EP0687312B1 - Elektrodenanordnung für gasbildende elektrolytische prozesse in zellen mit ionenaustauschermembran oder mit diaphragma - Google Patents
Elektrodenanordnung für gasbildende elektrolytische prozesse in zellen mit ionenaustauschermembran oder mit diaphragma Download PDFInfo
- Publication number
- EP0687312B1 EP0687312B1 EP94906164A EP94906164A EP0687312B1 EP 0687312 B1 EP0687312 B1 EP 0687312B1 EP 94906164 A EP94906164 A EP 94906164A EP 94906164 A EP94906164 A EP 94906164A EP 0687312 B1 EP0687312 B1 EP 0687312B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- membrane
- gas
- electrode arrangement
- arrangement according
- 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
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000011148 porous material Substances 0.000 claims 1
- 239000003014 ion exchange membrane Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 28
- 239000003792 electrolyte Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 230000007774 longterm Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
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
- 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
-
- 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
Definitions
- the invention relates to an electrode arrangement for gas-forming electrolytic processes, in particular processes in membrane cells, consisting of a flat electrode structure with at least two electrically conductive and mechanically firmly connected electrode elements, between each of which a gap is provided for gas discharge, the electrode elements along the column bearing surfaces for an ion exchange membrane or a diaphragm and edge regions adjacent to the gap are designed as a gas discharge device and their use.
- a membrane electrolysis cell of the filter press type with pairs of planar electrodes is known, the electrodes each containing at least one open active part and a membrane being arranged between the pairs of electrodes; a seal is arranged between the electrode edge and the membrane edge; the perforated central part of the electrodes has a grid-like structure, the grid rods of the electrodes assigned in pairs being offset from one another by a maximum of half a rod width and the grid rods of an electrode being arranged such that their distance from one another is smaller than the projection of their width; the grids have a convex curvature at least on the active side, the thickness of the seal between the electrode edge and the membrane edge being equal to or less than the height of the portion of the grid rod projecting beyond the electrode edge. It turns out to be problematic that with one Such an arrangement with depletion and gas bubbles in the area of the storage surface must be expected, which has an unfavorable effect on the membrane and the electrode coating.
- the electrolytic cell is intended for the electrolysis of an aqueous halide-containing electrolyte, such as brine, in order to produce an aqueous alkali metal hydroxide solution and halogen and hydrogen.
- an aqueous halide-containing electrolyte such as brine
- an electrode arrangement for gas-forming electrolysers in particular membrane electrolysers, with a vertically arranged plate electrode, a counter electrode and a membrane between the two electrodes is known; the plate electrode is divided into horizontal strips, the entire active electrode surface of which is arranged parallel and at the shortest distance from the counterelectrode, but a gap is provided between the membrane and the electrode for discharging the gas formed during the electrochemical reaction;
- the horizontal strips in the area of their upper edge are each provided with an angled gas discharge element, on which the rising gas expands and is partly guided behind the electrode.
- the electrode gap between the membrane and the two electrodes which is always required for gas discharge, proves to be problematic, such a relatively large electrode spacing also resulting in an increase in the cell voltage.
- an electrode arrangement for gas-forming electrolyzers in particular for monopolar membrane electrolyzers with vertically arranged plate electrodes and counter electrodes and a membrane between plate electrode and counter electrode is known;
- electrically conductive and electrically connected surface structures are known as pre-electrodes, which run in parallel planes to the plate electrodes.
- the fabric serving as an electrode is in the form of perforated sheets, expanded metals, wire mesh or wire mesh, the distance between the fabrics being between 1 and 5 mm; the plate electrodes are continuously divided horizontally into several separate units in order to improve the current distribution in the membrane and to reduce the voltage drop on the surfaces facing the membrane.
- EP-OS 0 150 018 discloses a process for the electrolysis of liquid electrolytes by means of perforated electrodes in electrolysis cells divided by ion exchange membrane, a gas space being formed laterally to the main flow direction of the electrolyte due to gas bubble formation. By bursting at the phase boundary, the resulting gas bubbles give off their gas content to the gas space adjacent to the main flow direction, which is formed in the case of plate-shaped electrodes by the rear space behind the electrode.
- the perforated electrodes can consist of expanded metal or sheet metal strips, among other things.
- EP-OS 0 150 018 A problem with the arrangements known from EP-OS 0 150 018 is the relatively complex construction of electrodes with gas flow-guiding elements, which are composed of individual sheet metal strips.
