EP1073780B1 - Elektrolyseapparat zur herstellung von halogengasen - Google Patents

Elektrolyseapparat zur herstellung von halogengasen Download PDF

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Publication number
EP1073780B1
EP1073780B1 EP99916899A EP99916899A EP1073780B1 EP 1073780 B1 EP1073780 B1 EP 1073780B1 EP 99916899 A EP99916899 A EP 99916899A EP 99916899 A EP99916899 A EP 99916899A EP 1073780 B1 EP1073780 B1 EP 1073780B1
Authority
EP
European Patent Office
Prior art keywords
electrolysis
cathode
housing
anode
horizontal
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
Application number
EP99916899A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1073780A1 (de
Inventor
Thomas Borucinski
Jürgen Gegner
Karl-Heinz Dulle
Martin Wollny
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.)
ThyssenKrupp Industrial Solutions AG
Original Assignee
Krupp Uhde GmbH
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Filing date
Publication date
Application filed by Krupp Uhde GmbH filed Critical Krupp Uhde GmbH
Publication of EP1073780A1 publication Critical patent/EP1073780A1/de
Application granted granted Critical
Publication of EP1073780B1 publication Critical patent/EP1073780B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar 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
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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

Definitions

  • the invention relates to an electrolysis apparatus for production of halogen gases from aqueous alkali halide solution with several arranged side by side in a stack and in plate-like electrical contact Electrolysis cells, each a housing made of two half-shells made of electrically conductive material with outside Have contact strips on at least one rear wall of the housing, wherein the housing means for feeding the Electrolysis currents and electrolysis input materials and Devices for discharging the electrolysis current and the Electrolysis products and two essentially flat surfaces Has electrodes (anode and cathode), the Anode and the cathode with blind-like openings for a flow through the electrolysis input materials and Electrolysis products provided and by a partition from each other are separated and arranged parallel to each other and by means of metallic stiffeners with the respectively assigned one Rear wall of the housing electrically connected are.
  • the individual electrolytic cells are manufactured in such a way that the respective housing from two half shells each Interposition of the necessary facilities and the cathode and anode as well as the partition and by fixation the same assembled by means of metallic stiffeners and anode and housing or cathode and housing be attached to each other in an electrically conductive manner, then the plate-shaped electrolytic cells thus produced arranged next to each other in a stack in an electrically conductive manner and against each other in the stack for sustainable contact be tense.
  • the electrolysis current is fed to the cell stack on one outer cell of the stack, it passes through the cell stack in a direction substantially perpendicular to the central planes of the plate-shaped electrolysis cells and it is discharged at the other outer cell of the stack. In relation to the middle level, the electrolysis current reaches mean current density values of at least 4 kA / m 2 .
  • Such an electrolysis apparatus is known from DE 196 41 125 A1 Applicant known.
  • this known electrolysis apparatus are the anode or the cathode with the respective rear wall the housing halves over vertical, web-like metallic Stiffeners connected.
  • On the back of the anodes or Half of the cathode shell is a vertical contact strip for the electrical contact to the neighboring, same electrolysis cell attached.
  • the current flows through the contact strip through the back wall into the vertical, web-like metallic stiffeners and of there it is distributed starting from the metallic contact points (Stiffening / anode) over the anode.
  • the current passed through the partition is, it is taken up by the cathode to over the vertical, web-like stiffeners in the rear wall flow to the cathode side and then back into the contact strip and from there to the next electrolytic cell enter.
  • the connection of the current-carrying components is done by welding. In the welds the electrolysis current bundles to form peak current densities.
  • the vertical, web-like metallic stiffeners are designed as webs aligned with the contact strips, the side edges over the entire height of the rear wall and the anode or cathode on the rear wall and the anode or cathode.
  • the vertical bars divide the electrode back space within the respective housing half into individual electrolyte-carrying Segments. So it doesn't become a complete one uneven concentration distribution in the electrolyte comes along the depth of the respective housing half an inlet distributor is provided in each half of the housing, through which the electrolysis input substances into the individual, segments formed by the webs in the half-shells are feedable.
  • gas generating electrolysis processes such as Chlor-alkali electrolysis, hydrochloric acid electrolysis or alkaline water electrolysis performed.
  • chlor-alkali electrolysis aqueous alkali halide solutions, for example sodium and potassium chloride, in the electrolysis cell under the influence of electric current in a aqueous alkali lye, e.g. sodium or potassium lye, and in a halogen gas such as chlorine and hydrogen decomposed.
