EP0051764A1 - Cellule électrolytique destinée à l'électrolyse de l'acide chlorhydrique pour la fabrication de chlore et d'hydrogène - Google Patents

Cellule électrolytique destinée à l'électrolyse de l'acide chlorhydrique pour la fabrication de chlore et d'hydrogène Download PDF

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Publication number
EP0051764A1
EP0051764A1 EP81108609A EP81108609A EP0051764A1 EP 0051764 A1 EP0051764 A1 EP 0051764A1 EP 81108609 A EP81108609 A EP 81108609A EP 81108609 A EP81108609 A EP 81108609A EP 0051764 A1 EP0051764 A1 EP 0051764A1
Authority
EP
European Patent Office
Prior art keywords
electrodes
grooves
electrolytic cell
chlorine
electrode
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
Application number
EP81108609A
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German (de)
English (en)
Other versions
EP0051764B1 (fr
Inventor
Helmut Dr. Klotz
Ernst Tepe
Lothar Dipl.-Ing. Sesterhenn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0051764A1 publication Critical patent/EP0051764A1/fr
Application granted granted Critical
Publication of EP0051764B1 publication Critical patent/EP0051764B1/fr
Expired legal-status Critical Current

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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms

Definitions

  • the present invention relates to an electrolysis cell for the electrolysis of hydrochloric acid, in particular an electrolysis cell with bipolar electrodes.
  • Such cells are assembled according to the filter press type and form a cell block that can consist of 30 to 50 individual cells. Electrodes made of graphite are usually used. Such cells are e.g. known from U.S. Patent 3,875,040.
  • the present invention therefore relates to an electrolysis cell with bipolar electrodes and electrode gaps subdivided by a diaphragm or a membrane for the production of chlorine and hydrogen from hydrochloric acid, the electrodes having vertical grooves, which is characterized in that the grooves at least in the upper region of the Electrodes have a depth of 20 to 35 mm, preferably 25 to 32 mm.
  • the grooves preferably have a width of 2 to 3 mm.
  • the webs generated between the grooves are preferably 4. to 6 mm wide.
  • the electrodes according to the invention make it possible to reduce the distance between the electrodes and the diaphragm or membrane to 0.05 to 2 mm, preferably to less than 1 mm, the voltage between the electrodes likewise decreasing with the same current strength. This is particularly surprising because, according to the prior art, an increase in voltage due to the increased influence of the gas bubbles would be expected. For diaphragms or membranes with a fabric structure, this means that the diaphragm or membrane can rest directly on the electrode.
  • Electrode 1 shows a cell block with any number of electrode frames 1, 8, 10, 11, 12, in which the graphite electrodes 2 are held in their position by means of elastic seals 13.
  • the electrode frames are pressed against one another via clamping screws 9.
  • Power is supplied to the outer electrodes at + or -.
  • Each electrode acts as an anode 4 on one side and as a cathode 3 (bipolar) on the other side.
  • the space between two electrodes is divided into an anolyte space 5 and a catholyte space 6 by a diaphragm or membrane 7.
  • the hydrochloric acid is introduced into each electrolytic cell from below (not shown). At the top, anolyte and catholyte emerge via separate channels (not shown) in order to avoid mixing of the gases resulting from the electrolysis.
  • Fig. 2 shows a section of a horizontal cross section through the electrolysis cell .
  • the numbers describe, as previously mentioned, the same items as in the description of Fig. 1.
  • FIG. 3 shows the partial section B from FIG. 2 on an enlarged scale.
  • the end faces 16 of the webs 15 have flattened regions 17 near the edges, which makes it easier for the gas bubbles generated between the electrode webs 15 to pass into the space between the webs formed by the grooves.
  • Fig. 4 represents an attempt to explain the phenomenon on which the present invention is based.
  • a partial section from a vertical section through the electrolytic cell along the line CC of FIG. 2 is shown.
  • the arrow 20 indicates the main flow direction of the electrolyte in the groove.
  • Chlorine is deposited on the anode side of the electrode, whereby essentially chlorine gas bubbles form on the front side of the electrode, which become larger over time and detach with a size of 50 to 100 ⁇ diameter.
  • the chlorine gas bubbles which are carried away by the hydrochloric acid coagulate and form larger bubbles. It is now assumed that the main flow 20 of hydrochloric acid is overlaid by vortices 17 and 17 '.
  • the vortices ensure that the small gas bubbles 18 are transported from the area near the diaphragm or membrane into the rear part of the groove, coagulate there or unite with larger gas bubbles 19 already present there.
  • the flow rate of the electrolyte is greatest in the rear area of the groove, where the larger gas bubbles are located, since the electrolyte is carried along by the rising gas bubbles. It will Now assume that the special depth of the grooves according to the invention favors the formation of stable vertebrae 17 due to a resonance-like effect.
  • the formation of the vortices is further favored by a small distance between the membrane or diaphragm and the electrode, since then the flow resistance between the diaphragm and the electrode is greater due to the friction, so that the electrolyte flow is delayed here.
  • the distance between the electrode and the diaphragm or membrane should therefore preferably be smaller than the width of the grooves.
  • FIG. 5 shows a partial section of a vertical section through the electrolytic cell analogous to FIG. 4.
  • the electrode here has grooves which have a depth that increases from bottom to top.
  • the groove depth in the area of the electrolyte inlet can be 10 to 15 mm and increase to 25 to 32 mm over the height of the electrode.
  • the naturally developing vertebrae 17 have a diameter of 10 to 15 mm. Since the gas volume in the cell increases over the height of the electrode, a groove depth is sufficient in the lower part, which corresponds approximately to the vortex diameter.
  • the electrolysis cell according to the invention not only leads to a considerable saving in specific electrical energy due to the lower voltage drop, but surprisingly, a lower chlorine content in the hydrogen is simultaneously determined.
  • the fluttering of the membrane, which is frequently observed with a larger electrode spacing, is eliminated, so that the service life of the membrane is significantly increased.
  • Hydrochloric acid with an HCl concentration of 20% is introduced at the bottom into a test electrolysis cell with a height of 110 mm and bipolar graphite electrodes, in which the anolyte and catholyte are separated by a diaphragm.
  • the cell is operated with a current density of 5 kA / m 2 .
  • the temperature of the hydrochloric acid at the outlet is 80 ° C.
  • the electrodes had a groove width of 2.5 mm and a web width of 5 mm. The distance between the electrodes was 6 mm.
  • the diaphragm has a sheet thickness of 85 mm. Electrodes with different groove depths are used. Table I below shows the voltage drop measured between the electrodes and the chlorine content in the hydrogen.
  • Electrode spacing reduced to 0.5 mm with a groove depth of 20 mm.
  • the voltage drop is 1.710 V.
  • the Cl 2 content in H 2 is 0.2 vol.%.