- the object of the invention is to develop an electrode arrangement with an open structure, possibly with a grid-like structure, in which rapid gas bubble discharge with increased electrolyte exchange in the region between the electrode and membrane is to be achieved with a high degree of efficiency; moreover, the electrode arrangement should be easy to manufacture, its long-term stability should be increased and the catalytically active surface should be enlarged.
- the simple manufacture of the electrode arrangement has proven to be particularly advantageous; Furthermore, the different usability can be regarded as advantageous, for example, as being supported directly on the membrane and as a cathode at a distance from the membrane.
- FIG. 1a shows a plan view of the surface of the electrode arrangement, while FIG. 1b shows a cut-out section A from FIG. 1a; Figure 1c shows a cross section in the profile of the electrode arrangement.
- Figure 2 shows a perspective view of a partially broken electrode arrangement
- Figure 3 shows the use of the electrode arrangement according to the invention in a membrane electrolysis cell schematically in a fragmentary partial representation.
- the electrode arrangement 1 made from a flat electrode sheet has a multiplicity of lamellar electrode elements 2 which are each separated from one another by a gap 3; the upper edges 4 of the electrode elements 2 are angled along a schematically represented line 5 on the side facing away from the membrane, in order to allow the gas bubbles formed in the region of the electrodes to be drawn off rapidly.
- the schematically illustrated essentially diamond-shaped openings 8 of the expanded metal can be seen from FIG. This means that the electrochemically active electrode area increases to an area of 1.15 cm 2 compared to a closed area of, for example, 1 cm 2 by expanded metal openings.
- Expanded metal with a web width in the range from 1.5 to 4 mm is advantageously used.
- the long dimension of the opening (LWD) is in the range of 2 to 4.5 mm
- the short dimension of the opening (SWD) is in the range of 1.2 to 3 mm.
- the angle between the upper edges 4 and the plane of the electrode arrangement 1 is approximately 30 °.
- a bevel angle in the range of 20-35 ° has proven to be advantageous.
- Particularly suitable materials for the electrode arrangement are titanium sheet with a noble metal and non-noble metal activation or nickel sheet with a noble metal activation.
- the electrode arrangement has proven particularly useful when used as an anode and cathode in a membrane cell for chlor-alkali electrolysis or for hydrogen oxygen generation.
- the edge strips 6 and 7 consist of either expanded metal or continuous sheet metal.
- the membrane lies directly on the area designated by reference number 10, while the rear area, which extends into the electrolyte space, is open for the purpose of gas discharge.
- spacer elements are provided between the end face 10 of the electrode arrangement 1 and the ion exchange membrane, not shown, which consist of an electrolyte-resistant material, but are also not shown here.
- FIG. 3 shows a schematic cross-sectional representation of a single membrane cell unit, only the ion exchange membrane with cathode and anode being shown in cross-section, and the representation of the associated one Peripherals such as clamping elements, power supply, gas discharge have been omitted for a better overview.
- the anodically connected electrode 1 rests with its end face 10 directly on the surface of the diaphragm 11 shown schematically, the requirement for rapid gas discharge being clearly recognizable due to the openings 8 shown here only schematically in the region of the electrode elements .
- a corresponding process also takes place on the opposite side of the membrane 11 by means of the cathodically connected electrode 1 '; however, it should be noted here that the cathodic electrode is arranged at a distance from the membrane for the purpose of mass exchange and stability of the membrane, for example is supported by spacer elements 13 with respect to the ion exchange membrane 11 in order to achieve a distance in the range of 1 to 3 mm; however, it is also possible to form a distance between the membrane and the cathodic electrode by means of the pressure difference.
- gas bubbles are discharged in a vertical direction from the catholyte 14, a gas collection device (not shown here) likewise being provided.
- the fragmentary cell vessel containing anolyte and catholyte is designated by reference number 15.
- the membrane cell arrangement is particularly suitable for electrolysis cells for chlorine production, but it can also be used for hydrogen / oxygen production.
