CN101707932B - Electrode for membrane electrolysis cells - Google Patents

Electrode for membrane electrolysis cells Download PDF

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Publication number
CN101707932B
CN101707932B CN2008800158766A CN200880015876A CN101707932B CN 101707932 B CN101707932 B CN 101707932B CN 2008800158766 A CN2008800158766 A CN 2008800158766A CN 200880015876 A CN200880015876 A CN 200880015876A CN 101707932 B CN101707932 B CN 101707932B
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electrode
electrolyzer
groove
technology
abrasion
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CN101707932A (en
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A·欧塔维尼
L·卡雷廷
D·F·迪佛朗格
C·莫加纳
M·佩里戈
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Industrie de Nora SpA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making

Abstract

The invention relates to an electrode for membrane electrolysis cells comprising a grooved metal support favouring the gas release and the electrolyte renewal on its surface. The grooved geometrical structure of the support may be obtained by erosion of a metal sheet with abrasive media in a continuous process.

Description

The electrode that is used for membrane electrolyser
Technical field
The present invention relates to be used for the electrode of electrochemical applications, particularly be used for the electrode that on metal support, prepares of membrane electrolyser.
Background technology
The electrolysis process that carries out in the electrolyzer of being separated by ion-exchange membrane is that maximally related electrochemistry in industry one of is used.Some examples of this application are electrolysis (chloric alkali electrolysis) of alkali metal chloride brines, especially referring to the electrolysis of the sodium chloride brine that is used to produce chlorine and caustic soda and the electrolysis of hydrochloric acid soln.
In the following description, will be sodium chloride electrolysis as at the most representative example aspect the whole production, but not should be understood to the present invention is only limited to this application.
In the film chloric alkali electrolysis, utilize ion-exchange membrane that the anolyte compartment and the cathode compartment of electrolyzer are separated.Concentration is the sodium chloride brine of about 300g/l for example to supply for the anolyte compartment of electrolyzer; Usually be no more than 4kA/m 2Current density under, chlorine is separated out (evolution) and is occurred in anode surface, and salt solution is consumed thus and exit concentration is reduced to usually between 200 to 220g/l.By electric field film is passed in the sodium ion conveying and arrive cathode compartment, generate weight percent concentration there and be not higher than 33% alkaline product usually.Outside electrolyzer, extract and the concentrated alkaline product then by evaporating.Hydrogen evolution also takes place on cathode surface.Require reducing capital investment makes must design the device that moves under high current density more: in fact, older device is usually at 3kA/m 2Following work, and those newer structures are at about 5kA/m 2Following operation.The current trend of device design is further to make this value increase to 6kA/m 2Or it is more.Its flow velocity may cause pressure surge with the separating out of gas of the bubble form that current density increases, this pressure surge has potential hazard to the mechanical integrity of film: for this reason, usually accurately control the pressure reduction of two Room and it is maintained below the 3000Pa, this makes electrolytic cell operation complicated.In addition, product gas has the trend of gathering between film and electrode surface on the other side, causes the ohmmic drop that consumes chlorine ion concentration partly and increased contact area owing to the renewal of electrolytic solution is bad.The brinish dilution has promoted the part of oxygen to separate out and bring thereupon acidifying.The combination of these different aspects (chlorine gathers, oxygen gathers, hold back salt solution consumption, the acidifying of (trapped brine)) causes the early stage deterioration of film, especially sentence the foaming form in the void area between anode and the film particularly and take place, caused the increase of voltage and the reduction of electrolytic efficiency.Similarly deterioration also may occur in the void area between film and the negative electrode: in this case, liquid hold-up causes alkaline product concentration to increase, and it may reach the value up to 40-45%.So high basicity can be destroyed the chemical structure of film, and is described as the antianode side, and voltage increases and follows the beginning part to bubble thereupon.
Be detained relevant problem in order to alleviate with bubble, proposed certain methods and improved near the salt water cycle of electrode surface: US 4,608,144 disclose a kind of anode surface, it is equipped with the vertical parallel channels that alternately guides salt water supply and discharge, and further is equipped with the horizontal channel of the lower part that interconnects supply and exhaust channel.Realize compulsory salt water cycle by this way, stoped the adhesion of chlorine bubbles to a certain extent.US 5,114,547 disclose a kind of anode, and it is intended to utilize the structure of being made up of the vertical channel that is connected with the secondary channel that is arranged to lambdoid inclination to promote the salt water cycle at film-anodic interface place, thus avoid this at the interface the water consumption of delay salt and the resistance that brings increases.US 2006/0042935 is improved to the water supply of anodic salt by the irregular anode surface that is obtained by sandblast or acid etch is provided, and has solved identical problem.
