DE10152791A1 - Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister - Google Patents

Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister

Info

Publication number
DE10152791A1
DE10152791A1 DE10152791A DE10152791A DE10152791A1 DE 10152791 A1 DE10152791 A1 DE 10152791A1 DE 10152791 A DE10152791 A DE 10152791A DE 10152791 A DE10152791 A DE 10152791A DE 10152791 A1 DE10152791 A1 DE 10152791A1
Authority
DE
Germany
Prior art keywords
gas
diffusion electrode
gas diffusion
pocket
caustic soda
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.)
Withdrawn
Application number
DE10152791A
Other languages
German (de)
Inventor
Fritz Gestermann
Hans-Dieter Pinter
Walter Klesper
Andreas Bulan
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.)
Covestro Deutschland AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DE10152791A priority Critical patent/DE10152791A1/en
Priority to KR10-2004-7006032A priority patent/KR20040062953A/en
Priority to AU2002350591A priority patent/AU2002350591A1/en
Priority to US10/493,441 priority patent/US20040262153A1/en
Priority to HU0401580A priority patent/HUP0401580A3/en
Priority to PCT/EP2002/011787 priority patent/WO2003035939A2/en
Priority to CA002464638A priority patent/CA2464638A1/en
Priority to CNA028210026A priority patent/CN1575354A/en
Priority to EP02785267A priority patent/EP1442158A2/en
Priority to JP2003538433A priority patent/JP2005506455A/en
Publication of DE10152791A1 publication Critical patent/DE10152791A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Abstract

An electrochemical half cell, particularly suitable for the production of chlorine from an aqueous solution of an alkaline chloride, comprises an electrode chamber (10) for electrolyte. Several gas pockets (20, 22) for gas are also provided. A gas diffusion electrode (36) separates the gas pockets (20, 22) from the electrode chamber (10). A connecting channel (26) is also provided, by means of which the two gas pockets (20, 22) are connected to each other. Gas in the lower gas pocket (20) can flow into the connecting channel (26) through an outlet opening (28). Said gas climbs therein in the direction of the arrow (46) and arrives in a second gas pocket (22), lying thereabove, through an inlet opening (30). According to the invention, a non-return element (40) is arranged in the connecting channel (26) to avoid ingress of electrolyte (42) into the gas pocket (22).

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Chlor und Natronlauge durch Elektrolyse einer wässrigen NaCl-Lösung mittels Gasdiffusionselektroden. The invention relates to a process for the production of chlorine and sodium hydroxide solution by electrolysis of an aqueous NaCl solution using gas diffusion electrodes.

Verfahren zur Herstellung von Chlor und Natronlauge durch Elektrolyse mittels Gasdiffusionselektroden bei Einsatz einer Druckkompensation zwischen dem höhenabhängigen Druck der Natronlauge vor der Gasdiffusionselektrode und dem konstanten Druck des Sauerstoffs hinter der Gasdiffusionselektrode und der Führung des Sauerstoffs durch Gastaschen dadurch gekennzeichnet, dass der Sauerstoff vor Eintritt in die Gastasche durch eine Gas-/Flüssigkeitstrennvorrichtung geleitet wird. Process for the production of chlorine and caustic soda by means of electrolysis Gas diffusion electrodes when using pressure compensation between the height-dependent pressure of the sodium hydroxide solution in front of the gas diffusion electrode and the constant pressure of the oxygen behind the gas diffusion electrode and the guide of oxygen characterized by gas pockets in that the oxygen before Entry into the gas pocket is passed through a gas / liquid separation device.

