EP0540080B1 - Elektrolysezelle zur Herstellung von Gas - Google Patents

Elektrolysezelle zur Herstellung von Gas Download PDF

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Publication number
EP0540080B1
EP0540080B1 EP92203142A EP92203142A EP0540080B1 EP 0540080 B1 EP0540080 B1 EP 0540080B1 EP 92203142 A EP92203142 A EP 92203142A EP 92203142 A EP92203142 A EP 92203142A EP 0540080 B1 EP0540080 B1 EP 0540080B1
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EP
European Patent Office
Prior art keywords
valve
electrolyte
chamber
cell according
electrolysis
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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
Application number
EP92203142A
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English (en)
French (fr)
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EP0540080A1 (de
Inventor
Luciano Chiti
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Solvay SA
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Solvay SA
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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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the present invention relates to an electrolysis cell in which a gas is produced.
  • an electrolysis cell of the type comprising at least two respectively anodic and cathodic electrolysis chambers, at least one of which is in communication, at its lower part, with an electrolyte intake duct and, at its upper part, with an electrolyte degassing chamber arranged above it.
  • An electrolysis cell of this type is described in patent application EP-A 0412600 (SOLVAY & CIE), where it is used for the manufacture of chlorine by electrolysis of an aqueous solution of alkali metal chloride, for example of sodium.
  • a membrane selectively permeable to cations for example a membrane made of perfluorinated polymer comprising functional groups derived from carboxylic or sulfonic acid
  • an aqueous solution of sodium chloride is introduced continuously into the anode chamber via the aforementioned intake duct and chlorine is produced at the anode under the effect of the electrolysis current.
  • the chlorine generated at the anode ensures, by gazosiphon, a natural ascending circulation of the electrolyte in the anode chamber and a chlorine emulsion is collected in a dilute aqueous solution of sodium chloride, in the degassing chamber surmounting the anode chamber . In this chamber there is a separation of the chlorine and the dilute sodium chloride solution which are collected separately.
  • Monopolar electrolysis cells of the type described above generally comprise several anode chambers alternating with cathode chambers and it is desirable that the composition of the electrolyte in the anode (or cathode) chambers be uniform.
  • the active chlorine present in the anolyte then risks passing into the cathode chamber and forming there, by reaction with the sodium hydroxide solution therein, sodium hypochlorite capable of damaging the cathode.
  • EP-A-75401 describes an electrolysis cell which comprises a valve in the electrolyte recycling line connecting the degassing chamber to the electolyte intake pipe.
  • the invention aims to improve the known electrolysis cell described above, by standardizing the composition of the electrolyte in the electrolysis chambers and by minimizing the amount of active chlorine capable of passing through the membrane and passing in the cathode chamber in the event of the cell's electrical supply being stopped.
  • the invention relates to an electrolysis cell for the production of a gas, comprising at least two electrolysis chambers, respectively anodic and cathodic, at least one of which is in communication, at its lower part, with an electrolyte intake duct and, at its upper part, with an electrolyte degassing chamber arranged above it and provided with a gas discharge opening and a discharge opening electrolyte;
  • an electrolyte recycling pipe connects the degassing chamber to the intake pipe and includes a valve which is opened or closed automatically, depending on whether the pressure downstream of the valve is lower or higher than the pressure in upstream of the valve.
  • upper part and lower part of the electrolysis chamber is intended to denote the zones of the latter which are respectively located above and below the middle of its height. In practice, the upper part is the upper third of the chamber and the lower part is the lower third.
  • upstream and downstream are defined with respect to the direction of circulation in the recycling line, from the degassing chamber to the electrolyte intake pipe.
  • the intake duct electrolyte is used to introduce fresh electrolyte into the electrolysis chamber.
  • the degassing chamber located above the electrolysis chamber is well known in the art and is used to collect the emulsion produced in the electrolysis chamber and to separate the gas and a diluted electrolyte therefrom.
  • the gas discharge opening is generally located in the upper part of the degassing chamber.
  • the recycling line connects the degassing chamber to the electrolyte intake line. It opens into the lower part of the degassing chamber and has the function of recycling in the electrolysis chamber a fraction of the electrolyte released in the degassing chamber, the balance being evacuated by the aforementioned evacuation opening of electrolyte. This opening is located at an intermediate level between that of the gas discharge opening and that where the recycling pipe opens.