Though all methods that propose may help all to a certain extent to prevent that ion-exchange membrane from worsening that under common processing condition they can not guarantee the best function under the abominable processing condition that require for the satisfied current market requirement that is intended to higher electrolyzer productivity.
Therefore expect to have and a kind ofly can overcome the circumscribed electrode that is used for membrane electrolyser of prior art, especially membrane lifetime, higher concentration, the salt solution that applies gained alkaline product in current density, operating voltage, the electrolyzer utilize degree or the maximum parameter aspect that can apply pressure reduction to have the possibility of more high performance membrane electrolyser about for example operating in.
Summary of the invention
All respects of the present invention have been stated in the appended claim.
An embodiment provides a kind of electrode that obtains on metal base, it has the degree of depth is 0.005 to 0.02mm and slot pitch (pitch) (being defined as the distance between adjacent grooves) is 0.01 to the parallel groove in a plurality of parts of 0.5mm.
Local parallel groove refers to a plurality of grooves with the shape of opening or sealing, and it is parallel on its partial-length at least; The route of local parallel groove can take to pass with straight line or any type curve the almost parallel trend of entire electrode structure.In one embodiment, electrode surface presents and has local parallel groove close-shaped and that intersect each other.
The electrolysis that the above electrode that limits is used in any electrolysis, particularly directly contacted with ion-exchange membrane and works all can be favourable in using; Under the situation of chloric alkali electrolysis, above-mentioned electrode can be assembled into its groove surfaces and directly contact with film, and it all has surprising advantageous results as anode and/or negative electrode.Metal base can be made with differing materials, and this material includes but not limited to be used for the titanium and the titanium alloy of anode application and is used for nickel, nickelalloy and the stainless steel that negative electrode is used.The geometrical shape of substrate can be an any kind: as the example of indefiniteness, can perforation plate or porous plate (expanded sheet), reticulated structure with by the structure of forming along the parallel band of horizontal rotational shaft alternatively (being also referred to as the venetian blind type electrode) on groove surfaces is provided.
Can on the groove surfaces of electrode basement, provide known catalyst coatings: for example, when planning in chlor-alkali electrolytic cells when acting on the anode of separating out chlorine, can be this electrode basement coating based on precious metal or its oxide compound is provided.Limited as mentioned the electrode that obtains in the substrate in chlor-alkali electrolytic cells as the anode of separating out chlorine with when separating out the negative electrode of hydrogen, particularly particularly useful when directly contacting with film when being assembled into groove surfaces.Under the parallel situation of passing entire structure of straight groove, make groove be oriented to circulation and the bubble that vertical direction will improve electrolytic solution and discharge from the surface.Be assembled as according to configuration known in the art at electrolyzer under the situation of zero stand-off (wherein two electrodes all directly contact with film), the contriver observes and aforesaidly makes may exceed 6kA/m in a large number when having complete acceptable bath voltage making anode and negative electrode in the reeded substrate 2, reach 10kA/m 2Current density under work.Also be lower than under the situation that pressure reduction that 200g/l (being low to moderate 150g/l especially), alkaline product concentration be higher than 33% (especially up to 37%) and keep two chambers is higher than 3000Pa (especially up to 10000Pa) and carried out life test at anode electrolyte concentration, and obtained good result, when under similarity condition, adopting electrode of the prior art, cause the rapid deterioration of film usually.
Do not wish to be limited by any specific theory, may be because the more shallow groove that reaches of intensive assembling helps the capillary transport phenomenon opposite with circulation of elecrolyte, therefore can suspect with reeded electrode of the prior art and compare that the electrode that obtains in the reeded substrate defined in this allows special to discharging bubble effectively.
The electrode that is limited can obtain by simple and cheap method, and this method is for example for utilizing sand paper or the emery cloth method of continuous rotation (alternatively with), sheet emery wheel or grinding stone to carry out surface abrasion; According to selected geometrical shape, other technology comprises uses cold drawing bench or rolling mill, also has more proven technique in addition, such as laser ablation or photoetching technique.For example the abrasion of being undertaken by grinding stone is suitable for obtaining having close-shaped and local parallel groove intersected with each other, and sheet emery wheel, cold drawing bench or rolling mill are more suitable in obtaining usually along the parallel groove in whole surface.
Compare with other reeded electrode known in the art, the electrode that obtains with above mentioned technology can be significantly reduced to this, and has the characteristics of much bigger depth of groove, and this can't obtain by simple abrasion.
