CN104271809B - The stainless steel cathode that surface for electrolyzer is modified - Google Patents
The stainless steel cathode that surface for electrolyzer is modified Download PDFInfo
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- CN104271809B CN104271809B CN201380021398.0A CN201380021398A CN104271809B CN 104271809 B CN104271809 B CN 104271809B CN 201380021398 A CN201380021398 A CN 201380021398A CN 104271809 B CN104271809 B CN 104271809B
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- stainless steel
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- chlorate
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/046—Alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/06—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for producing matt surfaces, e.g. on plastic materials, on glass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C11/00—Selection of abrasive materials or additives for abrasive blasts
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
- C25B1/265—Chlorates
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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
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- Inorganic Chemistry (AREA)
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Sodium chlorate is industrially produced by the electrolysis of salt solution, and is therefore a kind of energy intensive method.It is a kind of be used for this and other commercial runs improved negative electrode be a kind of stainless steel of low nickel-content, the surface of the stainless steel is suitably modified.By the surface coarsening of appropriate amount, the negative electrode provides improved overvoltage while corrosion resistance is remained in that in electrolytic process.
Description
Technical field
The present invention relates to for industrial electrolysis, the cathode electrode in the saline electrolysis of chloric acid product salt is such as produced.Specifically
Ground, the present invention relates to the modification of the surface for such purposes, low nickel-content stainless steel cathode.
Background technology
Sodium chlorate is industrially mainly by being electrolysed to sodium chloride brine to produce chlorine, sodium hydroxide and hydrogen
Come what is produced.Chlorine forms sodium hypochlorite with sodium hydroxide immediate response, and then sodium hypochlorite changes into chlorate.In whole electricity
In solution preocess, the complicated electrochemistry and chemical reaction that are related to depend on following parameter：The temperature of electrolyte, pH, composition and dense
The potential and overvoltage of degree, anode and negative electrode, and the design of equipment and electrolysis system.It is important in order to obtain optimal result
Be groove parameter selection, such as electrode size, thickness, material, anodic coating selection and tail gas.
The material of cathode electrode in chlorate electrolyser selects and configured efficiency and negative electrode for electrolysis in the electricity
It is especially important to solve for the durability under the harsh conditions in device.Material and design combination are selected, so as to obtain
Possible surge characteristic in the process of running is together with corrosion resistance and blister resistance, cost, manufacturability and durability
The best of breed of characteristic.If using the negative electrode comprising coated substrate, the compatibility of substrate and these coatings must take into consideration.It is excellent
Selection of land, any improved cathode electrode can substitute those in the design of current electrolysis device, without for miscellaneous part
Other major designs and material of (as they are attached into support plate thereon by welding) change.
By the improvement of the overpotential to being found in electrolytic process at negative electrode, conventional chlorate electrolysis perhaps can be improved
The efficiency of device.Breakdown is lost according to caused one kind is typical in electrolyzer, cathode overpotential accounts for about the 38% of total losses
(430mV), wherein other key losses and bath resistance, anode overpotential, metallic resistance and " bichromate effect " (this
It is by when using sodium dichromate as buffer and for suppressing the reduction of hypochlorite and chloranion in negative electrode
On negative electrode caused by film forming) it is relevant.
In the unipolarity and mixing chlorate electrolyser design of commercialization, negative electrode is typically uncoated carbon steel type,
As Domex levels steel, C1008 andIt is latterNegative electrode using what is selected there is element-specific to form
Steel, hydrogen blister and hydrogen embrittlement during to avoid and/or reduce use.Just service condition normal range (NR) (for example, from
2.5kA/m2To 4.0kA/m2Current density and temperature from 60 DEG C to 90 DEG C) in tank voltage and overpotential for, such the moon
Pole and routineThe performance of (dimensional stable anode) anode combination is fairly good.A kind of relatively low cost of they or electrolyzer
Part.