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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)
EP81108609A 1980-11-06 1981-10-21 Cellule électrolytique destinée à l'électrolyse de l'acide chlorhydrique pour la fabrication de chlore et d'hydrogène Expired EP0051764B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3041897 1980-11-06
DE19803041897 DE3041897A1 (de) 1980-11-06 1980-11-06 Salzsaeure-elektrolysezelle zur herstellung von chlor und wasserstoff

Publications (2)

Publication Number Publication Date
EP0051764A1 true EP0051764A1 (fr) 1982-05-19
EP0051764B1 EP0051764B1 (fr) 1984-03-28

Family

ID=6116129

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108609A Expired EP0051764B1 (fr) 1980-11-06 1981-10-21 Cellule électrolytique destinée à l'électrolyse de l'acide chlorhydrique pour la fabrication de chlore et d'hydrogène

Country Status (4)

Country Link
US (1) US4402811A (fr)
EP (1) EP0051764B1 (fr)
JP (1) JPS6056435B2 (fr)
DE (2) DE3041897A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159138A1 (fr) * 1984-03-27 1985-10-23 Imperial Chemical Industries Plc Electrode et cellule d'électrolyse
RU2126461C1 (ru) * 1993-02-12 1999-02-20 Де Нора С.п.А. Способ хлорщелочного электролиза и диафрагменный электролизер
EP1103636A1 (fr) * 1999-11-25 2001-05-30 Bayer Ag Plaque pour cellule d'électrolyse
KR100464703B1 (ko) * 2001-12-28 2005-01-05 김병일 붕규산유리조성물 및 이를 이용한 발포유리제조방법