Landscapes
- 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)
- Measurement Of Radiation (AREA)
- Hybrid Cells (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4306889A DE4306889C1 (de) | 1993-03-05 | 1993-03-05 | Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung |
DE4306889 | 1993-03-05 | ||
PCT/EP1994/000240 WO1994020649A1 (de) | 1993-03-05 | 1994-01-28 | Elektrodenanordnung für gasbildende elektrolytische prozesse in membran-zellen und deren verwendung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0687312A1 EP0687312A1 (de) | 1995-12-20 |
EP0687312B1 true EP0687312B1 (de) | 1997-01-08 |
Family
ID=6482002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94906164A Expired - Lifetime EP0687312B1 (de) | 1993-03-05 | 1994-01-28 | Elektrodenanordnung für gasbildende elektrolytische prozesse in zellen mit ionenaustauschermembran oder mit diaphragma |
Country Status (17)
Country | Link |
---|---|
US (1) | US5660698A (xx) |
EP (1) | EP0687312B1 (xx) |
JP (1) | JPH08507327A (xx) |
AU (1) | AU679038B2 (xx) |
BG (1) | BG99882A (xx) |
BR (1) | BR9405884A (xx) |
CA (1) | CA2154692A1 (xx) |
CZ (1) | CZ284530B6 (xx) |
DE (2) | DE4306889C1 (xx) |
ES (1) | ES2097032T3 (xx) |
NO (1) | NO953111D0 (xx) |
PL (1) | PL177633B1 (xx) |
SA (1) | SA94140724B1 (xx) |
SK (1) | SK108395A3 (xx) |
TW (1) | TW325927U (xx) |
WO (1) | WO1994020649A1 (xx) |
ZA (1) | ZA941191B (xx) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1279069B1 (it) * | 1995-11-22 | 1997-12-04 | Permelec Spa Nora | Migliorato tipo di elettrodo per elettrolizzatori a membrana a scambio ionico |
US5849164A (en) * | 1996-06-27 | 1998-12-15 | Eltech Systems Corporation | Cell with blade electrodes and recirculation chamber |
DE19816334A1 (de) * | 1998-04-11 | 1999-10-14 | Krupp Uhde Gmbh | Elektrolyseapparat zur Herstellung von Halogengasen |
CA2357717C (en) * | 1999-01-08 | 2005-12-06 | Moltech Invent S.A. | Aluminium electrowinning cells with oxygen-evolving anodes |
US10916674B2 (en) * | 2002-05-07 | 2021-02-09 | Nanoptek Corporation | Bandgap-shifted semiconductor surface and method for making same, and apparatus for using same |
DE10333853A1 (de) * | 2003-07-24 | 2005-02-24 | Bayer Materialscience Ag | Elektrochemische Zelle |
DE102004023161A1 (de) * | 2004-05-07 | 2005-11-24 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Elektrolysezelle mit Mehrlagen-Streckmetall-Kathoden |
WO2010096503A1 (en) * | 2009-02-17 | 2010-08-26 | Mcalister Technologies, Llc | Electrolytic cell and method of use thereof |
US8075750B2 (en) | 2009-02-17 | 2011-12-13 | Mcalister Technologies, Llc | Electrolytic cell and method of use thereof |
KR101263593B1 (ko) * | 2009-02-17 | 2013-05-10 | 맥알리스터 테크놀로지즈 엘엘씨 | 전기분해 중에 가스 포집을 위한 장치 및 방법 |
US9040012B2 (en) | 2009-02-17 | 2015-05-26 | Mcalister Technologies, Llc | System and method for renewable resource production, for example, hydrogen production by microbial electrolysis, fermentation, and/or photosynthesis |
MX2011008711A (es) | 2009-02-17 | 2011-11-29 | Mcalister Technologies Llc | Aparato y metodo para controlar la nucleacion durante electrolisis. |
DE102010021833A1 (de) * | 2010-05-28 | 2011-12-01 | Uhde Gmbh | Elektrode für Elektrolysezelle |
US20130034489A1 (en) * | 2011-02-14 | 2013-02-07 | Gilliam Ryan J | Electrochemical hydroxide system and method using fine mesh cathode |
US9222178B2 (en) | 2013-01-22 | 2015-12-29 | GTA, Inc. | Electrolyzer |