  • the expressions "upper part” and "lower part" of the degassing chamber have the definition given above in relation to the electrolysis chamber.
  • the valve on the recycling line has the function of allowing the circulation of the electrolyte in the recycling line during normal operation of the cell and of immediately shutting off this line in the event of the power supply to the cell being stopped. . Closing the valve results in immediate evacuation of the electrolyte contained in the electrolysis chamber, by sweeping with a stream of fresh electrolyte from the supply line.
  • the valve is designed so as to be operated automatically under the effect of pressure variations in the recycling line upstream and downstream of said valve.
  • the upstream is the area of the recycling pipe, which is located between the degassing chamber and the valve and immediately adjacent to it
  • the downstream is the area of this pipe which is between the pipe electrolyte intake and the valve and immediately adjacent to it.
  • the valve is designed so that it is open when the downstream pressure is lower than the upstream pressure and that it is closed when the downstream pressure is higher than the upstream pressure.
  • Valves which can be used in the cell according to the invention are well known in the art. Examples of such valves include oscillating check valves, valves and float valves.
  • the invention finds particular application in electrolysis cells for the production of chlorine, in which the anode chamber is separated from the cathode chamber by an ion separator.
  • the ion separator used in this embodiment of the invention is a sheet interposed between the electrolysis chambers and made of a material capable of being traversed by an ion current during the operation of the cell. It can either be a diaphragm permeable to aqueous electrolytes or a membrane with selective permeability.
  • diaphragms which can be used in the cell according to the invention are asbestos diaphragms, such as those described in patent US-A-1,855,497 (STUART) and diaphragms made of organic polymers, such as those described in patent application EP -A-7674 (SOLVAY & Cie).
  • membrane with selective permeability is understood to mean a thin, non-porous membrane comprising an ion-exchange material.
  • the choice of the material constituting the membrane and of the ion exchange material will depend on the nature of the electrolytes subjected to the electrolysis and on the products which it is sought to obtain.
  • the membrane material is chosen from those which are capable of withstanding the thermal and chemical conditions normally prevailing in the cell during electrolysis, the ion exchange material being chosen from anion exchange materials or cation exchange materials, depending on the electrolysis operations for which the cell is intended.
  • membranes which are well suited are cationic membranes polymer fluorinated, preferably perfluorinated, containing cationic functional groups derived from sulfonic acids, carboxylic acids or phosphonic acids or mixtures of such functional groups.
  • membranes of this type are those described in patents 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 which are particularly suitable for this application of the cell according to the invention are those known under the names "NAFION” (DU PONT DE NEMOURS & Co) and "FLEMION” (ASAHI GLASS COMPANY LTD).
  • the anode chamber is supplied with sodium chloride brine and the cathode chamber is supplied with water or a dilute solution of alkali metal hydroxide. It is recommended that the electrolysis chamber which is connected to the degassing chamber and to the supply duct is the anode chamber. In this case, closing the recycling circuit valve (caused by an interruption in the electrical supply to the cell) has the effect of replacing the anolyte with the brine supplied in the anode chamber.
  • the cell may comprise a second degassing chamber which is in communication, on the one hand with the upper part of the cathode chamber and, on the other hand with the conduit serving for the admission of water or aqueous solution diluted alkali metal hydroxide in the cathode chamber.
  • the connection of the degassing chamber with the intake duct of the cathode chamber is, according to the invention, a recycling duct comprising a valve which is open or closed depending on whether the pressure downstream of the valve is lower or higher than the pressure upstream of the valve.
  • the cell according to the invention can comprise a single anode chamber and a single cathode chamber, or a plurality of alternately anode and cathode chambers.
  • the cell comprises several anode chambers alternating with cathode chambers from which they are isolated by ionic separators, the anode (or cathode) chambers being connected bypass to the degassing and to the electrolyte supply duct.
  • the cell according to the invention finds an interesting application for the production of chlorine and aqueous solutions of alkali metal hydroxide, for example sodium hydroxide.
  • Figure 1 is a block diagram of the cell according to the invention, in longitudinal elevation.
  • Figure 2 is a partial view, in longitudinal elevation, of a particular embodiment of the cell according to the invention.
