CA1053177A - Bipolar system electrolytic cell - Google Patents
Bipolar system electrolytic cellInfo
- Publication number
- CA1053177A CA1053177A CA236,235A CA236235A CA1053177A CA 1053177 A CA1053177 A CA 1053177A CA 236235 A CA236235 A CA 236235A CA 1053177 A CA1053177 A CA 1053177A
- Authority
- CA
- Canada
- Prior art keywords
- anode
- electrolytic cell
- partition wall
- cathode
- titanium
- 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
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
- 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
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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)
Abstract
BIPOLAR SYSTEM ELECTROLYTIC CELL
Abstract of the disclosure:
A bipolar system electrolytic cell having a partition wall made of explosion-bonded titanium plate and iron plate which is electrically connected to anode of titanium substrate at its titanium side and to cathode of iron at its iron side; space is preferably given between anode and the partition wall and also between cathode and the partition wall An assembly having a number of such unit cells arranged in series is useful for electrolysis of sodium chloride which can be performed under a low voltage per unit cell.
Abstract of the disclosure:
A bipolar system electrolytic cell having a partition wall made of explosion-bonded titanium plate and iron plate which is electrically connected to anode of titanium substrate at its titanium side and to cathode of iron at its iron side; space is preferably given between anode and the partition wall and also between cathode and the partition wall An assembly having a number of such unit cells arranged in series is useful for electrolysis of sodium chloride which can be performed under a low voltage per unit cell.
Description
~53~'~7 This invention relates to a novel electrolytic cell~
There have been known var~ous bipolar system ~.
electrolytic cells wherein partition walls between anode ,~
chamber and cathode chamber are made of plastics excel~
lent in corrosion resistance and electric insula,tion ,~
such as polyvinyl chlor~deg heat-resistant p~lyvinyl . ,~;
chlor~de~ polyethylene~ polypropyleneg polyesterg epoxy . .,,'-,'-resin9 rubber and/or iron plates llned with these ..
plasticsg concreteg etc. However, when partition walls are made o~ plastics or concrete onlyg they are neces~
sarily required to be thick ~rom the standpoint of ~ :, ` strengthO Accordinglyg no small electrolytic cell narrow - in thickness can be producedO On the other handg while :
15 partition walls made of iron plates lined wlth plastics~ :
etc. are less expensiveg plastics linings are generally -easily peeled off. When anode and cathode are intended . ~.
to~be electrically connected through partition wall in ;~
,~ construct~on o~ bipolar system electrolytic cell ~; 20 plastics lining is especially liable to be peeled o~f ~ : ~ at the surrace through which such a connection is passedg ~hereby electrolytic cell is required to have a com~
plicated s.tructureO Furthermoreg ~enerally speaking, the temperature of electrolyte is preferably as high as ~; 25 posslbleg for examp~le3 higher than 80C ln order to increase the electric conductivity thereof. Thererbre, plastics in general exc~pt ~or~special ones cannot ;' :
. : stand:such a high temperature~ In additiong anode :, c~hambers are generally subjected to severe oxidizing :
', ~ 30 atmosphere, Conventional plas~cs cannot stand such a :
~: 2 , .
. ,, .... , . . . ~ . ~ .. . .
~5 ~
severe oxidl~lng atmo~phere~
Metalllc titanium~ which is Icnown to be resist~
ant to severe oxidizing atmosphere at high temperature a cannot directl~ be welded wi.th iron. Metallic titanium is readily oxldized in oxidizing atmosphere to ~orm `
strong oxide coating which has excellent electricall.y insulating propertyO Accordinglya when metallic ~:
titanium is connected with iron by, for example a mech~
anical connection such as setsscrewa electrically insu--lating coating is formed at the connected sur~ace to : render the connection electrically insulated. Thus a no ~ -bipolar system electrolytic cell~ which can stably be :.
operated f'or a long term~ can be produced by use of ..
.
such a combination. Furthermore~ metallic titanium is~:
not corrosion reistant in reducing atmosphere~ while it is corrosion~resistant in oxidiæing atmosphere.
Therefore~ metallic titanium cannot be exposed in cathode chamberO Due to the reasons as set forth above a it has been difficu1t to employ titanium as partit1on wall of bipolar system electrolytic cell.
he present ~invention provides a novel bipolar system electrolytic cell a comprising a parti-tion wall made of explosion~bonded titanium plate and iron plate which partitions said cell into anode chamber ~.:
and cathode ohambera an anode of titanium substrate hav- -;
: ing platinum group metal oxides coated thereon ~hich.~ :
is connected electrically to titanium of said partitlon `~
wall and a cathode of iron which is connected electri~
cally to iron Or sa~d partition wall.
According to one preferred embodiment of the ...'`:
':
~[)53~
present lnvention~ the bipolar system electrolytic cell compris~s a partitlon wall made of explosion-bonded titanium plate and iron plate which partitions said cell into anode chamber and cathode chamberg an anode of titanlum substrate having platinum group metal oxides coated thereon which is connected electrlcally to titanium of said part1tion wall in a manner such that space i5 provided between said anode and titanium o~
said partition wall and a cathode of iron which is connected electrically to iron of said partition wall in a manner such that space is provided between said cathode and iron of said partition,~
According to another pre~erred embodiment of :
the present invention~ there is provided an electrolytic cell having a number o~ bipolar system electrolytic unit cells arranged in series and having cation exchange membranes lnterposed between cathode chamber and anode ; ;~
chamber of neighboring unit cellsg respectively9 each unit cell comprising a partitlon wall made o~ explosion-bonded titanium plate and iron plate which partitiorls each unit cell into said cathode and anode chambers~
an anode of titanium plate having platinum group metal : `;
oxides coated thereon which is connected electrica~
to titanium plate of said partition wall and a cathode :
of iron plake which:is connected electrically to iron :
plate o~ said partitlon wall, One of the most important ~eatures of the present invention resides ln use of explosion-bonded ~:
titanium plate and iron plate as partition plate. :~
The "explosion bonded titanium plate and iron pIate"
.
- 4 - .
`;
' .,.. , . .. ... ., . . . . , ~ . ~ . ,, .. -~o53~77 herein used rerers to titanlum plate and iron plate wh:ich are pressure bonded to each other by utilizlng explosive force of explosive powder. The bonded plate may also be subjected to hot or cold rolling before use~
In general~ a bonded plate sub~ected to hot rolling is preferred~ since a thin titanium plate can be welded therewi'h ~nd it is excellent in flatness and low in :
costO The titanium plate and the iron plate in the aforesaid explosion~bonded plate are completely attached to each other and there is substantially no oxide coating.