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4119606A1 (de) * 1991-06-14 1992-12-17 Sigri Great Lakes Carbon Gmbh Verfahren und vorrichtung zur aufarbeitung von salzsaeurehaltigem, mit begleitstoffen verunreinigtem wasser
DE102006023261A1 (de) 2006-05-18 2007-11-22 Bayer Materialscience Ag Verfahren zur Herstellung von Chlor aus Chlorwasserstoff und Sauerstoff
US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
TWI633206B (zh) 2013-07-31 2018-08-21 卡利拉股份有限公司 使用金屬氧化物之電化學氫氧化物系統及方法
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
WO2019060345A1 (fr) 2017-09-19 2019-03-28 Calera Corporation Systèmes et procédés utilisant un halogénure de lanthanide
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361656A (en) * 1966-05-16 1968-01-02 Hooker Chemical Corp Wicking electrode for an electrolytic cell
GB1153172A (en) * 1965-05-28 1969-05-29 Metal And Pipeline Endurance L Improvements in or relating to electrodes
DE2209917A1 (de) * 1972-03-02 1973-09-20 Metallgesellschaft Ag Elektrode, insbesondere anode
US4124464A (en) * 1977-10-19 1978-11-07 Rca Corporation Grooved n-type TiO2 semiconductor anode for a water photolysis apparatus

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242065A (en) * 1960-12-21 1966-03-22 Oronzio De Nora Impianti Cell for electrolysis of hydrochloric acid
US3654120A (en) * 1969-07-29 1972-04-04 Nora Int Co Electrolytic cell including bipolar electrodes with resin-impregnated holes in the electrode body
DE2213603A1 (de) * 1972-03-21 1973-10-04 Georg Dr Messner Verfahren und vorrichtung zur elektrolytischen behandlung von chlorwasserstoff enthaltenden loesungen an graphitelktroden unter getrennthaltung der gebildeten gase chlor und wasserstoff
DE2222637A1 (de) * 1972-05-09 1973-11-29 Bayer Ag Halterahmen fuer elektroden von elektrolysevorrichtungen
US4056452A (en) * 1976-02-26 1977-11-01 Billings Energy Research Corporation Electrolysis apparatus
US4013537A (en) * 1976-06-07 1977-03-22 The B. F. Goodrich Company Electrolytic cell design
DE2816152C2 (de) * 1978-04-14 1980-07-03 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Chlor aus Salzsäure durch Elektrolyse und Salzsäure-Elektrolysezelle
US4210511A (en) * 1979-03-08 1980-07-01 Billings Energy Corporation Electrolyzer apparatus and electrode structure therefor
US4256554A (en) * 1980-03-28 1981-03-17 Energy Development Associates, Inc. Electrolytic cell for separating chlorine gas from other gases

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1153172A (en) * 1965-05-28 1969-05-29 Metal And Pipeline Endurance L Improvements in or relating to electrodes
US3361656A (en) * 1966-05-16 1968-01-02 Hooker Chemical Corp Wicking electrode for an electrolytic cell
DE2209917A1 (de) * 1972-03-02 1973-09-20 Metallgesellschaft Ag Elektrode, insbesondere anode
US4124464A (en) * 1977-10-19 1978-11-07 Rca Corporation Grooved n-type TiO2 semiconductor anode for a water photolysis apparatus

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159138A1 (fr) * 1984-03-27 1985-10-23 Imperial Chemical Industries Plc Electrode et cellule d'électrolyse
RU2126461C1 (ru) * 1993-02-12 1999-02-20 Де Нора С.п.А. Способ хлорщелочного электролиза и диафрагменный электролизер
EP1103636A1 (fr) * 1999-11-25 2001-05-30 Bayer Ag Plaque pour cellule d'électrolyse
KR100464703B1 (ko) * 2001-12-28 2005-01-05 김병일 붕규산유리조성물 및 이를 이용한 발포유리제조방법

Also Published As

Publication number Publication date
DE3041897A1 (de) 1982-06-09
EP0051764B1 (fr) 1984-03-28
JPS6056435B2 (ja) 1985-12-10
DE3162905D1 (en) 1984-05-03
JPS57108280A (en) 1982-07-06
US4402811A (en) 1983-09-06

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