  • Figures 3 and 4 are views similar to Figures 2, of two other embodiments of the cell according to the invention.
  • the reference notation 1 designates an electrolysis cell of the filter press type, intended for the manufacture of chlorine and aqueous sodium hydroxide solutions by electrolysis of aqueous sodium chloride solutions.
  • the cell 1 comprises a series of anode electrolysis chambers 2, alternating with cathode electrolysis chambers 3.
  • Membranes 18 selectively permeable to cations separate the anode chambers 2 from the cathode chambers 3.
  • the anode chambers 2 contain anodes connected to the positive terminal of a direct current source and the cathode chambers 3 contain cathodes which are connected to the negative terminal of the current source.
  • the anodes, cathodes and current source are not shown in the drawings.
  • Tubes 4 connect the lower part of the anode chambers 2 to a conduit 5 for admitting an aqueous solution of sodium chloride.
  • Other pipes 6 connect the upper part of the anode chambers 2 to a degassing chamber 7 disposed above the cell 1.
  • the degassing chamber 7 is in communication at its upper part, via a conduit 8, with a collector of chlorine 9.
  • a pipe 10 connects its lower part to the pipe 5.
  • a pipe 16 opens into the degassing chamber, at a level 17 situated between those where the pipe 8 and the pipe 10 open respectively into the degassing room. It is used to drain the electrolyte from the degassing chamber, when it reaches level 17.
  • the pipe 10 serves as a pipe for recycling the anolyte, from the degassing chamber 7 to the inlet pipe 5. It comprises a valve 11 which has the function of '' be open during normal cell operation and closed if electrolysis stops. To this end, the valve 11 is designed so that it is open in the case where the difference in pressures in the pipe 10, between the points A and B located respectively upstream and downstream of the valve 11 is positive and that it be closed when this difference is negative. Embodiments of the valve 11 are shown diagrammatically in FIGS. 2, 3 and 4 commented on below.
  • the pipe 10 may also include an adjustment valve 19, intended to regulate the flow of electrolyte in the recycling pipe 10, when the valve 11 is in the open position.
  • the anode chambers are no longer the seat of a generation of chlorine gas, so that the difference in the hydrostatic pressures between the zones A and B of the pipe 10 becomes approximately zero, this which results in the closing of the valve 11 which thus closes the line 10.
  • the closure of the recycling line 10 prevents the flow of fresh electrolyte from the line 5 back up through the line 10 and escapes through the conduit 16, bypassing the anode chambers 2; it thus has the immediate result of a scanning of the anode chambers 2 with an ascending current of fresh electrolyte coming from the conduit 5.
  • the electrolyte leaving the anode chambers 2 passes through the degassing chamber 7 from which it escapes through the conduit 16 .
  • FIG. 2 shows on a larger scale a particular embodiment of the cell according to the invention.
  • vertical frames 20 and 21 contiguous to the membranes 18 respectively delimit the anode chambers 2 and the cathode chambers 3.
  • the frames 20 are crossed by the pipes 4 and 6 which bring the anode chambers 2 into communication respectively with the intake duct 5 and with the degassing chamber 7.
  • the electrolyte discharge duct 16 comprises a vertical tube 22 which passes through the bottom of the chamber 7 and opens into the latter at the level 17.
  • the valve 11 comprises a box 12 in which a float 13, mounted on a joint 14 secured to the box 12, can oscillate between a rest position, visible in FIG. 2, and a high position against a seat 15.
  • the float 13 closes the pipe 10, while in the rest position shown in Figure 2, it allows the passage of electrolyte through the valve 11.
  • the float is made of a material whose specific mass is less than that of the electrolyte brought to flow in line 10, during the operation of the cell.
  • the pressure at A is higher than the pressure at B and sufficient to push back the float 13 and move it away from its seat 15, so that the valve 11 is open. If the electrolysis stops, the difference in pressures between zones A and B becomes negligible so that the float 13 is pushed back against its seat 15 and closes the valve 11.
  • the valve 11 is mounted in a horizontal section 23 of the pipe 10 and includes a valve 24, oscillating on a horizontal shaft 25.
  • the pressure at A is higher than the pressure at B and sufficient to move the valve 24 from its vertical position, so that the valve 11 is open.
  • the difference in pressures between zones A and B becomes negligible so that the valve falls back against its seat under the effect of its own weight and closes the valve 11.
  • the cell in FIG. 4 differs from the cells in FIGS. 2 and 3 in that the pipes 6 open into the chamber 7 above the level 17, but below the level of the opening 8.
  • the valve 11 comprises a housing 26 in which a valve 27 is free to move between its seat 28 and a stop 29.
  • the pressure at A is higher than the pressure at B so that the valve 27 rests on the stop 29 and opens the valve 11.
  • the pressure at B quickly becomes greater than the pressure at A, which results in the valve 27 being pushed against its seat 28 and closing the valve 11.