  • a aqueous alkali lye e.g. sodium or potassium lye
  • a halogen gas such as chlorine and hydrogen decomposed.
  • water electrolysis Water is decomposed and Hydrogen and oxygen are formed on the electrodes.
  • the spatial separation of the electrode spaces is done using the partition mentioned above, generally one Diaphragm or a so-called ion exchange membrane.
  • the Diaphragm is made of a porous material that is related the media, temperatures and Pressing is chemically, thermally and mechanically stable.
  • at the ion exchange membrane is generally perfluorinated hydrocarbons. These membranes are gas and almost liquid-tight, but leave an ion transport in the electric field too.
  • Electrodes that are designed so that they are affected by the electrolysis input materials and the electrolysis products are flowable.
  • Such electrodes are preferably included Provide perforations (perforated sheet, expanded metal, wattle or thin sheets with blind-like openings), so that despite their flat arrangement in the electrolysis cell those formed in the boundary layer during electrolysis Gases enter the back of the electrolytic cell more easily can.
  • Edges or edges of the openings agglomerate the gas bubbles rising in the electrolyte and remain there the gussets between the adjacent partition (membrane) and the break through edges.
  • These bubbles disturb electricity transport, i.e. the mass transport through the Partition because they block the membrane exchange surface and thus make it inaccessible, i.e. inactive.
  • the electrodes are profiled, for example by providing them with grooves and holes. In this way, on the one hand, the gas can escape more easily and, on the other hand, fresh electrolyte can get into the electrolytically active boundary layer between the electrode and the membrane.
  • electrodes with a profile of this type are subjected to current densities above 4 kA / m 2 , however, the gas evolution increases and the profiled electrode then reaches the limit of its gas dissipation capability.
  • the foam formation leads to pressure fluctuations within the electrochemical cell, since the foam at least temporarily closes the cell outlet for the gas formed.
  • the outlet is blown free again by a slight increase in pressure within the cell, which leads to the known effect of the surge flow and to the pressure fluctuations mentioned. This is disadvantageous for the operation of an electrolyzer.
  • the life span of membranes in particular influenced by the concentration distribution.
  • To ensure a homogeneous electrolyte distribution reach either via externally arranged pumps generated additional circulation, or by installing one Baffles in the cell due to internal circulation of a density difference.
  • the object of the invention is to provide an electrolysis apparatus which can also be operated at current densities above 4 kA / m 2 and, accordingly, increased gas generation in the boundary layer while maintaining long-term service life of the membrane and with low pulsation.
  • This task is done with an electrolysis machine at the beginning designated type solved according to the invention in that the blind-like openings of the anode and cathode against the horizontal are inclined.
  • the gas removal from the electrolyte boundary layer close to the membrane can be improved in such a way that current densities of 6 to 8 kA / m 2 are achieved for the first time while maintaining a long service life of the membrane. Due to the inclination of the electrode rods relative to the horizontal, the gas bubbles that form roll along the lower edge of the electrode, collide with bubbles still adhering to the electrode edge and coalesce. This in turn leads to the gas bubbles being accelerated due to the increasing volume, ie the effect accelerates itself. At the same time, the gas volume in the electroactive zone decreases, as a result of which a lower cell voltage is achieved.
  • a suction effect which is caused by the movement of the glass bubbles along the edge of the electrode, ensures that the fresh electrolyte is sucked into the electroactive zone between the membrane or diaphragm and the electrode, which is a necessary prerequisite for long alkali life, for example in chlor-alkali electrolysis.
  • there is a directional flow since all gas bubbles are forced in one direction.
  • the density of the electrolyte / gas mixture decreases on one side due to the increasing gas content, which leads to an internal circulation which is 10 to 100 times greater than when entering the electrolyte stream. Excellent homogenization of the electrolyte is thereby achieved.
  • the angle of inclination towards the blind-like openings the horizontal is between 7 ° and 10 °.
  • each case is parallel arranged to the horizontal and the blind-like Breakthroughs of the anode and cathode against the bottom of the respective housing are arranged inclined.
  • the electrolysis machine in itself is then compared to known electrolysis apparatus to modify only slightly, only the The anode and the cathode must be installed at an angle and on the edge be designed accordingly so that they are appropriate can be installed.
  • the underside of the respective housing inclined to the horizontal is arranged.