However, under the normal running (operation) conditions with cathodic protection, uncoated carbon steel electrode corrosion-vulnerable is (raw
Rust), this causes negative electrode to be thinned, it is undesirable to metal ion enter in electrolyte, and reduce cathode life.In the pre- of electrolyzer
In life-span phase, shut-down and power failure are there may typically be, these accelerate the corrosion of negative electrode.Metal ion deposition in electrolyte
Anode and cathode performance may be influenceed on electrode and simultaneously by such fouling, produce the rise of groove potential and oxygen
The symptom of gas generation, and cause higher operating cost.Negative electrode is shown main on whole working region more or less
The equally distributed spot corrosion formula surface erosion in ground.Such corrosion is for being typical case exposed to the carbon steel cathodes of hypochlorite
's.Due to using central and must be driven off the dirt before reusing and (such as pass through, it is necessary to carry out mechanical chipping to negative electrode
Sandblasting) and pickling.Typically, the material (most of is iron) of significant quantity is removed in such a process so that carbon steel cathodes
Sizable corrosion allowance is needed to carry out the loss of compensating material, so as to result in the need for thicker negative electrode and therefore reduce every list
The active electrode area of position volume.In addition, when negative electrode is renovated and is put back in use, in electrolyzer between negative electrode and anode
Gap will increase, and cause voltage to increase.
Alternately, it may be considered that other materials is used as chlorate electrolyser negative electrode.However, it is different from
Related industrial chloric alkali electrolysis process (wherein, sodium chloride brine is subjected to electrolysis to form sodium hydroxide, hydrogen and chlorine product)
In, it is impossible to using the negative electrode of the nickel based on nickel or comprising significant quantity.The presence of nickel causes the decomposition rate of hypochlorite to increase, and
And therefore reduce product yield and produce oxygen more higher levels of than normal condition.Which results in the worry of security, because
Oxygen potentially may be combined to obtain unsafe, volatile mixture with existing hydrogen.Thus, by not nickeliferous or
The negative electrode that person at least has low nickel content (for example, less than by weight about 6%) is used for chlorate electrolysis.
The stainless steel (for example, ferritic, martensite, two-phase and precipitation-hardening) of some grades is low nickel
The stainless steel of content rating, and the advantage better than carbon steel can be provided in terms of its anti-corrosive properties.It is used as chlorine however, working as
Hydrochlorate electrolysis in negative electrode when, the stainless steel of these types and actually general stainless steel are at least when they are typically made
When being ready for use on commercial use, overvoltage substantially higher than carbon steel is shown.
As another alternative solution, in the art it has been proposed that a variety of coatings are used to prepare as in saline electrolysis device
Electrode coated substrate purpose.For example, Canadian patent application CA2588906 discloses the coating as chlorate electrolysis
Nanometer crystal alloy.Also RuO is had been proposed that2Type coating is as the electrode coating in saline electrolysis.However, the moon using carbon steel substrates
Pole can not easily with typical noble metal and containing Ru, Ir, Ti, or the like mixed oxide coatings coat.When making
When being coated with conventional method, the problem of tack and degraded be present.And then this causes the endurance issues of these coatings, due to
When the carbon steel substrates of bottom are corroded, they simply " are peeled off (exfoliate) " or " coming off (flake off) ".(
In US7122219, it is intended to solve this problem for being intended to the electrode for chloric alkali electrolysis.) be very difficult to obtain and chlorate electricity
The carbon steel coated cathode that 5 to 8 years life expectancies of the standard commercial anode in solution device match.
It is well known that the appropriate surface treatment (such as sandblasting) of metallic substrates can cause to improve coated painting
The tack of layer.And it is known that (for example, as disclosed in US6017430), is electrolysed to aqueous alkali metal chloride
The middle negative electrode used, which carries out spray coarse sand processing, to reduce the hydrogen overvoltage at the negative electrode by increasing its surface area.However,
Also it is well known that surface smoothness is important for more preferable stainless steel corrosion resistance.Due to when stainless steel is clean and
When smooth, they are most corrosion-resistant, have especially sought low surface roughness in extreme corrosive environment, such as salt water power
Solve the environment in device.