Hence~ titanium and iron are excellent in electric contact without change i~ electric conduc~ivity with passage of' timeO Furthermore, there îs little voltage drop at the contacted portion between iron and tif,anium and electrolysis can be performed at a high temperature.
Since the anode chamber side of the partition wall of the present invention is made of titanium9 it can :::
directly or indirectly through titanium pIate or rod ~ ~
:: . ~ :
be welded with anode. Likewise~ cathode can be welded ~;
with the partition wall at the cathode chamber side thereofO Thus a there is no fear of formation of' elec- ;
tric insulating coating .~ilm.
The 'ititanlum plate" herein used for the par-~ tition walI as well as for the substrate of anode ; 25 includes not only those made of metallic titanlum but also those made of titanîum alloys. ;
The "iron platei' herein used for the~partition wall as well a~s for the s~ubstrate of cathode includes ; not only those made of irsn only but alsG those made of iron alloys containing nickel~ chromium~ molybdenumg ~ i ` ; .' ~ ''~' ~ 5 ~ ~
`
.,. .. , , . , .
~ 53~7 ; :~
carbon~ etc. In addi.tion~ modifiecl cathode lmproved in corrosion resistance or lowered in hydrQgen overvoltage such as those made by plating with nîckel or nickel rhodanide are also included in the presenk invention.
The anode to be employed in the electrolytic . ~
cell o~ the present invention consists of titarlium sub- ~.
strate and platinum metal group oxides coated thereon. :-Sald platinum metal oxlde includes oxides of platinum metal group such as rutheniumg rhodium~ palladium, : :
osmium~ iridium~ platinum~ etc0 In addition to those coated with platinum metal group oxides only~ the anode may be coated with a mixture or an eutectic mixture .
of platinum group metal oxides with other metal oxides such as titanium oxideg zirconium oxide 3 silicon oxide~
aluminum oxide~ boron oxide,etcO Furthermore~ metallic platinum group metal may also be contained in s~id coatingO Alternatively~ an anode of titanium plated with a platinum group metal may also be usedO
The structure o~ anode is preferably such that : 20 it has a gas-permeable structure including large propor-: : :
tion of interstlces or openings~ eOgO in shapes such as a porous plate~ parallel rods~ nets~ etc~ This is because titanium substrate is very expensive, on one hand~ and also because gas dlscharge is alleviated by such a : 25 structure, on the otherO By the presence o~ openings~ ~
back sur-~ace as ~ell as the side surface of a.node can function as ef~ective electrode areaO Furthermore~ since : anode is generally accompanied by generation of gases : such as chlorine gas or oxygen gas, the anode having much openings suoh as porous plate~ parallel rods, nets~
,~ .
.
etc. can permit the gases to be dischar~ed backside of the anode~ whereby electrolysis current is prevented frorn shielding by gas to lower the electrolysis voltage.
The ';porous platel' includes not only a perforated flat plate but also such a product as expanded metalO In view :
of easy fabrication as well as low costg expanded metal is preferably usedO
As mentioned aboveg it is preferred to provide space between the partition wall and the anode in the electrolytic cell of the present inventionO Such a space ls preferably as large as possibley since the ~as is discharged backside of the anode 3 whereby separation of gas is alleviated to lower the electrolysls voltage.
In order to electrically connect the parti~ion wall with the anode~ while providing a space therebetween3 the titanium surface of the partition wall may directly be connected with the titanium substrate of the anode.
- Alternativelyg it may indirectly be connected with the titanium substrate of the anode through a support such as titanium plateg or titanium rodg etc. In particularg when titanium plate support is arranged vertically, the ~
partition wall can be reinforced thereby and the afore- ~ ;
said effect of gas phase is not disturbed at all.
The cathode to be employed in the present inven tiong which is made of iron material as mentioned above~
has preferably such a structure as porous platesg parallel ~-rods, nets9 etcO by the same reasons as described with reference to the anodeg especially when gas such as hydrogen gas is generated from the cathodeg e.gO in case of production of caustic soda. Furthermoreg the cathode ~,:
and the partition wall are electrically connected and it is also prererred ~o prov~de a space with an lnterval of 10 mm or more between the cathode and the par~ition wall~ since titanium plate is prevented from degradation or peel-orf caused by the atomic hydrogen generated at the cathode which penetra~es through the iron sur~ace of the partition wallO Thus~ the electrolytic cell is prevented from increase in electrolysis voltage caused by shielding o~ el.ectrolysis current by khe generated gasO
A number of unit cells as described above are arranged in series like an assembly o~ a ~ilter press and cation exchange membranes are interposed ~etween -~
unit cells, respectively~ to separate anode chambers from cathode chambers~ thus providing an assembly o~ a bipolar system electrolytic cell which is pro~ide~ for use. The number o~ unit cells is 2 or more~ pre~erably -20 or more. In construction o~ said assembly~ care is - :
taken so that there may~be no leak. Each anode chamber has parallel inlet and outlet ~or supply and dischargeg respectively~ of anolyte~ each cathode chamber has also a~smilar structure for supply and discharge of catholyte.
When a direct current is charged between both termlnals of such an electrolytic cell3 current ~lows in ~eries.
The~cat~ion exchange membranes to be used in , .
the present invention include fluorine~containing resins having cation exchange groups such as sulfonic acid type~
carboxyl~c acid type~ phosphoric acid type, etc. and ~ -~
catio~ exchange membranes of which substrate polymers are cross-lin~ed hydrocarbon resins such as styrene~divinyl benzene.
'~' ;
~, ~05331'7~ :
In order that the inventlon may be clearly understood and readily carried into erf'ect~ embodimen'cs thereof will now be described by way Or example with reference to the accompanylng drawings~ ln which.
~igo 1 is a cross-sectional view of one embodi-ment of the electrolytic cell of the lnvention~
FigD 2 is a slant view, viewed from the anode side~ and FigD 3 is an assembly of bipolar system elec-trolytic cell of the inventionO ;~
- The partition wall 3~ having the titanium plate 1 and the iron plate 2 explosion--bonded at the titanium surface thereof, is welded through the titanium plate 5 which is arranged vertically with the anode 4 wherein expanded titanium plate is coated with a platinum group metal oxide. There is also formed a space which provides the anode chamber 6. The cathode 7 which is made of ; ~ .
expanded iron plate is welded with the partition wall at the iron plate 2 through iron plate 8 vertically arrangedg :
and a space is formed for the cathode chamber 9~ There is the iron frame 10 in the circumference o~ khe anode chamber 6 and the cathode chamber 9O Said iron frame is lined with titanium at the surface which can be contacted with the anolyteD The iron frame 10 is welde~ with the iron side of the partition wall at the circum~erence thereof. The titanium lining l1 is also welded with the titanium side 1 o~ the partition wall at the cir-cumference thereofO Thus~ the anode chamber is complete-ly separated from the cathode chamberD The anode chamber ~;~ 30 1s provided wlth the supply nozzle 12 and the dischar~e - 9 ~
~05~
nozzle 13 for anolyte~ which are made o~ titanium. The cathode chamber is provlded with the supply nozzle 14 and the discharge nozzle 15 for catholyte~ which are made of iron. rrhe ~rame 10 may either be provided or ..
not provided with o-ring channel 16 for liquid seal.