  • the individual housings must then face each other previously known housings are practically unchanged, they just have to be inclined to the horizontal can be built in, which automatically makes the blind-like Breakthroughs of cathode and anode in relation to the horizontal are inclined.
  • a generally designated 1 electrolysis apparatus for Production of halogen gases from aqueous alkali halide solution has several, arranged side by side in a stack and plate-like in electrical contact Electrolysis cells 2, examples of which are shown in FIG. 1 two such electrolysis cells 2 arranged side by side are shown.
  • Each of these electrolytic cells 2 has one Housing consisting of two half-shells 3, 4 with flange-like Edges are provided, between which by means of seals 5 a partition (membrane) 6 is clamped in each case. The clamping of the membrane 6 can, if necessary, also on others Way.
  • the anode 8 or the cathode 9 each in alignment with the contact strips 7 arranged stiffeners are connected as webs 10 are formed.
  • the webs 10 are preferred along its entire side edge 10A at the anode or Cathode 8, 9 attached in a metallically conductive manner.
  • a suitable one is to supply the electrolysis products Device provided for the respective electrolysis cell 2, such a device is indicated by 11. Likewise is a device for every electrolysis cell Removal of the electrolysis products is provided, but this is not shown.
  • the electrodes are designed such that they are the electrolysis input product or the output products 3 flow through or let flow through, for what the anode 8 and the cathode 9 are designed like blinds, i.e. each from individual blind-like electrode rods exist and exist between the blind-like openings are.
  • a suction effect caused by the movement of the glass bubbles along the edge of the electrode will ensure that fresh electrolyte in the electroactive Zone between membrane 6 or diaphragm and electrode 8, 9 is taken care of, for example, in chlor-alkali electrolysis a necessary requirement for a long Membrane life is.
  • the structure of the electrolysis apparatus is otherwise different not from known electrolysis devices.
  • the sequence several plate-shaped electrolysis cells 2 happens in a framework, the so-called cell framework.
  • the plate-shaped electrolytic cells 2 are between the hooked into the two upper longitudinal beams of the cell frame, that their plate plane is perpendicular to the side member axis stands. So that the plate-shaped electrolytic cells 2 you Transfer weight to the top flange of the side member can have them on the top edge of the plate on each Side of a cantilever-like holder.
  • the holder extends horizontal in the direction of the plate level and protrudes the edges of the flanges.
  • the plate-shaped electrolytic cells are attached Lower edge of the cantilever-like holder on the upper flange on.
  • the plate-shaped electrolysis cells 2 hang comparatively like folders in a hanging file in the cell structure.
  • the plate surfaces of the electrolysis cells stand in a cell frame in mechanical and electrical contact, as if they were be stacked.
  • Electrolysers of this design are Called electrolysers in hanging stack type.
  • the electrolysis cells 2 By lining up several electrolytic cells 2 in Hanging stack construction using known tensioning devices the electrolysis cells 2 via the contact strips 7 each with adjacent electrolytic cells in a stack electrically connected. From the contact strips 7 the current then flows through the half-shells over the webs 10 into the anode 8. After passing through the membrane 6 the current from the cathode 9 is taken up via the lands 10 to flow into the other half shell or the rear wall 3A and here in the contact strip 7 of the next cell convert. In this way the electrolysis current penetrates the entire electrolytic cell stack, whereby he initiated on one outer cell and on the other outer cell is derived.
  • the configuration is not shown in detail in the figures of the electrolytic cells 2 in the lower area the electrolyte inlet.
  • the electrolyte entry can both selectively as well as with a so-called inlet distributor respectively.
  • the inlet distributor is designed so that a tube is arranged in the element, which has openings.
  • the sum of the Cross-sectional area of the openings in the inlet manifold should smaller than or equal to the inner cross section of the distributor pipe his.
  • the electrolysis apparatus 1 can consist of a single cell or preferably by stringing together of several electrolytic cells 2 in a hanging stack design. Are several single cells according to the hanging stack principle pressed together, the single cells be aligned plane-parallel before the jig is closed, otherwise the current transfer from one Single cell to the next not over all contact strips 7 can be done.
  • the invention is not limited to that in the drawings illustrated embodiments limited. Further Refinements are possible without the basic idea leave. So can to the inclination of the blind-like Breakthroughs 8B, 9B and the electrode rods 8A, 9A of the two Electrodes 8, 9 with respect to the horizontal, as shown, the respective electrode 8, 9 obliquely in the respective electrolytic cell 2 are installed. alternative but can also be provided that the entire electrolytic cell is arranged at an angle, such that the bottom the respective housing half-shell with respect to the horizontal is inclined, so that inevitably the blind-like openings 8A, 9B are arranged inclined are and that described in relation to Figures 2 and 3 Effect.