Der Einsatz von Gasdiffusionselektroden in unterschiedlichen Elektrolyseprozessen ist bekannt und vielfach beschrieben. Im Falle der Alkalihalogenid-Elektrolyse, bei der die Gasdiffusionselektrode als Sauerstoffverzehrkathode betrieben wird, ist die Gasdiffusionselektrode eine offenporige Membran. Diese ist zwischen Elektrolyt und Gasraum angeordnet und ermöglicht an der Dreiphasengrenze zwischen Elektrolyt, Katalysator und Sauerstoff eine Sauerstoffreduktion. Die Gasdiffusionselektrode kann z. B. nach dem in der DE-A-37 10 168 beschriebenen Verfahren hergestellt werden. The use of gas diffusion electrodes in different electrolysis processes is known and widely described. In the case of alkali halide electrolysis, at The gas diffusion electrode is operated as an oxygen consumption cathode Gas diffusion electrode an open-pore membrane. This is between electrolyte and Gas space arranged and enables on the three-phase boundary between electrolyte, Catalyst and oxygen an oxygen reduction. The gas diffusion electrode can e.g. B. prepared by the method described in DE-A-37 10 168 become.

Die Dichtigkeit der Gasdiffusionselektrode ist jedoch nur bis zu einem endlichen Druckgefälle zwischen Gasseite und Flüssigkeitsseite vorhanden. Ist der Gasdruck zu hoch, bricht Gas durch die Elektrode und die Funktion der Elektrode ist gestört. Ist hingegen der Flüssigkeitsdruck zu hoch, wird zunächst die Dreiphasengrenze in Richtung Gasseite verlagert oder aber es kommt zu einem Flüssigkeitsdurchbruch von Elektrolyt in den Gasraum. However, the tightness of the gas diffusion electrode is only finite There is a pressure drop between the gas side and the liquid side. Is the gas pressure too high, gas breaks through the electrode and the function of the electrode is disturbed. is on the other hand, if the liquid pressure is too high, the three-phase limit in Relocated towards the gas side or there is a liquid breakthrough of electrolyte in the gas space.

Bei technischen Elektrolyseuren, die mit einer Druckkompensation versehen sind, sind die Bauhöhen der einzelnen Gastaschen auf ca. 30-40 cm begrenzt, was zu Druckdifferenzen zwischen Gasseite und Flüssigkeitsseite von 0 bis ca. 40 cm Flüssigkeitssäule führt (siehe DE-A-44 44 114, DE-A-196 22 744, DE-A-197 15 429). In technical electrolysers that are equipped with pressure compensation, the overall heights of the individual gas pockets are limited to approx. 30-40 cm, which too Pressure differences between gas side and liquid side from 0 to approx. 40 cm Liquid column leads (see DE-A-44 44 114, DE-A-196 22 744, DE-A-197 15 429).

Die Gaszuführung (13) in die unterste Gastasche (6) erfolgt von außen, z. B. über einen Stutzen direkt in die Gastasche. Wie in Skizze 1 ersichtlich, erfolgt die Gaszuführung in die nächst höhere Gastasche (6b) über eine Gaseintrittsöffnung (4). Das aus der unteren Gastasche (6a) über die Auslasslöcher (3) entweichende Gas wird in der Gasglocke (8) gesammelt und über die Gaseintrittöffnung (4) der nächst höheren Gastasche (6b) zugeführt. Über den Gasauslass (3) gelangt auch das sich gebildete Kondensat aus der Gaskammer in den Flüssigkeitsraum (2) hinter der Gasglocke (8). The gas supply ( 13 ) in the lowest gas pocket ( 6 ) takes place from the outside, for. B. via a nozzle directly into the gas pocket. As can be seen in sketch 1 , the gas is fed into the next higher gas pocket ( 6 b) via a gas inlet opening ( 4 ). Selected from the lower gas pocket (6a) over the outlet holes (3) escaping gas is collected in the gas bell (8) and fed via the gas inlet opening (4) of the next highest gas pocket (6 b). Via the gas outlet ( 3 ), the condensate that is formed also passes from the gas chamber into the liquid space ( 2 ) behind the gas bell ( 8 ).