The cation exchange membrane 17 is interposed as dia-phragm between the cathode 7 and the anode 4. The pack-ing 18 may be provided between the i.ron frame 10 and the catlon exchange membrane 17 ~or the purpose of adjustment of inter-~electrode dlstance and/or electric insulationO Controlling plates (not shown) may also be provided in the cathode chamber and the anode chamber in order to improve stirring effect of electrolyte by gas.
Headers ~not shown) may also be provided at the top of the cathode chamber and ~he anode chamber for separation ~ , .
of gas from liquid.
A number of unlt cells as described above are arranged in series and the cation exchange membranes are interposed between unit cells~ respectivelyO At the both endsg there~are arranged the electrolytic cell 19 having anode chamber only and a termlnal for passa~e , of current and the electrolytic cell 20 having cathode chamber only and a terminal for passage of currentO
Thus~ the un~t cells are assembled together to be liqu~d tight without leak to form bipolar system electrolytic cell. For convenlence;or assemblyg the arms 21 are provided at both sides of the iron frame 10 of the unit electroly~ic cell. Said~arms are mounted on the press stand 22 having side bar.
The bipolar system electrolytis cell o~ the :
:
:;
. ... . . . ... . . . . . .. . .. .. . . .
7 ;9 present invention can be used for various uses. ~or example~ it is particularly suitable foI~ production of chlorine gas~ hydrogen gas a~d caustic soda by supplyin~
aqueous sodium chloride solution as anolyte and aqueous caustic soda solutlon as catholyte..
The present invention is illustrated ln f'urther .~ .
: detail by referring to the ~ollowing Examples~ which are shown for the purpose of illustration onlyO
Example 1 In the elec~rolytic cell as shown in the accom-panying drawings~ the partition wall 3 which is 1.2 m long and 2.4 m wide is prepared by explosion-bonding ~ :~
iron plate with titanium plateg ~ollowed by hot rolling~
The titanium plate 1 is 1 mm and the iron plate 9 mm in ;
1~ thickness~ A porous titanium plate which is prepared ~
by expanding titanium plate with thicXness of 1.5 mm9 having opening ratio o~ 60 %9 is coated3 5 ~ thick~ with :. :
~: an eutectic mixture comprising 60 mol ,0 ruthenium oxide 3 :
30 mol ,0 titanium oxide and 10 mol ~ zirconium oxide to provide the anode 4, In order to provide 25 mm of the space 6 for the anode chamber between the anode 4 and the titanium o~ ~he partition wal].~ the titanium plate .
- 5 whîch is 4 mm thick~ 25 mm wide and lo 2 m long is .
arranged at the interval of lQ cmO Said tltanium plate ~ :
is arranged vertically so as not to disturb the stirring ef'fect by gas and provided wlth lC holes of about 10 mm in diameter so as to permit horizontal mixing of the liquid. The titanium plate 59 the titanium 1 of the partition wall and the anode 4 are connected to one another by means of welding so as to reduce the electric ~: `
~053~7~
resistance as ~uctl as po~sib3e, As the c~-thode 7, an expanded poro!~s plate wlth opening ratlo of 60 % wh~ch is prepared from 1.6 mm iron plate is used. In order to provide 45 mm of the space 9 for the cathode chamber between the cathode 7 and the partition wall, there is vertically arranged the iron plate 8 which is ~ mm thick~
45 mm wide and about L.2 m long and provlcled with 10 holes of about 10 mm in diameter. The cathode 7~ the iron plate 8 and the iron 2 of the partition wall are connected to one another by means o~ welding so as to reduce the electric res~s~ance as much as possible.
There is the iron ~rame with thickness of 16 mm around the partition wall 3 and it is lined wlth titanium plate 11 with thickness of 2 mm at the surface in contact with the anolyte. The interval between the cathode 7 and the anode ll are maintained at about 2 mm by the packing of ethylene~propylene rubber with thickness of 2 mm. As the cation exchange resin 17~ a sulfonic acid type resin made from fluoro-resin substrate reinforced with ~luoro~fiber cloth is used.
A bipolar system electrolytic cell assembly is made by arrangement o~ ~0 unit electrolytic cells as described above~ and at both ends thereo~ the electrolytic cell 20 having only cathode chamber and the electrolytic cell 1~ havlng only anode chamber~ ~ollowed by pressing on the press stand 22 having side bar.
; To the liquld supply nozzle 12 of each anode chamber is supplied an aqueous sodium chloride solution through the pipes arranged paralle] to each other from the anolyte tank. From the liquid discharge nozzle 13 , :
9.g~53~77 :
is discharged t,he anolyte comprising sodium chloride solution ancl chlorine gas throu~h the pipes arranged similarly parallel to each other~ which is then returned ~;
to the anolyte tankv To the liquid supply nozzle lLI o~ each cathode chamber is supplied an aqueous caustic soda solution through the pipes arranged parallel to each other from the catholyte tank and from the liquid discharge nozzle 15 is discharged 20 w~,. % aqueous caustic soda solution and hydrogen gas~ which is then returned to the catholyte ~
tankO ~, When direct current of 14000 ampere is passed through the bipolar system electrolytic cell as described ;~
above at an electrolysis temperature of 92C~ the volta~e per unit cell is only 3.6 volt. The voltage drop between the cathode 7 and the anode 4 through the partition wall 3 is merely several millivolt~ whlch clearly shows the advantage of the structure having explosion-bonded parti~
tion wall.
:
~ 20 Reference example 1 . .
In this reference example, heat--resistant poly-vinyl chlorlde resin plate is used as the partition wall. ~ ~ ?`
The same anode and cathode as in Example 1 are used. The corresponding titanium plates 5 are arranged at the intervals of 10 cm and titanium plates with thickness o~ 10 mm and width o~ 15 cm are arranged ~ ~
~or distribution of current between said titanlum plates -` `
5 horizontally along the partition wall. A titanium rod of lQ cm in diameter whlch is~welded with the~ ;
a~oresaid titanium plate is penetrated through the ~ , .'' `.'.~
~ - 13 ::
-~05~1~7 partition wall o~ heat-reslstant polyvin~l chloride.