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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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP99916899A 1998-04-11 1999-03-31 Elektrolyseapparat zur herstellung von halogengasen Expired - Lifetime EP1073780B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19816334 1998-04-11
DE19816334A DE19816334A1 (de) 1998-04-11 1998-04-11 Elektrolyseapparat zur Herstellung von Halogengasen
PCT/EP1999/002200 WO1999053122A1 (de) 1998-04-11 1999-03-31 Elektrolyseapparat zur herstellung von halogengasen

Publications (2)

Publication Number Publication Date
EP1073780A1 EP1073780A1 (de) 2001-02-07
EP1073780B1 true EP1073780B1 (de) 2002-02-13

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ID=7864380

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Application Number Title Priority Date Filing Date
EP99916899A Expired - Lifetime EP1073780B1 (de) 1998-04-11 1999-03-31 Elektrolyseapparat zur herstellung von halogengasen

Country Status (20)

Country Link
US (1) US6503377B1 (es)
EP (1) EP1073780B1 (es)
JP (1) JP4460770B2 (es)
KR (1) KR100549653B1 (es)
CN (1) CN1142326C (es)
AR (1) AR019037A1 (es)
AT (1) ATE213286T1 (es)
AU (1) AU742537B2 (es)
BR (1) BR9909589A (es)
CA (1) CA2328150C (es)
DE (2) DE19816334A1 (es)
JO (1) JO2116B1 (es)
MA (1) MA24828A1 (es)
NO (1) NO20005082L (es)
PL (1) PL343179A1 (es)
RU (1) RU2215064C2 (es)
TN (1) TNSN99037A1 (es)
TW (1) TW494144B (es)
WO (1) WO1999053122A1 (es)
ZA (1) ZA992619B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005003527A1 (de) * 2005-01-25 2006-07-27 Uhdenora S.P.A. Elektrolysezelle mit erweiterter aktiver Membranfläche