Da das gesamte Gas, das über die Gaszuführung (13) in die unterste Gastasche eingebracht wird durch die Gasglocke gesammelt wird, entsteht innerhalb der Gasglocke eine hohe Strömungsgeschwindigkeit. Somit können Flüssigkeitstropfen mit in die Gastasche gerissen werden und dadurch die Funktion der Gasdiffusionselektrode verschlechtert. Since all of the gas that is introduced into the lowermost gas pocket via the gas feed ( 13 ) is collected by the gas bell, a high flow velocity occurs within the gas bell. Liquid droplets can thus be torn into the gas pocket and thereby impair the function of the gas diffusion electrode.

Die Gasdiffusionselektrode wird im Gaseintrittbereich mit Natronlaugetröpfchen kontaktiert, was zu einem Verlust von aktiver Elektrodenoberflächen führen kann. Ebenso nachteilig wirkt sich aus, dass größere Mengen Natronlauge in die Gastasche gelangen und dementsprechend wieder entfernt werden müssen. Es wurde beobachtet, dass diese Natronlauge nicht immer vollständig aus der Gastasche entfernt werden kann, wodurch sich die Natronlauge in dieser Gastasche anreichert. Die Natronlaugeanreicherung in der Gastasche wird dadurch begünstigt, dass sich der Gas-/Flüssigkeitsauslass der Gastasche gegenüber der Sauerstoffeinlassstelle befindet. Bemerkbar wird die vermehrte Flüssigkeitszufuhr durch eine Erhöhung der Elektrolysespannung. The gas diffusion electrode is covered with sodium hydroxide droplets in the gas inlet area contacted, which can lead to a loss of active electrode surfaces. Another disadvantage is that larger quantities of sodium hydroxide in the gas pocket arrive and must be removed accordingly. It was observed that this caustic soda is not always completely out of the gas pocket can be removed, whereby the sodium hydroxide solution accumulates in this gas pocket. The sodium hydroxide enrichment in the gas pocket is favored by the fact that the Gas / liquid outlet of the gas pocket opposite the oxygen inlet point located. The increased fluid intake is noticeable by an increase in the Electrolysis voltage.

Aufgabe der Erfindung war es, die Gaszuführung in die Gastasche so zu gestalten, dass der einströmende Sauerstoff keine Flüssigkeit in die Gastasche einbringt. The object of the invention was to design the gas supply into the gas pocket in such a way that the inflowing oxygen does not bring any liquid into the gas pocket.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, dass das Gas in der Gasglocke (8) bevor es in die Gastasche gelangt, durch eine Gas-/Flüssigkeitstrennvorrichtung (7) geleitet wird. Hierzu kann z. B. in den oberen Teil der Gasglocke ein poröses Metallfilzgewebe eingebaut werden. Ebenfalls sind Kunststoffschwämme, offenporige Sintermetalle aus geeigneten Werkstoffen, die eine ausreichende Beständigkeit gegen Natronlauge aufweisen wie z. B. Nickel oder Kunststoff wie z. B. Polytetrafluorethylen. Ebenso sind Kunststoff oder Metallfliese einsetzbar. Eine weitere Möglichkeit der Ausführung des erfindungsgemäßen Verfahrens besteht darin, das Gas durch entsprechend geformte Gasumlenkbleche so zu führen, dass eine Tropfenabscheidung erfolgt. Eine weitere Ausführungsform ist in Skizze 4 dargestellt, darin wird die Gasglocke (8) in einen Bereich getrennt, in dem das Gas aufsteigt (9) und einen Bereich in dem kein Gas aufsteigt (10). Die beiden Bereiche der Gasglocke werden durch ein Blech (11) getrennt und werden z. B. über eine Bohrung (12) miteinander verbunden. The object is inventively achieved in that the gas in the gas bell (8) before it passes into the gas bag, is passed through a gas / liquid separator (7). For this purpose, e.g. B. a porous metal felt fabric can be installed in the upper part of the gas bell. Also plastic sponges, open-pore sintered metals made of suitable materials that have sufficient resistance to caustic soda such as. B. nickel or plastic such. B. polytetrafluoroethylene. Plastic or metal tiles can also be used. Another possibility of executing the method according to the invention is to guide the gas through appropriately shaped gas deflection plates in such a way that droplet separation takes place. Another embodiment is shown in sketch 4 , in which the gas bell ( 8 ) is separated into an area in which the gas rises ( 9 ) and an area in which no gas rises ( 10 ). The two areas of the gas bell are separated by a sheet ( 11 ) and are z. B. connected to each other via a bore ( 12 ).