The cathode side is also provided with the same structure as the anode side and both sides ar~ connected by sets-screw on the penetrated portion of the heat-resistant polyvinyl chlorideO
Although the siæe of the cathode chamberg the ; size of the anode chamber, the cation ex~hange membraneg the anolyte concentration and the catholyte concentra-tion are the same as in Example 19 -the voltage drop between the cathode and the anode through the partition wall is as much as about 200 millivolt when direct current of 14000 ampere is passedO The heat-resistant - polyvinyl chloride is observed to be molten at the ; penetrated portion by the heat evolved at an electrolysis temperature of 70Co Thereforeg electrolysis can no lon~er be ~ontinuedO Furthermoreg the electrolysls voltage is as high as 4.7 volt per unit cell, since the electrolysis temperature cannot be elevated to a high temperature. Thusg no large scale eIectrolytic cell can be produced by using heat~resistant polyvlnyl ~;
chloride as the partition wall~ because no great current can be passed and the electrolysis voltage cannok suf-ficiently be elevated.
Example 2 In this Exampleg explosion-bonded titanium plate and iron plate is used as the partition wall, but plate electrodes having no space therebehind are used in the bipolar system electrolytic cellO
The same partition wall as in Example 1 is used.
A flat plate anodeg wherein the surface o~ titanium 1 - 14 - ;
. ~
:1~5;~77 of the partitlon wall is coated dlrectly~ 5 ~ thick~
with the same eutectic mixture as in Example 1 comprising 60 mol % ruthenium oxide~ 30 mol % titanium oxide and 10 mol % ~irconium oxide a i5 used O As for cathode; the iron of the partition wall is shaped ln flat plate to be provided for use as cathode. The same cation exchange membrane as in Example 1 is used.
The distance between the cathode and the cation exchange membrane and that between the anode and the cation exchange membrane are 3O5 mma respectively. This ls because there must be provided slits ~or supply and discharge o~ liquids to and from the anode and the cathode chambers, respectively~ and packings for prevention of leak, etc.
Using this electrolytlc cell~ electrolysis is ~;
per~ormed under the same conditions with respect to the -anolyte concentration, the catholyte concentration, the ~?~
amount o~ the anolyte a the amount of the catholyte and the electrolysis temperature~ When a current of only , : ~
2500 ampere is passed, the electrolysis voltage becomes as muc~ as 3.6 volt per unit cella because the current is shlelded by chlorine gas and hydrogen gas generated. ,!~`
This result clearly shows khe advantageous e~fect o~ an electrolytic cell having a porous plate electrode struc-ture and having apace between the partition wall and electrode.
Example 3 The same electrolytic cell as in Example 1 is useda except that the cathode surface ls subjected to nickel plating ln a bath contaîning 250 g/l NiS04O7H20 -( ' '' ' :
~ 5~17'7 50 g/1 NiC12 6H20 and 45 g/1 ~)oric acid at 2 A/dm2 to thickness of lO microns and further to plating in a bath containing 200 g/'L NiSOLIo7H20~ 30 g/l NiCl2o6H20~ 20 g/l of boric acid and 16 g/l amrnonium rhodanide at l A/dm2 ~ .
to thickness of about 15 rnicrons.
The cathode is low in hydrogen overvoltage and the voltage per unit cell is only 305 volt when electrol~
ysis is performed under the same con~itions as in Exarnple l.
. : ,:
,:
,'
There have been known var~ous bipolar system ~.
electrolytic cells wherein partition walls between anode ,~
chamber and cathode chamber are made of plastics excel~
lent in corrosion resistance and electric insula,tion ,~
such as polyvinyl chlor~deg heat-resistant p~lyvinyl . ,~;
chlor~de~ polyethylene~ polypropyleneg polyesterg epoxy . .,,'-,'-resin9 rubber and/or iron plates llned with these ..
plasticsg concreteg etc. However, when partition walls are made o~ plastics or concrete onlyg they are neces~
sarily required to be thick ~rom the standpoint of ~ :, ` strengthO Accordinglyg no small electrolytic cell narrow - in thickness can be producedO On the other handg while :
15 partition walls made of iron plates lined wlth plastics~ :
etc. are less expensiveg plastics linings are generally -easily peeled off. When anode and cathode are intended . ~.
to~be electrically connected through partition wall in ;~
,~ construct~on o~ bipolar system electrolytic cell ~; 20 plastics lining is especially liable to be peeled o~f ~ : ~ at the surrace through which such a connection is passedg ~hereby electrolytic cell is required to have a com~
plicated s.tructureO Furthermoreg ~enerally speaking, the temperature of electrolyte is preferably as high as ~; 25 posslbleg for examp~le3 higher than 80C ln order to increase the electric conductivity thereof. Thererbre, plastics in general exc~pt ~or~special ones cannot ;' :
. : stand:such a high temperature~ In additiong anode :, c~hambers are generally subjected to severe oxidizing :
', ~ 30 atmosphere, Conventional plas~cs cannot stand such a :
~: 2 , .
. ,, .... , . . . ~ . ~ .. . .
~5 ~
severe oxidl~lng atmo~phere~
Metalllc titanium~ which is Icnown to be resist~
ant to severe oxidizing atmosphere at high temperature a cannot directl~ be welded wi.th iron. Metallic titanium is readily oxldized in oxidizing atmosphere to ~orm `
strong oxide coating which has excellent electricall.y insulating propertyO Accordinglya when metallic ~:
titanium is connected with iron by, for example a mech~
anical connection such as setsscrewa electrically insu--lating coating is formed at the connected sur~ace to : render the connection electrically insulated. Thus a no ~ -bipolar system electrolytic cell~ which can stably be :.
operated f'or a long term~ can be produced by use of ..
.
such a combination. Furthermore~ metallic titanium is~:
not corrosion reistant in reducing atmosphere~ while it is corrosion~resistant in oxidiæing atmosphere.
Therefore~ metallic titanium cannot be exposed in cathode chamberO Due to the reasons as set forth above a it has been difficu1t to employ titanium as partit1on wall of bipolar system electrolytic cell.
he present ~invention provides a novel bipolar system electrolytic cell a comprising a parti-tion wall made of explosion~bonded titanium plate and iron plate which partitions said cell into anode chamber ~.:
and cathode ohambera an anode of titanium substrate hav- -;
: ing platinum group metal oxides coated thereon ~hich.~ :
is connected electrically to titanium of said partitlon `~
wall and a cathode of iron which is connected electri~
cally to iron Or sa~d partition wall.
