1 (de
Inventor
Edgard Nicolas
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Solvay SA
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Solvay SA
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Publication date
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds

Definitions

  • the present invention relates to a process for the manufacture of alkali metal sulfide.
  • a known method for manufacturing sodium sulfide consists in reacting a sodium polysulfide solution with a sodium amalgam obtained by electrolysis of an aqueous solution of sodium chloride in a mercury cathode electrolysis cell (JS SCONCE - Chlorine, Its Manufacture, Properties and Uses - Reinhold Publishing Corporation, 1962 - page 180).
  • This known method has the drawback of involving the use of a sodium amalgam, the production of which by electrolysis is an expensive operation, which is further complicated by the need to avoid contamination of the environment by mercury.
  • it is difficult to avoid the presence of mercury in the sodium sulphide produced which constitutes another disadvantage of this known process.
  • the invention aims to provide a new method which avoids the aforementioned drawbacks.
  • the invention therefore relates to a process for manufacturing alkali metal sulfide, according to which an electrolysis cell is used in which a membrane which is selectively permeable to cations separates an anode chamber containing an anode from a cathode chamber containing a cathode, an electrolyte containing cations of said alkali metal is electrolyzed in the anode chamber and an aqueous polysulfide solution of the alkali metal is simultaneously electrolyzed in the cathode chamber.
  • the method according to the invention involves the use of an electrolysis cell of the membrane type selectively permeable to cations. It can be a membrane cell designed on the model of those suitable for the production of chlorine and sodium hydroxide by electrolysis of aqueous solutions of sodium chloride.
  • the function of the membrane is to physically separate the electrolyte contained in the anode chamber from the polysulfide solution contained in the cathode chamber, allowing only the transfer of cations from the anode chamber to the cathode chamber. It must be made of a material inert with respect to the electrolyte used in the anode chamber and with respect to the alkali metal polysulfide solution. Fluoropolymer membranes containing functional groups derived from carboxylic, phosphonic or sulfonic acids can generally be used. Preferred membranes are those made of perfluorinated polymer containing functional groups derived from sulfonic and / or carboxylic acids.
  • membranes of this type are those described in documents GB-A-1497748 and GB-A-1497749 (ASAHI KASEI KOGYO KK), GB-A-1518387, GB-A-1522877 and US-A-4126588 (ASAHI GLASS COMPANY LTD) and GB-A-1402920 (DIAMOND SHAMROCK CORP.).
  • membranes suitable for the process according to the invention are those known under the brands NAFION (DU PONT DE NEMOURS & CO) and FLEMION (ASAHI GLASS COMPANY LTD).
  • cathodes which can be used in the process according to the invention are those in which the active material catalyzing the electrolysis reaction is selected from molybdenum sulfide, copper sulfide, metals from group 8 of the periodic table of elements and alloys , sulfides and oxides of these metals. Nickel, cobalt, platinum, rhodium, ruthenium, osmium, iridium, the oxides of these metals, molybdenum sulfide and copper sulfide are preferred.
  • the choice of anode depends on the electrolyte used in the anode chamber of the electrolysis cell, to generate electrochemical oxidation of the electrolyte under normal electrolysis conditions.
  • the electrolyte containing alkali metal cations is preferably an aqueous electrolyte. It is advantageously chosen from aqueous solutions of alkali metal hydroxide and aqueous solutions of water-soluble salts of alkali metals.
  • the salts giving rise to the emission of a gas at the anode during the electrolysis are preferred, such as chlorides, fluorides, carbonates, sulfates and phosphates for example.
  • the anode is chosen so as to obtain a release of halogen or oxygen under normal electrolysis conditions.