Characterize roughness in many ways in the industry.Roughness parameter (arithmetic mean of instantaneous value of such as roughness, represents
For Ra, and the mean-square value of roughness, it is expressed as Rq) it is usually used to quantifying surface roughness, and carried out by standard method
It is determined that.Further, it is also possible to surface is characterized with more qualitatively terms (such as " finish ").No.4 finish is stainless
Steel is a general polishing finish, and than other, common finish is dimer, and is generally used for wherein outward appearance and cleaning
Important working surface or the like is spent (for example, being set for what is used in food, dairy produce, beverage and pharmaceuticals industry
It is standby).According to ASTM A480, the R of No.4 finisha0.64 micron can be generally up to.RaCan be RqAbout 80%, and
Therefore the R of No.4 finishq1 micron will be less than to a certain extent.
However, although phase be present between these various surface roughness characteristics and other characteristics (such as outward appearance and corrosion resistance)
Guan Xing, two surfaces can have identical Ra(and/or identical Rq) but depend on how to obtain surface condition and there is difference
Outward appearance or corrosion resistance.For example, this class feature can depend on finish whether be orientation or it is random (for example, respectively
Obtained by belt abrasion or sandblasting) and other factors (such as be orientated) change.
Although industrial chlorate electrolysis method is fairly advanced, however it remains to increasing efficiency, the electrolyzer life-span,
And the hope that cost reduces.
The content of the invention
The present invention shown by providing the improved electrolysis cathode of desired overvoltage and anti-corrosive properties come
Solve these demands.It is for instance possible to obtain with those similar or more preferable overvoltage seen by carbon steel cathodes, and with normal
Advise the similar corrosion resistance desired by negative electrode made of stainless steel.Such negative electrode is useful for chlorate electrolysis and can
For other industrial electrolysis methods.
Unexpectedly, if being modified or handling to surface to obtain certain surface roughness, with some
Negative electrode made of the stainless steel of not nickeliferous or low nickel-content (for example, less than by weight about 6%) can realize both characteristics.
Being potentially suitable for the low nickel-content stainless steel of this purpose includes some ferritic, martensite, two-phase and precipitation firmly
The stainless steel of change.Can advantageously it use comprising one or more stainless steels for stabilizing dopant.Suitable dopant bag
Include Cu, Mo, N, Nb, Sn, Ti, V and W.Can also be advantageously in certain embodiments using stainless with low carbon content
Steel, for example, being less than by weight about 0.03% and preferably smaller than by weight about 0.005%.
Specifically, low nickel-content stainless steel can be a kind of ferritic stainless steel, 430,430D, 432 or 436S etc.
The stainless steel of level, or a kind of ferritic stainless steel for including Mo, Sn, Ti, and/or V dopant.The stainless steel allusion quotation of ferritic grade
Contain p and ses impurity type.The stainless steel, which can be included preferably, is less than by weight about 0.03% phosphorus and less than by weight
The sulphur of gauge about 0.003%.In addition, low nickel-content stainless steel can be a kind of two phase stainless steel, such as S31803, S32101,
S32205, S32304, S32404, S82011 or S82122 be poor/two phase stainless steel of low-alloy grade.
It has been found that the surface roughness R between about 1.0 microns with 5.0 micronsqIt is suitable on overvoltage
Close, and improved corrosion resistance can also be provided.Specifically, there is the R less than about 2.5 micronsqFerritic stainless steel
Appear to be suitable.
The stainless steel that surface is modified can directly (uncoated) negative electrode as in industrial electrolysis, such as sodium chlorate,
Potassium chlorate or sodium perchlorate electrolyzer.For in this embodiment, cathode weld can be made to by carbon steel or stainless steel
Support plate on.Advantageously, if by cathode weld to made of a kind of appropriate stainless steel on support plate and electrolyzer it is surplus
Remaining part point is also to be made up of a kind of appropriate stainless steel, then the electrolyzer is not required to use cathodic protection unit.