According to one preferred embodiment of the ...'`:
':
~[)53~
present lnvention~ the bipolar system electrolytic cell compris~s a partitlon wall made of explosion-bonded titanium plate and iron plate which partitions said cell into anode chamber and cathode chamberg an anode of titanlum substrate having platinum group metal oxides coated thereon which is connected electrlcally to titanium of said part1tion wall in a manner such that space i5 provided between said anode and titanium o~
said partition wall and a cathode of iron which is connected electrically to iron of said partition wall in a manner such that space is provided between said cathode and iron of said partition,~
According to another pre~erred embodiment of :
the present invention~ there is provided an electrolytic cell having a number o~ bipolar system electrolytic unit cells arranged in series and having cation exchange membranes lnterposed between cathode chamber and anode ; ;~
chamber of neighboring unit cellsg respectively9 each unit cell comprising a partitlon wall made o~ explosion-bonded titanium plate and iron plate which partitiorls each unit cell into said cathode and anode chambers~
an anode of titanium plate having platinum group metal : `;
oxides coated thereon which is connected electrica~
to titanium plate of said partition wall and a cathode :
of iron plake which:is connected electrically to iron :
plate o~ said partitlon wall, One of the most important ~eatures of the present invention resides ln use of explosion-bonded ~:
titanium plate and iron plate as partition plate. :~
The "explosion bonded titanium plate and iron pIate"
.
- 4 - .
`;
' .,.. , . .. ... ., . . . . , ~ . ~ . ,, .. -~o53~77 herein used rerers to titanlum plate and iron plate wh:ich are pressure bonded to each other by utilizlng explosive force of explosive powder. The bonded plate may also be subjected to hot or cold rolling before use~
In general~ a bonded plate sub~ected to hot rolling is preferred~ since a thin titanium plate can be welded therewi'h ~nd it is excellent in flatness and low in :
costO The titanium plate and the iron plate in the aforesaid explosion~bonded plate are completely attached to each other and there is substantially no oxide coating.
Hence~ titanium and iron are excellent in electric contact without change i~ electric conduc~ivity with passage of' timeO Furthermore, there îs little voltage drop at the contacted portion between iron and tif,anium and electrolysis can be performed at a high temperature.
Since the anode chamber side of the partition wall of the present invention is made of titanium9 it can :::
directly or indirectly through titanium pIate or rod ~ ~
:: . ~ :
be welded with anode. Likewise~ cathode can be welded ~;
with the partition wall at the cathode chamber side thereofO Thus a there is no fear of formation of' elec- ;
tric insulating coating .~ilm.
The 'ititanlum plate" herein used for the par-~ tition walI as well as for the substrate of anode ; 25 includes not only those made of metallic titanlum but also those made of titanîum alloys. ;
The "iron platei' herein used for the~partition wall as well a~s for the s~ubstrate of cathode includes ; not only those made of irsn only but alsG those made of iron alloys containing nickel~ chromium~ molybdenumg ~ i ` ; .' ~ ''~' ~ 5 ~ ~
`
.,. .. , , . , .
~ 53~7 ; :~
carbon~ etc. In addi.tion~ modifiecl cathode lmproved in corrosion resistance or lowered in hydrQgen overvoltage such as those made by plating with nîckel or nickel rhodanide are also included in the presenk invention.
The anode to be employed in the electrolytic . ~
cell o~ the present invention consists of titarlium sub- ~.
strate and platinum metal group oxides coated thereon. :-Sald platinum metal oxlde includes oxides of platinum metal group such as rutheniumg rhodium~ palladium, : :
osmium~ iridium~ platinum~ etc0 In addition to those coated with platinum metal group oxides only~ the anode may be coated with a mixture or an eutectic mixture .
of platinum group metal oxides with other metal oxides such as titanium oxideg zirconium oxide 3 silicon oxide~
aluminum oxide~ boron oxide,etcO Furthermore~ metallic platinum group metal may also be contained in s~id coatingO Alternatively~ an anode of titanium plated with a platinum group metal may also be usedO
The structure o~ anode is preferably such that : 20 it has a gas-permeable structure including large propor-: : :
tion of interstlces or openings~ eOgO in shapes such as a porous plate~ parallel rods~ nets~ etc~ This is because titanium substrate is very expensive, on one hand~ and also because gas dlscharge is alleviated by such a : 25 structure, on the otherO By the presence o~ openings~ ~
back sur-~ace as ~ell as the side surface of a.node can function as ef~ective electrode areaO Furthermore~ since : anode is generally accompanied by generation of gases : such as chlorine gas or oxygen gas, the anode having much openings suoh as porous plate~ parallel rods, nets~
,~ .
.
etc. can permit the gases to be dischar~ed backside of the anode~ whereby electrolysis current is prevented frorn shielding by gas to lower the electrolysis voltage.
The ';porous platel' includes not only a perforated flat plate but also such a product as expanded metalO In view :
of easy fabrication as well as low costg expanded metal is preferably usedO
As mentioned aboveg it is preferred to provide space between the partition wall and the anode in the electrolytic cell of the present inventionO Such a space ls preferably as large as possibley since the ~as is discharged backside of the anode 3 whereby separation of gas is alleviated to lower the electrolysls voltage.
In order to electrically connect the parti~ion wall with the anode~ while providing a space therebetween3 the titanium surface of the partition wall may directly be connected with the titanium substrate of the anode.
- Alternativelyg it may indirectly be connected with the titanium substrate of the anode through a support such as titanium plateg or titanium rodg etc. In particularg when titanium plate support is arranged vertically, the ~
partition wall can be reinforced thereby and the afore- ~ ;
said effect of gas phase is not disturbed at all.
The cathode to be employed in the present inven tiong which is made of iron material as mentioned above~
has preferably such a structure as porous platesg parallel ~-rods, nets9 etcO by the same reasons as described with reference to the anodeg especially when gas such as hydrogen gas is generated from the cathodeg e.gO in case of production of caustic soda. Furthermoreg the cathode ~,:
and the partition wall are electrically connected and it is also prererred ~o prov~de a space with an lnterval of 10 mm or more between the cathode and the par~ition wall~ since titanium plate is prevented from degradation or peel-orf caused by the atomic hydrogen generated at the cathode which penetra~es through the iron sur~ace of the partition wallO Thus~ the electrolytic cell is prevented from increase in electrolysis voltage caused by shielding o~ el.ectrolysis current by khe generated gasO
A number of unit cells as described above are arranged in series like an assembly o~ a ~ilter press and cation exchange membranes are interposed ~etween -~
unit cells, respectively~ to separate anode chambers from cathode chambers~ thus providing an assembly o~ a bipolar system electrolytic cell which is pro~ide~ for use. The number o~ unit cells is 2 or more~ pre~erably -20 or more. In construction o~ said assembly~ care is - :
taken so that there may~be no leak. Each anode chamber has parallel inlet and outlet ~or supply and dischargeg respectively~ of anolyte~ each cathode chamber has also a~smilar structure for supply and discharge of catholyte.