  • the aqueous alkali metal polysulfide solution can be obtained by any suitable means. It is advantageously obtained by dissolving sulfur in an aqueous solution of alkali metal sulfide, according to the reaction: M2S + xS ⁇ M2S 1 + x in which M denotes the alkali metal.
  • an aqueous solution of alkali metal sulfide is collected from the cathode chamber.
  • the alkali metal sulfide can then be extracted from the solution, for example by evaporation of the latter.
  • the invention applies in particular to the manufacture of sodium sulfide, in the anhydrous or hydrated state (generally nonahydrate).
  • the electrolysis cell shown in the figure comprises an enclosure 1 which is divided, by a separator 2, into two chambers, respectively anode 3 and cathode 4.
  • the separator 2 is a membrane with selective permeability to cations; it is for example a NAFION membrane (DU PONT DE NEMOURS & CO), which consists of a sheet of perfluorinated polymer comprising functional groups derived from sulfonic acids.
  • NAFION membrane DU PONT DE NEMOURS & CO
  • the anode chamber 3 contains an anode 5 and the cathode chamber 4 contains a cathode 6.
  • the anode 5 and the cathode 6 are coupled respectively to the positive terminal and to the negative terminal of a direct current source, not shown.
  • the anode chamber 3 is supplied with a substantially saturated aqueous solution of sodium chloride 7; simultaneously, the cathode chamber 4 is supplied with an aqueous solution of sodium polysulfide 8 obtained by dissolving sulfur 9 in an aqueous solution of sodium sulfide 10, upstream of the cell.
  • chlorine is produced at the anode and sulfur is reduced at the cathode.
  • sodium cations from the anode chamber 3 pass through the membrane 2 and penetrate into the cathode chamber 4.
  • the sodium chloride solution 7 is replaced by a concentrated aqueous solution of sodium hydroxide.
  • oxygen is produced at the anode.
  • An electrolysis cell having the following characteristics was used: - anode: perforated titanium plate, covered with a layer formed by an equimolar mixture of ruthenium oxide and titanium dioxide; - cathode: expanded sheet of nickel; - area of the useful electrolysis surface: 14 cm2; - gap between the anode and the cathode: 2 mm; - perfluorinated membrane of the sulfonic type, NAFION (DU PONT DE NEMOURS & CO).
  • the anode chamber of the cell was supplied with an aqueous solution containing 220 g of sodium chloride per kg, with a flow rate of 100 cm3 / hour.
  • a potential difference of 3.22 V was imposed across the terminals of the electrolysis cell; we have also maintained the cathode potential at -1.1 V by means of a potentiostatic circuit. The temperature in the cell was maintained at 73 ° C.
  • Example 1 A cell similar to that of Example 1 was used, in which the anode consisted of an expanded nickel sheet, identical to the cathode.
  • Example 2 The procedure was as in Example 1, under the following conditions: - electrolyte in the anode chamber: aqueous solution of sodium hydroxide (320 g / kg), at a flow rate of 70 cm3 / hour; - electrolyte in the cathode chamber: aqueous solution containing 4 moles of sodium sulfide and 1 mole of sulfur per liter; - potential difference across the cell, at the start of electrolysis: 3.01 V; - constant potential imposed on the cathode: -0.91V; - temperature: 75 ° C.
  • Example 2 The conditions of Example 2 were reproduced, this time imposing a constant current density, equal to 4 kA per m2 of area of the anode, throughout the duration of the electrolysis. Furthermore, the potential of the cathode was no longer imposed.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Glass Compositions (AREA)
EP90200216A 1989-02-10 1990-01-30 Verfahren zur Herstellung von Alkalimetallsulfid Expired - Lifetime EP0382284B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90200216T ATE94589T1 (de) 1989-02-10 1990-01-30 Verfahren zur herstellung von alkalimetallsulfid.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT1941289 1989-02-10
IT8919412A IT1230714B (it) 1989-02-10 1989-02-10 Procedimento di fabbricazione di un solfuro di un metallo alcalino.