US8808512B2 (en) | 2013-01-22 | 2014-08-19 | GTA, Inc. | Electrolyzer apparatus and method of making it |
US9127244B2 (en) | 2013-03-14 | 2015-09-08 | Mcalister Technologies, Llc | Digester assembly for providing renewable resources and associated systems, apparatuses, and methods |
JP2016014381A (ja) * | 2014-07-03 | 2016-01-28 | ナブテスコ株式会社 | 車両用空気圧縮装置 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1581348A (en) * | 1976-08-04 | 1980-12-10 | Ici Ltd | Bipolar unit for electrolytic cell |
DE3219704A1 (de) * | 1982-05-26 | 1983-12-01 | Uhde Gmbh, 4600 Dortmund | Membran-elektrolysezelle |
DE3228884A1 (de) * | 1982-08-03 | 1984-02-09 | Metallgesellschaft Ag, 6000 Frankfurt | Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure |
DE3345530A1 (de) * | 1983-07-13 | 1985-06-27 | Basf Ag, 6700 Ludwigshafen | Gasentwickelnde metallelektrode fuer elektrolysezellen |
DE3401637A1 (de) * | 1984-01-19 | 1985-07-25 | Hoechst Ag, 6230 Frankfurt | Verfahren zum elektrolysieren von fluessigen elektrolyten |
DE3640584A1 (de) * | 1986-11-27 | 1988-06-09 | Metallgesellschaft Ag | Elektrodenanordnung fuer gasbildende elektrolyseure mit vertikal angeordneten plattenelektroden |
DE4119836A1 (de) * | 1991-06-12 | 1992-12-17 | Arnold Gallien | Elektrolysezelle fuer gasentwickelnde bzw. gasverzehrende elektrolytische prozesse sowie verfahren zum betreiben der elektrolysezelle |
-
1993
- 1993-03-05 DE DE4306889A patent/DE4306889C1/de not_active Expired - Fee Related
-
1994
- 1994-01-28 CZ CZ952256A patent/CZ284530B6/cs unknown
- 1994-01-28 US US08/513,817 patent/US5660698A/en not_active Expired - Fee Related
- 1994-01-28 WO PCT/EP1994/000240 patent/WO1994020649A1/de active IP Right Grant
- 1994-01-28 EP EP94906164A patent/EP0687312B1/de not_active Expired - Lifetime
- 1994-01-28 PL PL94310407A patent/PL177633B1/pl not_active IP Right Cessation
- 1994-01-28 CA CA002154692A patent/CA2154692A1/en not_active Abandoned
- 1994-01-28 BR BR9405884A patent/BR9405884A/pt not_active IP Right Cessation
- 1994-01-28 DE DE59401542T patent/DE59401542D1/de not_active Expired - Fee Related
- 1994-01-28 JP JP6519500A patent/JPH08507327A/ja active Pending
- 1994-01-28 ES ES94906164T patent/ES2097032T3/es not_active Expired - Lifetime
- 1994-01-28 SK SK1083-95A patent/SK108395A3/sk unknown
- 1994-01-28 AU AU59996/94A patent/AU679038B2/en not_active Ceased
- 1994-02-22 ZA ZA941191A patent/ZA941191B/xx unknown
- 1994-03-01 TW TW086200048U patent/TW325927U/zh unknown
- 1994-05-11 SA SA94140724A patent/SA94140724B1/ar unknown
-
1995
- 1995-08-08 NO NO953111A patent/NO953111D0/no unknown
- 1995-08-24 BG BG99882A patent/BG99882A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
SK108395A3 (en) | 1997-05-07 |
CZ225695A3 (en) | 1996-04-17 |
BG99882A (en) | 1996-02-29 |
ZA941191B (en) | 1994-09-20 |
PL177633B1 (pl) | 1999-12-31 |
PL310407A1 (en) | 1995-12-11 |
US5660698A (en) | 1997-08-26 |
TW325927U (en) | 1998-01-21 |
WO1994020649A1 (de) | 1994-09-15 |
AU5999694A (en) | 1994-09-26 |
BR9405884A (pt) | 1995-12-12 |
NO953111L (no) | 1995-08-08 |
EP0687312A1 (de) | 1995-12-20 |
SA94140724B1 (ar) | 2005-09-12 |
AU679038B2 (en) | 1997-06-19 |
CA2154692A1 (en) | 1994-09-15 |
DE4306889C1 (de) | 1994-08-18 |
JPH08507327A (ja) | 1996-08-06 |
ES2097032T3 (es) | 1997-03-16 |
DE59401542D1 (de) | 1997-02-20 |
NO953111D0 (no) | 1995-08-08 |
CZ284530B6 (cs) | 1998-12-16 |
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