Embodiment
Example 1
Six 1 grade of titanium sheets that 1mm is thick and 600mm * 800mm is wide are degreased and denude processing, on all samples, obtain the groove of the various degree of depth of 0.2mm slot pitch with the sheet emery wheel; With above-mentioned expansion, obtaining diagonal lines is that 10mm * 5mm and displacement step-length (displacement step) are the rhomboid of 1.6mm (rhomboidal) mesh geometry according to known technology.After finishing spread step, profilograph records groove and shows mean depth as shown in table 1:
Table 1
Sample number into spectrum Depth of groove (mm)
A1 0.003
A2 0.006
A3 0.01
A4 0.02
A5 0.05
A6 0.2
Similarly, three nickel sheets that 1mm is thick and 600mm * 800mm is wide are degreased and carry out that identical abrasion is handled and expansion subsequently, thereby obtain identical geometry.After finishing spread step, profilograph records groove and shows mean depth as shown in table 2:
Table 2
Sample number into spectrum Depth of groove (mm)
C1 0.002
C2 0.01
C3 0.05
Using silicon carbide to carry out sandblasting and subsequently as known in the art in HCl after the etching, to carrying out the extension process identical with above-mentioned sample with a titanium sheet and a nickel sheet of being marked as A0 and C0 respectively of aforementioned sample same size; These samples are not carried out extra milled processed.
Subsequently all titanium samples are coated be covered with that the anode that is used for chlorine is separated out, based on the catalyzer of ruthenium and titanyl compound, the total loading capacity of catalyzer is 12g/m 2Depth of groove is carried out new detection, and the demonstration coating step is not introduced any obvious variation.
Example 2
The all samples for preparing in the previous examples is cut into the wide piece of 150mm * 200mm, and is being used for its feature of multi-job platform (multiple bench) test of chloric alkali electrolysis accelerated aging test in conjunction with coming with various array modes.Each measuring point (station) in the multi-job platform all disposes a membrane electrolyser, this membrane electrolyser be suitable for holding 1mm thick and with the sulfo group/carboxyl duplicature of reference (du pont company is produced
Figure G2008800158766D00051
982) anode and negative electrode that directly contacts.The electrode sample of table 1 and table 2 is assembled into the groove of vertical direction.Putting into practice than general industry under the much abominable processing condition, the electrolyzer that starts all various combinations with anode and negative electrode simultaneously carries out life test, determine the time that ion-exchange membrane damages, be defined in that bath voltage increases needed time of 0.5V with respect to its initial value under the current density of this technology this time.
Processing condition are set to as follows:
Exit ,-anolyte compartment brine concentration: 150g/l
The weight percent concentration of-product caustic soda: 37%
Pressure reduction between-two Room: 5000Pa
-current density: 12kA/m 2
What obtain the results are shown in the table 3:
Table 3
The test sequence number Anode Negative electrode Time length (h)
1 A0 C0 514
2 A0 C0 562
3 A0 C2 580
4 A0 C3 565
5 A1 C0 729
6 A2 C0 904
7 A3 C0 1213
8 A4 C0 1417
9 A5 C0 866
10 A6 C0 578
11 A2 C1 940
12 A3 C1 1283
13 A4 C1 1646
14 A5 C1 1108
15 A1 C2 887
16 A2 C2 959
17 A3 C2 1682
18 A4 C2 1704
19 A5 C2 1011
20 A6 C2 622
21 A3 C3 1088
22 A4 C3 1544
23 A3 C1 1305
24 A4 C1 1593
Example 3
Putting into practice than general industry under the obvious worse processing condition, having or not the electrolyzer of groove anode sample A0 and no groove cathode sample C0 to carry out life test the electrolyzer that disposes anode sample A4 and cathode sample C2 as in the example 2 and another similar configuration.
Processing condition are set to as follows:
Exit ,-anolyte compartment brine concentration: 180g/l
The weight percent concentration of-product caustic soda: 35%
Pressure reduction between-two Room: 4000Pa
-current density: 10kA/m 2
After about 900 hours test, dispose the electrolyzer of electrode sample A0 and C0 and have to close, because the deterioration gradually of film has caused bath voltage acutely to increase, this has obtained the high numerical value of surging in time.Take electrolyzer apart back and confirm that foaming is generally arranged from the teeth outwards, the foaming of higher quantity is arranged at salt solution relief outlet nozzle place accordingly, wherein can also observe the initial local delamination (delamination) of two-layer appearance of film.
Continuing test under the substantially invariable voltage after 2400 hours, take the electrolyzer that disposes anode A 4 and negative electrode C2 apart.On the electrolyzer of taking apart, do not observe concrete film degradation phenomena.
The description of front and indefinite the intent of the present invention can put into practice according to different embodiment under the situation that does not break away from its scope, and its scope only are limited to the appended claims.
In the application's whole specification sheets and claim, term " comprises (comprise) " and various variant does not mean other key element of eliminating or accrete existence.
The discussion to document, behavior, material, equipment, material etc. that comprises in this manual only is for context of the present invention is provided.Be not hint or expression, before the priority date of each claim of the application, any one in these things or all constitute the prior art basic component or field related to the present invention in common practise.