Alternately, the stainless steel that surface is modified may be used as the substrate in negative electrode, and the negative electrode is included and is applied in substrate
Electrolysis enhancing coating.Surface modification can improve the tack of suitable electrolysis enhancing coating.And in addition, although surface changes
Property substrate overvoltage advantage be not perhaps in new coated cathode it is required immediately or observe, but when the coating most
When wearing away eventually, then the stainless steel base that the surface of bottom is modified is exposed.At this moment, exposed substrate shows this hair this moment
The overvoltage and corrosion resistance advantage of bright combination, and so as to extend the useful life of negative electrode, more than existing industrial standardUseful life.
Therefore, the table by the surface coarsening of low nickel-content stainless steel cathode extremely between about 1.0 microns and 5.0 microns is passed through
Surface roughness Rq, while the corrosion resistance of negative electrode is kept, it is cloudy that chlorate electrolyser in the electrolytic process of salt solution can be reduced
The overvoltage of pole.A variety of method of roughening can be used, such as sandblasting is carried out with alumina powder foot couple cathode surface.
Brief description of the drawings
Fig. 1 compares SS430 cathode samples, a kind of comparative SS430 samples that several representational surface is modified
A kind of and micro-groove voltage versus current density curve map of conventional mild steel sample.
Fig. 2 depict SS430 cathode samples in example become with surface roughness in several representational electric currents
Miniature tank voltage under density.
Fig. 3 compares a variety of RuO2Coating, surface modification SS430 cathode samples are micro- with a kind of conventional mild steel sample
Type groove voltage versus current density curve map.
Fig. 4 compares the micro- of ferrite cathode sample that several representational surface is modified and a kind of conventional mild steel sample
Type groove voltage versus current density curve map.
Fig. 5 compare the groove comprising conventional carbon steel negative electrode with comprising according to the present invention carried out surface treatment
Curve of the electrolysis pilot scale tank voltage of the groove of SS430 negative electrodes and the ferrite negative electrode of doping under normal operation to days running
Figure.
Embodiment
Unless the context requires otherwise, in entire description and claims, term " including (comprise) ",
" including (comprising) " etc. should be interpreted opening, pardon meaning.Term " one/a kind of (a/an) "
Etc. should be considered as meaning at least one and being not limited to only one.
In addition, make intentionally defined below.Under numerical value background, term " about ", which should be interpreted that, means to add deduct 10%.
Stainless steel refers to the steel alloy with minimum by mass 10.5% chromium content.
Surface roughness RqThe mean-square value of the roughness as determined according to standard JIS2001 or ISO1997 is referred to, and
And it is used in following example.
And here, electrolysis enhancing coating refers to the coating in chlorate electrolyser on electrode, the coating causes just
The reduction of overvoltage in normal running.A variety of such coating compositions are well known in the art, and are typically comprised
Precious metal composition such as RuO2。
In the other conventional electrolysis device for industrial production chlorate, have unexpectedly discovered that if some low nickel
The surface of content stainless steel is suitably modified, then they are used as the improved material of cathode electrode.Such negative electrode exists
Keep from desired corrosion resistance desired by conventional stainless steel while, show it is similar with those obtained with carbon steel or
Preferably desired surge characteristic.
Suitable stainless steel be free from nickel or with less than by weight about 6% nickel content.Several species it is stainless
Steel meets this requirement, including ferritic, martensite, two-phase and precipitation-hardening stainless steel.It is furthermore, it is possible to favourable
Ground stabilizes dopant in stainless steel using one or more.Suitable such dopant include Cu, Mo, N, Nb, Sn, Ti,
V, and W.0.03% or small can also be less than about by weight advantageously with low carbon content or unusual low carbon content
In the stainless steel of about 0.005% phosphorus content.(known carbon to form methane to promote hydrogen embrittlement by being reacted with hydrogen.Therefore, analysing
Carbon present in hydrogen negative electrode is more, then is more possible to form methane in cathode substrate.Methane grain boundary in the substrate or
Accumulation in defect (field trash of such as sulfide or oxide type) can cause bubbling and the embrittlement of substrate).