When a direct current is charged between both termlnals of such an electrolytic cell3 current ~lows in ~eries.
The~cat~ion exchange membranes to be used in , .
the present invention include fluorine~containing resins having cation exchange groups such as sulfonic acid type~
carboxyl~c acid type~ phosphoric acid type, etc. and ~ -~
catio~ exchange membranes of which substrate polymers are cross-lin~ed hydrocarbon resins such as styrene~divinyl benzene.
'~' ;
~, ~05331'7~ :
In order that the inventlon may be clearly understood and readily carried into erf'ect~ embodimen'cs thereof will now be described by way Or example with reference to the accompanylng drawings~ ln which.
~igo 1 is a cross-sectional view of one embodi-ment of the electrolytic cell of the lnvention~
FigD 2 is a slant view, viewed from the anode side~ and FigD 3 is an assembly of bipolar system elec-trolytic cell of the inventionO ;~
- The partition wall 3~ having the titanium plate 1 and the iron plate 2 explosion--bonded at the titanium surface thereof, is welded through the titanium plate 5 which is arranged vertically with the anode 4 wherein expanded titanium plate is coated with a platinum group metal oxide. There is also formed a space which provides the anode chamber 6. The cathode 7 which is made of ; ~ .
expanded iron plate is welded with the partition wall at the iron plate 2 through iron plate 8 vertically arrangedg :
and a space is formed for the cathode chamber 9~ There is the iron frame 10 in the circumference o~ khe anode chamber 6 and the cathode chamber 9O Said iron frame is lined with titanium at the surface which can be contacted with the anolyteD The iron frame 10 is welde~ with the iron side of the partition wall at the circum~erence thereof. The titanium lining l1 is also welded with the titanium side 1 o~ the partition wall at the cir-cumference thereofO Thus~ the anode chamber is complete-ly separated from the cathode chamberD The anode chamber ~;~ 30 1s provided wlth the supply nozzle 12 and the dischar~e - 9 ~
~05~
nozzle 13 for anolyte~ which are made o~ titanium. The cathode chamber is provlded with the supply nozzle 14 and the discharge nozzle 15 for catholyte~ which are made of iron. rrhe ~rame 10 may either be provided or ..
not provided with o-ring channel 16 for liquid seal.
The cation exchange membrane 17 is interposed as dia-phragm between the cathode 7 and the anode 4. The pack-ing 18 may be provided between the i.ron frame 10 and the catlon exchange membrane 17 ~or the purpose of adjustment of inter-~electrode dlstance and/or electric insulationO Controlling plates (not shown) may also be provided in the cathode chamber and the anode chamber in order to improve stirring effect of electrolyte by gas.
Headers ~not shown) may also be provided at the top of the cathode chamber and ~he anode chamber for separation ~ , .
of gas from liquid.
A number of unlt cells as described above are arranged in series and the cation exchange membranes are interposed between unit cells~ respectivelyO At the both endsg there~are arranged the electrolytic cell 19 having anode chamber only and a termlnal for passa~e , of current and the electrolytic cell 20 having cathode chamber only and a terminal for passage of currentO
Thus~ the un~t cells are assembled together to be liqu~d tight without leak to form bipolar system electrolytic cell. For convenlence;or assemblyg the arms 21 are provided at both sides of the iron frame 10 of the unit electroly~ic cell. Said~arms are mounted on the press stand 22 having side bar.
The bipolar system electrolytis cell o~ the :
:
:;
. ... . . . ... . . . . . .. . .. .. . . .
7 ;9 present invention can be used for various uses. ~or example~ it is particularly suitable foI~ production of chlorine gas~ hydrogen gas a~d caustic soda by supplyin~
aqueous sodium chloride solution as anolyte and aqueous caustic soda solutlon as catholyte..
The present invention is illustrated ln f'urther .~ .
: detail by referring to the ~ollowing Examples~ which are shown for the purpose of illustration onlyO
Example 1 In the elec~rolytic cell as shown in the accom-panying drawings~ the partition wall 3 which is 1.2 m long and 2.4 m wide is prepared by explosion-bonding ~ :~
iron plate with titanium plateg ~ollowed by hot rolling~
The titanium plate 1 is 1 mm and the iron plate 9 mm in ;
1~ thickness~ A porous titanium plate which is prepared ~
by expanding titanium plate with thicXness of 1.5 mm9 having opening ratio o~ 60 %9 is coated3 5 ~ thick~ with :. :
~: an eutectic mixture comprising 60 mol ,0 ruthenium oxide 3 :
30 mol ,0 titanium oxide and 10 mol ~ zirconium oxide to provide the anode 4, In order to provide 25 mm of the space 6 for the anode chamber between the anode 4 and the titanium o~ ~he partition wal].~ the titanium plate .
- 5 whîch is 4 mm thick~ 25 mm wide and lo 2 m long is .
arranged at the interval of lQ cmO Said tltanium plate ~ :
is arranged vertically so as not to disturb the stirring ef'fect by gas and provided wlth lC holes of about 10 mm in diameter so as to permit horizontal mixing of the liquid. The titanium plate 59 the titanium 1 of the partition wall and the anode 4 are connected to one another by means of welding so as to reduce the electric ~: `
~053~7~
resistance as ~uctl as po~sib3e, As the c~-thode 7, an expanded poro!~s plate wlth opening ratlo of 60 % wh~ch is prepared from 1.6 mm iron plate is used. In order to provide 45 mm of the space 9 for the cathode chamber between the cathode 7 and the partition wall, there is vertically arranged the iron plate 8 which is ~ mm thick~
45 mm wide and about L.2 m long and provlcled with 10 holes of about 10 mm in diameter. The cathode 7~ the iron plate 8 and the iron 2 of the partition wall are connected to one another by means o~ welding so as to reduce the electric res~s~ance as much as possible.
There is the iron ~rame with thickness of 16 mm around the partition wall 3 and it is lined wlth titanium plate 11 with thickness of 2 mm at the surface in contact with the anolyte. The interval between the cathode 7 and the anode ll are maintained at about 2 mm by the packing of ethylene~propylene rubber with thickness of 2 mm. As the cation exchange resin 17~ a sulfonic acid type resin made from fluoro-resin substrate reinforced with ~luoro~fiber cloth is used.
A bipolar system electrolytic cell assembly is made by arrangement o~ ~0 unit electrolytic cells as described above~ and at both ends thereo~ the electrolytic cell 20 having only cathode chamber and the electrolytic cell 1~ havlng only anode chamber~ ~ollowed by pressing on the press stand 22 having side bar.