Claims (18)

1. electrolyzer, comprise ion-exchange membrane and at least one electrode that directly contacts with described ion-exchange membrane, described electrode comprises metal base, it has at least one surface that disposes a plurality of local parallel grooves, the depth range of described groove is 0.001-0.1mm, and the distance range between adjacent grooves is 0.1-0.5mm.
2. electrolyzer according to claim 1, the described depth range of wherein said groove is 0.005-0.02mm.
3. electrolyzer according to claim 1 and 2, wherein said groove is substantially parallel along whole surface.
4. electrolyzer according to claim 1 and 2, wherein said local parallel groove is intersected with each other.
5. electrolyzer according to claim 1, the material of the substrate of wherein said electrode are selected from the group of being made up of titanium and alloy, nickel and alloy thereof, stainless steel.
6. electrolyzer according to claim 1, the substrate of wherein said electrode have the geometry that is selected from the group of being made up of perforation plate or porous plate, reticulated structure and venetian blind type structure.
7. electrolyzer according to claim 1, wherein said electrode further are included in provides the catalyst coatings that applies on the reeded described surface.
8. electrolyzer according to claim 7, wherein said catalyst coatings comprise precious metal or its oxide compound.
9. electrolyzer according to claim 1, wherein said at least one electrode are assembled into the main vertical direction that is oriented to along the substantially parallel described groove in whole surface.
10. a manufacturing comprises the step that forms described a plurality of grooves by continuous abrasion on the described metal base of described electrode according to the method for any one described electrolyzer in the claim 1 to 9.
11. method according to claim 10, wherein said abrasion are to utilize at least one equipment that is selected from following group to carry out continuously: the roller of sand paper or emery cloth, grinding stone and sheet emery wheel.
12. method according to claim 10, wherein said abrasion utilize cold drawing bench or rolling mill to carry out.
13. one kind by applying the electrolysis process of the alkali metal chloride brines that direct current carries out in according to any one described membrane electrolyser in the claim 1 to 9, be included in the step of bubbing product on the surface of described at least one electrode.
The hydrogen that chlorine that 14. technology according to claim 13, wherein said gaseous product are anodes to be separated out or negative electrode are separated out.
15. according to any one described technology in the claim 13 to 14, wherein said galvanic density is 5kA/m at least 2
16. technology according to claim 13, wherein the pressure reduction of the film both sides of electrolyzer is 3000Pa at least.
17. technology according to claim 13, wherein the described brinish concentration in exit, anolyte compartment is 200g/l at the most.
18. technology according to claim 13, wherein the weight concentration of the basic solution of cathode compartment generation is at least 33%.
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IT000980A ITMI20070980A1 (en) 2007-05-15 2007-05-15 ELECTRODE FOR ELECTROLYTIC MEMBRANE CELLS
ITMI2007A000980 2007-05-15
PCT/EP2008/055887 WO2008138945A2 (en) 2007-05-15 2008-05-14 Electrode for membrane electrolysis cells

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ITMI20070980A1 (en) 2008-11-16
CL2008001402A1 (en) 2008-08-22
AU2008249990B2 (en) 2012-02-02
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EG25970A (en) 2012-11-13
WO2008138945A2 (en) 2008-11-20
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JP5193287B2 (en) 2013-05-08
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EP2147133A2 (en) 2010-01-27
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