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  • Chemical & Material Sciences (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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)
  • Treating Waste Gases (AREA)

Claims (10)

  1. Elektrolysezelle für die Erzeugung eines Gases, umfassend mindestens zwei Elektrolysekammern, eine anodische (2) bzw. eine kathodische (3), von denen mindestens eine in ihrem unteren Teil mit einer Elektrolyteinlaßleitung (5) und in ihrem oberen Teil mit einer Elektrolytentgasungskammer (7) in Verbindung steht, welche über ihr angeordnet und mit einer Gasabzugsöffnung (8) und einer Elektrolytabzugsöffnung (16) versehen ist, dadurch gekennzeichnet, daß eine Elektrolytrückführleitung (10) die Entgasungskammer (7) mit der Einlaßleitung (5) verbindet und ein Ventil (11) aufweist, das automatisch geöffnet oder geschlossen wird, je nachdem, ob der Druck hinter (B) dem Ventil (11) niedriger oder höher als der Druck vor (A) dem Ventil ist.
  2. Zelle nach Anspruch 1, dadurch gekennzeichnet, daß das Ventil (11) einen Ventilkörper (27) umfaßt, der sich vertikal zwischen einem Sitz (28) und einem Anschlag (29) bewegen kann.
  3. Zelle nach Anspruch 1, dadurch gekennzeichnet, daß das Ventil (11) eine um eine horizontale Achse (25) schwingende Klappe (24) in einem horizontalen Teilstück (23) der Rückführleitung (10) umfaßt.
  4. Zelle nach Anspruch 1, dadurch gekennzeichnet, daß das Ventil (11) einen Schwimmer (13) mit einem geringeren spezifischen Gewicht als demjenigen des Elektrolyten umfaßt.
  5. Zelle nach einem beliebigen der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sich die Elektrolytabzugsöffnung (16) auf einem Niveau (17) befindet, das unter demjenigen der Gasabzugsöffnung (8) und über demjenigen liegt, wo die Rückführleitung in die Entgasungskammer (7) mündet.
  6. Zelle nach Anspruch 5, dadurch gekennzeichnet, daß die Verbindung der Elektrolysekammer (2) mit der Entgasungskammer (7) einen Rohrstutzen (6) umfaßt, der über dem Niveau (17) der Elektrolytabzugsöffnung und unter dem Niveau der Gasabzugsöffnung (8) in die Entgasungskammer (7) mündet.
  7. Zelle nach einem beliebigen der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß eine Ionentrennwand (18) die anodische Kammer (2) von der kathodischen Kammer (3) trennt.
  8. Zelle nach Anspruch 6, dadurch gekennzeichnet, daß die Ionentrennwand (18) eine selektiv für Kationen permeable Membran ist.
  9. Zelle nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß sie mehrere anodische Kammern (2) umfaßt, welche sich mit kathodischen Kammern (3) abwechseln, von denen sie durch Ionentrennwände (18) getrennt sind, wobei die anodischen (oder kathodischen) Kammern parallel zueinander mit der Entgasungskammer (7) und der Elektrolyteinlaßleitung (5) verbunden sind.
  10. Zelle nach einem beliebigen der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß die Elektrolysekammer (2), welche mit der Entgasungskammer (7) in Verbindung steht, die anodische Kammer ist, wobei diese dazu ausersehen ist, mit einer wäßrigen Alkalimetallchloridlösung gespeist zu werden.
EP92203142A 1991-10-23 1992-10-13 Elektrolysezelle zur Herstellung von Gas Expired - Lifetime EP0540080B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI912813 1991-10-23
ITMI912813A IT1251419B (it) 1991-10-23 1991-10-23 Cella di elettrolisi per la produzione di un gas