Publications (2)

Publication Number Publication Date
EP0382284A1 true EP0382284A1 (de) 1990-08-16
EP0382284B1 EP0382284B1 (de) 1993-09-15

Family

ID=11157587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90200216A Expired - Lifetime EP0382284B1 (de) 1989-02-10 1990-01-30 Verfahren zur Herstellung von Alkalimetallsulfid

Country Status (7)

Country Link
US (1) US4992148A (de)
EP (1) EP0382284B1 (de)
JP (1) JPH02277789A (de)
AT (1) ATE94589T1 (de)
DE (1) DE69003264T2 (de)
ES (1) ES2046669T3 (de)
IT (1) IT1230714B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995008009A1 (en) * 1993-09-13 1995-03-23 Dsm N.V. Process for the recovery of a heavy metal

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8663806B2 (en) * 2009-08-25 2014-03-04 Apple Inc. Techniques for marking a substrate using a physical vapor deposition material
EP2877614A1 (de) * 2012-07-27 2015-06-03 Basf Se Verfahren zur herstellung eines alkalimetalls
US12012664B1 (en) 2023-03-16 2024-06-18 Lyten, Inc. Membrane-based alkali metal extraction system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH253705A (de) * 1946-02-21 1948-03-31 Krebs & Co Verfahren zur Herstellung von Natriumsulfid.
US2669542A (en) * 1950-03-30 1954-02-16 American Viscose Corp Electrolysis of sodium sulfate

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2227547A (en) * 1935-06-15 1941-01-07 Luigi Achille Process for producing alkali metal sulphides
GB569192A (en) * 1942-05-07 1945-05-11 Krebs & Co Process for the preparation of alkali sulphide
BE790369A (fr) * 1971-10-21 1973-04-20 Diamond Shamrock Corp Procede et appareil pour la preparation d'hydroxydes de metaux alcalins de haute purete dans une cuve electrolytique.
US3864226A (en) * 1972-10-19 1975-02-04 Du Pont Process for electrolyzing aqueous sodium or potassium ion solutions
JPS551351B2 (de) * 1974-03-07 1980-01-12
GB1518387A (en) * 1975-08-29 1978-07-19 Asahi Glass Co Ltd Fluorinated cation exchange membrane and use thereof in electrolysis of an alkali metal halide
JPS5248598A (en) * 1975-10-17 1977-04-18 Asahi Glass Co Ltd Method for producing alkali hydroxide
US4126588A (en) * 1975-12-30 1978-11-21 Asahi Glass Company Ltd. Fluorinated cation exchange membrane and use thereof in electrolysis of alkali metal halide
US4248680A (en) * 1979-01-24 1981-02-03 Ppg Industries, Inc. Electrolytic process and apparatus
US4331523A (en) * 1980-03-31 1982-05-25 Showa Denko Kk Method for electrolyzing water or aqueous solutions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH253705A (de) * 1946-02-21 1948-03-31 Krebs & Co Verfahren zur Herstellung von Natriumsulfid.
US2669542A (en) * 1950-03-30 1954-02-16 American Viscose Corp Electrolysis of sodium sulfate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 104, 1986, page 433, résumé no. 26189j, Columbus, Ohio, US; Y.S. SHIH et al.: "Electrolytic recovery of sulfer and hydrogen from basic sulfide solution", & J. CHIN. INST. CHEM. ENG. 1985, 16(3), 297-9 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995008009A1 (en) * 1993-09-13 1995-03-23 Dsm N.V. Process for the recovery of a heavy metal
BE1007455A3 (nl) * 1993-09-13 1995-07-04 Dsm Nv Werkwijze voor het terugwinnen van een zwaar metaal.

Also Published As

Publication number Publication date
IT1230714B (it) 1991-10-29
IT8919412A0 (it) 1989-02-10
ATE94589T1 (de) 1993-10-15
JPH02277789A (ja) 1990-11-14
DE69003264T2 (de) 1994-03-24
US4992148A (en) 1991-02-12
EP0382284B1 (de) 1993-09-15
DE69003264D1 (de) 1993-10-21
ES2046669T3 (es) 1994-02-01

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