; To the liquld supply nozzle 12 of each anode chamber is supplied an aqueous sodium chloride solution through the pipes arranged paralle] to each other from the anolyte tank. From the liquid discharge nozzle 13 , :
9.g~53~77 :
is discharged t,he anolyte comprising sodium chloride solution ancl chlorine gas throu~h the pipes arranged similarly parallel to each other~ which is then returned ~;
to the anolyte tankv To the liquid supply nozzle lLI o~ each cathode chamber is supplied an aqueous caustic soda solution through the pipes arranged parallel to each other from the catholyte tank and from the liquid discharge nozzle 15 is discharged 20 w~,. % aqueous caustic soda solution and hydrogen gas~ which is then returned to the catholyte ~
tankO ~, When direct current of 14000 ampere is passed through the bipolar system electrolytic cell as described ;~
above at an electrolysis temperature of 92C~ the volta~e per unit cell is only 3.6 volt. The voltage drop between the cathode 7 and the anode 4 through the partition wall 3 is merely several millivolt~ whlch clearly shows the advantage of the structure having explosion-bonded parti~
tion wall.
:
~ 20 Reference example 1 . .
In this reference example, heat--resistant poly-vinyl chlorlde resin plate is used as the partition wall. ~ ~ ?`
The same anode and cathode as in Example 1 are used. The corresponding titanium plates 5 are arranged at the intervals of 10 cm and titanium plates with thickness o~ 10 mm and width o~ 15 cm are arranged ~ ~
~or distribution of current between said titanlum plates -` `
5 horizontally along the partition wall. A titanium rod of lQ cm in diameter whlch is~welded with the~ ;
a~oresaid titanium plate is penetrated through the ~ , .'' `.'.~
~ - 13 ::
-~05~1~7 partition wall o~ heat-reslstant polyvin~l chloride.
The cathode side is also provided with the same structure as the anode side and both sides ar~ connected by sets-screw on the penetrated portion of the heat-resistant polyvinyl chlorideO
Although the siæe of the cathode chamberg the ; size of the anode chamber, the cation ex~hange membraneg the anolyte concentration and the catholyte concentra-tion are the same as in Example 19 -the voltage drop between the cathode and the anode through the partition wall is as much as about 200 millivolt when direct current of 14000 ampere is passedO The heat-resistant - polyvinyl chloride is observed to be molten at the ; penetrated portion by the heat evolved at an electrolysis temperature of 70Co Thereforeg electrolysis can no lon~er be ~ontinuedO Furthermoreg the electrolysls voltage is as high as 4.7 volt per unit cell, since the electrolysis temperature cannot be elevated to a high temperature. Thusg no large scale eIectrolytic cell can be produced by using heat~resistant polyvlnyl ~;
chloride as the partition wall~ because no great current can be passed and the electrolysis voltage cannok suf-ficiently be elevated.
Example 2 In this Exampleg explosion-bonded titanium plate and iron plate is used as the partition wall, but plate electrodes having no space therebehind are used in the bipolar system electrolytic cellO
The same partition wall as in Example 1 is used.
A flat plate anodeg wherein the surface o~ titanium 1 - 14 - ;
. ~
:1~5;~77 of the partitlon wall is coated dlrectly~ 5 ~ thick~
with the same eutectic mixture as in Example 1 comprising 60 mol % ruthenium oxide~ 30 mol % titanium oxide and 10 mol % ~irconium oxide a i5 used O As for cathode; the iron of the partition wall is shaped ln flat plate to be provided for use as cathode. The same cation exchange membrane as in Example 1 is used.
The distance between the cathode and the cation exchange membrane and that between the anode and the cation exchange membrane are 3O5 mma respectively. This ls because there must be provided slits ~or supply and discharge o~ liquids to and from the anode and the cathode chambers, respectively~ and packings for prevention of leak, etc.
Using this electrolytlc cell~ electrolysis is ~;
per~ormed under the same conditions with respect to the -anolyte concentration, the catholyte concentration, the ~?~
amount o~ the anolyte a the amount of the catholyte and the electrolysis temperature~ When a current of only , : ~
2500 ampere is passed, the electrolysis voltage becomes as muc~ as 3.6 volt per unit cella because the current is shlelded by chlorine gas and hydrogen gas generated. ,!~`
This result clearly shows khe advantageous e~fect o~ an electrolytic cell having a porous plate electrode struc-ture and having apace between the partition wall and electrode.
Example 3 The same electrolytic cell as in Example 1 is useda except that the cathode surface ls subjected to nickel plating ln a bath contaîning 250 g/l NiS04O7H20 -( ' '' ' :
~ 5~17'7 50 g/1 NiC12 6H20 and 45 g/1 ~)oric acid at 2 A/dm2 to thickness of lO microns and further to plating in a bath containing 200 g/'L NiSOLIo7H20~ 30 g/l NiCl2o6H20~ 20 g/l of boric acid and 16 g/l amrnonium rhodanide at l A/dm2 ~ .
to thickness of about 15 rnicrons.
The cathode is low in hydrogen overvoltage and the voltage per unit cell is only 305 volt when electrol~
ysis is performed under the same con~itions as in Exarnple l.
. : ,:
,:
,'
Claims (11)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bipolar system electrolytic cell comprising a partition wall made of explosion-bonded titanium plate and iron plate which partitions said cell into anode chamber and cathode chamber, an anode of titanium substrate which is electrically connected to said titanium plate of said partition wall and which is coated with platinum group metal oxides and an iron cathode which is electrically connected to said iron plate of said partition wall.
2. An electrolytic cell as claimed in Claim 1, wherein the partition wall is made by explosion-bonding said titanium plate and said iron plate, followed by hot rolling.
3. An electrolytic cell as claimed in Claim 1 or 2, wherein the anode has a gas-permeable structure.
4. An electrolytic cell as claimed in Claim 1 or 2, wherein the cathode has a gas-permeable structure.
5. An electrolytic cell as claimed in Claim 1 or 2, wherein the anode is an expanded metal.
6. An electrolytic cell as claimed in Claim 1 or 2, wherein the cathode is an expanded metal.
7. An electrolytic cell as claimed in Claim 1, wherein a space is provided between the anode and the partition wall.
8. An electrolytic cell as claimed in Claim 1, wherein a space of 10 mm or more is provided between the cathode and the partition wall.
9. An electrolytic cell as claimed in Claim 7, wherein the space is provided by connecting the titanium substrate of the anode with the titanium plate of the partition wall by means of a vertically arranged titanium support.
10. An electrolytic cell as claimed in Claim 1, wherein a space is provided both between the anode and the partition wall and between the cathode and the partition wall.