Publications (2)

Publication Number Publication Date
EP0540080A1 EP0540080A1 (de) 1993-05-05
EP0540080B1 true EP0540080B1 (de) 1996-02-14

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EP92203142A Expired - Lifetime EP0540080B1 (de) 1991-10-23 1992-10-13 Elektrolysezelle zur Herstellung von Gas

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US (1) US5425863A (de)
EP (1) EP0540080B1 (de)
JP (1) JPH05239679A (de)
AT (1) ATE134225T1 (de)
BR (1) BR9204084A (de)
CA (1) CA2080519A1 (de)
CZ (1) CZ318392A3 (de)
DE (1) DE69208321T2 (de)
ES (1) ES2086642T3 (de)
HU (1) HUT63469A (de)
IT (1) IT1251419B (de)
PL (1) PL296343A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1528126A1 (de) * 2003-10-30 2005-05-04 Vandenborre Hydrogen Systems N.V. Integriertes Elektrolysiermodul mit internem Gas/Flüssigkeit-Abscheider
CN101981744A (zh) * 2007-04-03 2011-02-23 新空能量公司 用于产生可再生氢并截留二氧化碳的电化学系统、装置和方法
CA2637865A1 (en) * 2008-07-15 2010-01-15 1755610 Ontario Inc. Electrolyser module
WO2012129510A1 (en) 2011-03-24 2012-09-27 New Sky Energy, Inc. Sulfate-based electrolysis processing with flexible feed control, and use to capture carbon dioxide
CN105129922A (zh) * 2015-09-07 2015-12-09 太仓文广汇清洁设备有限公司 一种井水电解装置

Family Cites Families (15)

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Publication number Priority date Publication date Assignee Title
US1855497A (en) * 1928-05-07 1932-04-26 Hooker Electrochemical Co Electrolytic cathode-diaphragm structure
CH336805A (de) * 1956-01-14 1959-03-15 Lonza Ag Sicherheits-Schaltung für Druckelektrolyseure
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.
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
ZA793535B (en) * 1978-07-31 1980-07-30 Solvay Permeable diaphragm for an electrochemical cell
US4250126A (en) * 1979-03-30 1981-02-10 Dow Yates Chlorine generator and method
US4329215A (en) * 1980-06-13 1982-05-11 Frank Scoville Sodium hypochorite production and storage system
US4344833A (en) * 1980-12-08 1982-08-17 Olin Corporation Restrictor apparatus for electrolyte flow conduit
EP0075401A3 (de) * 1981-09-03 1983-06-15 Ppg Industries, Inc. Bipolare Elektrolysezelle
US4411759A (en) * 1982-02-04 1983-10-25 Olivier Paul D Electrolytic chlorine generator
BE1004364A3 (fr) * 1989-08-11 1992-11-10 Solvay Chassis pour electrolyseur du type filtre-presse et electrolyseur monopolaire du type filtre-presse.
IT1237543B (it) * 1989-12-28 1993-06-08 Solvay Elettrolizzatore per la produzione di un gas,comprendente un impilamento di quadri verticali

Also Published As

Publication number Publication date
ITMI912813A0 (it) 1991-10-23
US5425863A (en) 1995-06-20
JPH05239679A (ja) 1993-09-17
IT1251419B (it) 1995-05-09
ATE134225T1 (de) 1996-02-15
DE69208321T2 (de) 1996-09-19
CA2080519A1 (fr) 1993-04-24
DE69208321D1 (de) 1996-03-28
HU9203282D0 (en) 1993-03-01
EP0540080A1 (de) 1993-05-05
CZ318392A3 (en) 1993-06-16
HUT63469A (en) 1993-08-30
ITMI912813A1 (it) 1993-04-23
BR9204084A (pt) 1993-05-04
PL296343A1 (en) 1993-07-12
ES2086642T3 (es) 1996-07-01

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