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10249508A1 (de) * 2002-10-23 2004-05-06 Uhde Gmbh Elektrolysezelle mit Innenrinne
DE102005006555A1 (de) * 2005-02-11 2006-08-17 Uhdenora S.P.A. Elektrode für Elektrolysezellen
DE102006020374A1 (de) * 2006-04-28 2007-10-31 Uhdenora S.P.A. Mikrostrukturierter Isolierrahmen für Elektrolysezellen
DE102006046807A1 (de) * 2006-09-29 2008-04-03 Uhdenora S.P.A. Elektrolysezelle
DE102006046808A1 (de) * 2006-09-29 2008-04-03 Uhdenora S.P.A. Elektrolysezelle mit gewölbter Elektrodenstruktur
DE102006055709B3 (de) * 2006-11-23 2008-02-07 Uhdenora S.P.A. Messzelle für Elektroden und Elektrodenbeschichtungen und Verfahren zur Kontrolle von Elektroden
KR100992716B1 (ko) * 2009-10-13 2010-11-05 석상엽 접촉 비표면적을 증대시킨 유가금속 회수용 전해조
DE102010021833A1 (de) 2010-05-28 2011-12-01 Uhde Gmbh Elektrode für Elektrolysezelle
CN102912399B (zh) * 2012-11-13 2016-03-23 四川石棉华瑞电子有限公司 一种化成生产线用阴极极板结构
KR101764750B1 (ko) 2013-02-05 2017-08-03 애그리컬쳐럴 테크놀로지 리서치 인스티튜트 항-마이코플라즈마 에스피피. 아단위 백신
US10407783B2 (en) 2016-05-26 2019-09-10 Calera Corporation Anode assembly, contact strips, electrochemical cell, and methods to use and manufacture thereof
EP4053307A1 (en) 2021-03-01 2022-09-07 thyssenkrupp nucera AG & Co. KGaA Electrolysis cell, electrolysis device for chlor-alkali electrolysis and use of an electrolysis cell for chlor-alkali electrolysis

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FR850671A (es) * 1939-02-22 1939-12-22
DE2420011C2 (de) * 1974-04-25 1983-05-11 Sigri Elektrographit Gmbh, 8901 Meitingen Sinter-Elektrode für elektrochemische Prozesse
GB1595193A (en) * 1977-03-04 1981-08-12 Ici Ltd Diaphragm cell
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DE3228884A1 (de) * 1982-08-03 1984-02-09 Metallgesellschaft Ag, 6000 Frankfurt Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure
US4511440A (en) * 1983-12-22 1985-04-16 Allied Corporation Process for the electrolytic production of fluorine and novel cell therefor
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005003527A1 (de) * 2005-01-25 2006-07-27 Uhdenora S.P.A. Elektrolysezelle mit erweiterter aktiver Membranfläche

Also Published As

Publication number Publication date
US6503377B1 (en) 2003-01-07
JP2002511530A (ja) 2002-04-16
JO2116B1 (en) 2000-05-21
CA2328150C (en) 2009-12-08
ZA992619B (en) 2000-10-12
DE59900867D1 (de) 2002-03-21
AU742537B2 (en) 2002-01-03
ATE213286T1 (de) 2002-02-15
TW494144B (en) 2002-07-11
CN1142326C (zh) 2004-03-17
CN1296530A (zh) 2001-05-23
JP4460770B2 (ja) 2010-05-12
EP1073780A1 (de) 2001-02-07
RU2215064C2 (ru) 2003-10-27
DE19816334A1 (de) 1999-10-14
KR20010042594A (ko) 2001-05-25
AU3522099A (en) 1999-11-01
KR100549653B1 (ko) 2006-02-08
MA24828A1 (fr) 1999-12-31
CA2328150A1 (en) 1999-10-21
WO1999053122A1 (de) 1999-10-21
AR019037A1 (es) 2001-12-26
PL343179A1 (en) 2001-07-30
NO20005082D0 (no) 2000-10-09
NO20005082L (no) 2000-12-11
TNSN99037A1 (fr) 2001-12-31
BR9909589A (pt) 2000-12-19

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