Besonders vorteilhaft reicht die Gasglocke über zwei Gastaschenhöhen. Am unteren Rand der unteren Gastasche gelangt das Gas aus der Gastasche heraus und wird direkt durch eine Gassammelvorrichtung, wie z. B. einer Gasglocke, gesammelt und zur Gaseinlassöffnung der darüberliegenden Gastasche geleitet. Die Gaseinlassöffnung befindet sich am oberen Rand der Gastasche. Je nach Druckverhältnissen stellt sich ein entsprechender Flüssigkeitsstand in der Gastasche ein. Oberhalb dieses Flüssigkeitsstandes wird die Gas-/Flüssigkeitstrennvorrichtung eingebaut. The gas bell particularly advantageously extends over two gas pocket heights. At the bottom At the edge of the lower gas pocket, the gas comes out of the gas pocket and becomes directly through a gas collection device such as B. a gas bell, collected and directed to the gas inlet opening of the gas pocket above. The Gas inlet opening is at the top of the gas pocket. Depending on the pressure conditions there is a corresponding liquid level in the gas pocket. Above this Liquid level, the gas / liquid separation device is installed.

Claims (2)

1. Verfahren zur Herstellung von Chlor und Natronlauge durch Elektrolyse einer wässrigen NaCl-Lösung mittels Gasdiffusionselektroden bei Einsatz einer Druckkompensation zwischen dem höhenabhängigen Druck der Natronlauge vor der Gasdiffusionselektrode und dem konstanten Druck des Sauerstoffs hinter der Gasdiffusionselektrode und der Führung des Sauerstoffs durch Gastaschen dadurch gekennzeichnet, dass der Sauerstoff vor Eintritt in die Gastasche durch eine Gas-/Flüssigkeitstrennvorrichtung geleitet wird. 1. A process for the production of chlorine and caustic soda by electrolysis of aqueous solution of NaCl behind the gas diffusion electrode and the guide of the oxygen in a means of gas diffusion electrodes when using a pressure compensation between the height-dependent pressure of the caustic soda prior to the gas diffusion electrode and the constant pressure of the oxygen by gas pockets in that the oxygen is passed through a gas / liquid separation device before entering the gas pocket. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Gas-/Flüssigkeitstrennvorrichtung ein poröses Metallfilzgewebe, Kunststoffschwämme, offenporige Sintermetalle oder Kunststoff oder Metallfliese verwendet werden. 2. The method according to claim 1, characterized in that as Gas / liquid separation device a porous metal felt fabric, plastic sponges, Open-pore sintered metal or plastic or metal tile used become.
DE10152791A 2001-10-25 2001-10-25 Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister Withdrawn DE10152791A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DE10152791A DE10152791A1 (en) 2001-10-25 2001-10-25 Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister
KR10-2004-7006032A KR20040062953A (en) 2001-10-25 2002-10-22 Electrochemical half cell
AU2002350591A AU2002350591A1 (en) 2001-10-25 2002-10-22 Electrochemical half cell
US10/493,441 US20040262153A1 (en) 2001-10-25 2002-10-22 Electrochemical half cell
HU0401580A HUP0401580A3 (en) 2001-10-25 2002-10-22 Electrochemical half cell
PCT/EP2002/011787 WO2003035939A2 (en) 2001-10-25 2002-10-22 Electrochemical half cell
CA002464638A CA2464638A1 (en) 2001-10-25 2002-10-22 Electrochemical half cell
CNA028210026A CN1575354A (en) 2001-10-25 2002-10-22 Electrochemical half-cell
EP02785267A EP1442158A2 (en) 2001-10-25 2002-10-22 Electrochemical half cell
JP2003538433A JP2005506455A (en) 2001-10-25 2002-10-22 Electrochemical half-cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE10152791A DE10152791A1 (en) 2001-10-25 2001-10-25 Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister

Publications (1)

Publication Number Publication Date
DE10152791A1 true DE10152791A1 (en) 2003-05-08

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Family Applications (1)

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DE10152791A Withdrawn DE10152791A1 (en) 2001-10-25 2001-10-25 Process for the production of chlorine and caustic soda by electrolysis using a gas diffusion electrode demister

Country Status (10)

Country Link
US (1) US20040262153A1 (en)
EP (1) EP1442158A2 (en)
JP (1) JP2005506455A (en)
KR (1) KR20040062953A (en)
CN (1) CN1575354A (en)
AU (1) AU2002350591A1 (en)
CA (1) CA2464638A1 (en)
DE (1) DE10152791A1 (en)
HU (1) HUP0401580A3 (en)
WO (1) WO2003035939A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022210670A1 (en) 2022-10-10 2024-04-11 Volkswagen Aktiengesellschaft Process for manufacturing a battery pouch cell

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI568888B (en) 2011-09-15 2017-02-01 第諾拉工業公司 Gas-diffusion electrode
BR112014031220A2 (en) 2012-06-12 2017-06-27 Univ Monash breathable electrode structure and method and system for use in water separation
AU2014295914A1 (en) 2013-07-31 2016-02-11 Aquahydrex Pty Ltd Composite three-dimensional electrodes and methods of fabrication
CA3127358A1 (en) 2019-02-01 2020-08-06 Aquahydrex, Inc. Electrochemical system with confined electrolyte

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213833A (en) * 1978-09-05 1980-07-22 The Dow Chemical Company Electrolytic oxidation in a cell having a separator support
DE4444114C2 (en) * 1994-12-12 1997-01-23 Bayer Ag Electrochemical half cell with pressure compensation
DE19622744C1 (en) * 1996-06-07 1997-07-31 Bayer Ag Pressure-compensated electrochemical half-cell
US6093853A (en) * 1997-07-04 2000-07-25 Nok Corporation Phenylenediamine derivative, production method thereof and antioxidant for rubber using it as effective constituent
ATE497032T1 (en) * 1999-08-27 2011-02-15 Asahi Chemical Ind ELEMENTARY CELL FOR USE IN AN ELECTROLYSIS CELL WITH AQUEOUS ALKALINE METAL CHLORIDE SOLUTION

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022210670A1 (en) 2022-10-10 2024-04-11 Volkswagen Aktiengesellschaft Process for manufacturing a battery pouch cell
DE102022210670B4 (en) 2022-10-10 2024-04-18 Volkswagen Aktiengesellschaft Process for manufacturing a battery pouch cell

Also Published As

Publication number Publication date
US20040262153A1 (en) 2004-12-30
HUP0401580A2 (en) 2004-11-29
CN1575354A (en) 2005-02-02
HUP0401580A3 (en) 2005-07-28
CA2464638A1 (en) 2003-05-01
EP1442158A2 (en) 2004-08-04
WO2003035939A2 (en) 2003-05-01
KR20040062953A (en) 2004-07-09
AU2002350591A1 (en) 2003-05-06
WO2003035939A3 (en) 2004-01-08
JP2005506455A (en) 2005-03-03

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Owner name: BAYER MATERIALSCIENCE AG, 51373 LEVERKUSEN, DE

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