11. A bipolar system electrolytic cell, comprising a number of bipolar system electrolytic unit cells as claimed in Claim 1, 2 or 10, being arranged in series, having cation exchange membranes interposed between cathode chamber and anode chamber of neighboring unit cells, respectively.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49116695A JPS5232866B2 (en) | 1974-10-09 | 1974-10-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053177A true CA1053177A (en) | 1979-04-24 |
Family
ID=14693555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,235A Expired CA1053177A (en) | 1974-10-09 | 1975-09-24 | Bipolar system electrolytic cell |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5232866B2 (en) |
| BR (1) | BR7506536A (en) |
| CA (1) | CA1053177A (en) |
| DE (1) | DE2545339C2 (en) |
| FR (1) | FR2287528A1 (en) |
| GB (1) | GB1503799A (en) |
| IT (1) | IT1042958B (en) |
| NL (1) | NL165511C (en) |
| SE (1) | SE7511257L (en) |
| SU (1) | SU1291029A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225061A (en) * | 1991-05-24 | 1993-07-06 | Westerlund Goethe O | Bipolar electrode module |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5929677B2 (en) * | 1976-11-19 | 1984-07-21 | 旭硝子株式会社 | Filter press type electrolytic cell |
| JPS5421641U (en) * | 1977-07-15 | 1979-02-13 | ||
| DE2816440A1 (en) * | 1978-04-15 | 1979-10-25 | Uhde Gmbh | ELECTROLYSIS CELL |
| JPS5848366Y2 (en) * | 1978-09-13 | 1983-11-04 | 株式会社トクヤマ | anode chamber |
| GB2051870B (en) * | 1979-06-07 | 1983-04-20 | Asahi Chemical Ind | Method for electrolysis of aqueous alkali metal chloride solution |
| FR2484464A1 (en) * | 1980-02-04 | 1981-12-18 | Electricite De France | Pressurised electrolyser, esp. for mfg. hydrogen - where electrolysis cells are sepd. by insulating polymer seals resisting attack by hot aq. alkaline electrolyte |
| JPS57137486A (en) * | 1981-02-19 | 1982-08-25 | Tokuyama Soda Co Ltd | Electrolytic cell |
| JPS5732393A (en) * | 1981-06-25 | 1982-02-22 | Asahi Glass Co Ltd | Filter press type electrolytic cell |
| JPS59133384A (en) * | 1983-01-19 | 1984-07-31 | Toyo Soda Mfg Co Ltd | Electrolytic cell |
| DE3342449A1 (en) * | 1983-11-24 | 1985-06-05 | Uhde Gmbh, 4600 Dortmund | ELECTROLYTIC CELL FOR THE ELECTROLYSIS OF AQUEOUS HALOGENIDE-CONTAINING ELECTROLYT |
| JPS60187688A (en) * | 1985-01-10 | 1985-09-25 | Kanegafuchi Chem Ind Co Ltd | Manufacture of alkali metallic hydroxide of high purity |
| JPH0674513B2 (en) * | 1985-10-23 | 1994-09-21 | 旭化成工業株式会社 | Bipolar electrolytic cell unit |
| GB8530893D0 (en) * | 1985-12-16 | 1986-01-29 | Ici Plc | Electrode |
| GB8626010D0 (en) * | 1986-10-30 | 1986-12-03 | Ici Plc | Assembling filter press type structure |
| GB8626629D0 (en) * | 1986-11-07 | 1986-12-10 | Ici Plc | Electrolytic cell |
| JPH02130873U (en) * | 1989-04-05 | 1990-10-30 | ||
| JP3696137B2 (en) | 2000-09-08 | 2005-09-14 | 株式会社藤田ワークス | Method for producing electrolytic cell unit and electrolytic cell unit |
| CN100507087C (en) | 2002-11-27 | 2009-07-01 | 旭化成化学株式会社 | Bipolar zero-gap electrolytic cell |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3441495A (en) * | 1966-05-20 | 1969-04-29 | Electric Reduction Co | Bipolar electrolytic cell |
| US3451914A (en) * | 1966-08-31 | 1969-06-24 | Electric Reduction Co | Bipolar electrolytic cell |
| GB1348785A (en) * | 1970-05-26 | 1974-03-20 | Ici Ltd | Bipolar cell |
| US3759813A (en) * | 1970-07-17 | 1973-09-18 | Ppg Industries Inc | Electrolytic cell |
| US3755108A (en) * | 1971-08-12 | 1973-08-28 | Ppg Industries Inc | Method of producing uniform anolyte heads in the individual cells of a bipolar electrolyzer |
| JPS509384B2 (en) * | 1971-09-30 | 1975-04-12 | ||
| BE793045A (en) * | 1971-12-21 | 1973-06-20 | Rhone Progil | BIPOLAR ELECTRODES |
| BE793281A (en) * | 1971-12-23 | 1973-06-22 | Rhone Progil | FRAMES FOR ELECTROLYTIC CELLS OF THE FILTER-PRESS TYPE |
| BE781959A (en) * | 1972-04-12 | 1972-07-31 | Solvay | BIPOLAR CELL, |
-
1974
- 1974-10-09 JP JP49116695A patent/JPS5232866B2/ja not_active Expired
-
1975
- 1975-09-24 CA CA236,235A patent/CA1053177A/en not_active Expired
- 1975-09-24 GB GB39122/75A patent/GB1503799A/en not_active Expired
- 1975-09-29 IT IT27756/75A patent/IT1042958B/en active
- 1975-10-07 BR BR7506536*A patent/BR7506536A/en unknown
- 1975-10-08 FR FR7530776A patent/FR2287528A1/en active Granted
- 1975-10-08 SU SU752177557A patent/SU1291029A3/en active
- 1975-10-08 SE SE7511257A patent/SE7511257L/en unknown
- 1975-10-09 NL NL7511876.A patent/NL165511C/en not_active IP Right Cessation
- 1975-10-09 DE DE2545339A patent/DE2545339C2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225061A (en) * | 1991-05-24 | 1993-07-06 | Westerlund Goethe O | Bipolar electrode module |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2545339A1 (en) | 1976-04-22 |
| JPS5232866B2 (en) | 1977-08-24 |
| JPS5143377A (en) | 1976-04-14 |
| FR2287528B1 (en) | 1979-01-19 |
| SU1291029A3 (en) | 1987-02-15 |
| SE7511257L (en) | 1976-04-12 |
| GB1503799A (en) | 1978-03-15 |
| NL7511876A (en) | 1976-04-13 |
| DE2545339C2 (en) | 1982-04-01 |
| FR2287528A1 (en) | 1976-05-07 |
| BR7506536A (en) | 1976-08-17 |
| NL165511B (en) | 1980-11-17 |
| IT1042958B (en) | 1980-01-30 |
| NL165511C (en) | 1981-04-15 |
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