Specifically, ferritic stainless steel can be suitable, and it is chromium (from about to be distinguished by main alloy element
In the range of 10.5wt% to 27wt%), this provides the ferritic structure of stabilization at all temperatures.Contain because its is low
Carbon amounts, ferritic stainless steel has limited intensity, but can have good ductility, and they are seldom hardened.
The toughness of these alloys is at a fairly low, but this is not required for the negative electrode in as electrolyzer.In unshielded feelings
Under condition, rich Cr ferritic stainless steel is finally corroded in the chloride liquid of heat, but unlike carbon steel is so fast.Rich Cr stainless steels
To release Hydrogen over potential higher than carbon steel.Rich Cr stainless steels seem not corrode faster when being in contact with carbon steel, due to the former simultaneously
The sacrificial anode of the latter is not served as.This is important for replacing or upgrading being achieved in that for the carbon steel cathodes in commercial electrolyte device
, because the cathode side of support plate in electrolyzer may be still carbon steel, and therefore ferritic stainless steel will be compatible.It is a kind of example of potential suitable ferritic stainless steel, with about 12% Cr contents and shows good
Good solderability.Alternatively of course, the support plate made of being adapted to the stainless steel of grade can also be used, so as to eliminate all deposit
Carbon steel and therefore eliminate any problem brought using dissimilar metal.
Test is it has been shown that the ferritic grade including 430,430D, 432 and 436S can be suitable.It is and specific
Ground, the ferritic stainless steels in some ultralow gaps comprising dopant have shown significantly changing to electrolyzer overvoltage
Enter.It is also contemplated that other ferritic grades will be suitable, including (it is respectively at comprising Mo, Nb and V dopant
The exemplary value of by weight about 1.8%, 1.6% and 0.06%) 444 grades, and 434,439,441,442 and
The stainless steel of 446 grades.
The ferrite or martensitic stain less steel alloy of other low nickel-contents can contain molybdenum, and this is provided most of for them
It is far superior to the corrosion resistance of conventional carbon steel in chemical environment.These alloys of many types being present, they contain other elements,
Such as Mn, Si, Al, Se, Cb, Cu, Ta, N and W, these elements can be provided for such application electrical conductivity, surface-active, can
Extra benefit in terms of manufacturing and/or durability.For example, wherein Cr is double in the range of from about 4wt% to 18wt%
Phase stainless steel, also known as ferritic-austenitic stainless steel, there is welding characteristic more more preferable than ferritic stainless steel.It is contemplated that
Some double phase stainless steel alloys, such as UNS trades mark S32101, S32304 and S82441 grades are (for example, be respectively to be commercialized
LDX2101TM、LDX 2304TMOr LDX 2404TM) together with S31803, S32205 and S82122, there is provided except performance is excellent
Following advantage outside gesture, including superior corrosion resistance, manufacturability (also have welding more more preferable than ferritic stainless steel special
Property) and commercially available property.
In order to obtain the similar or more preferable overvoltage with being obtained with carbon steel, it is necessary to the low nickel-content stainless steel of routine
Surface be roughened, typically so that its surface roughness RqTo be greater than about 1.0 microns.Such as, it is intended to for following instance
In surface roughness R when such as obtaining of the ferritic stainless steels of conventional 430 gradesqFor less than 0.1 micron.Utilize blasting method
Its surface is suitably roughened with alumina powder foot couple.
It is contemplated that stainless steel surfaces are roughened with any one of distinct methods known in the art.Example
Such as, together with sandblasting, alternative abrasion techniques are (for example, desk-top sandblasting (table blasting), belt sandblasting (belt
Blasting), cartridge type sandblasting (cylinder blasting)) and exist including chemical etching, micromachined and micro- milling
Interior method may also be used for suitably increasing surface roughness.However, also as known in the art, these surface characteristics may
Changed according to method detailed used.For example, the surface characteristics obtained by sandblasting can be according to the type (example of powder used
Such as, aluminum oxide, sodium acid carbonate, carborundum, bead, cullet), powder diameter, jet size, pressure, distance, angle etc. and
Change.And as the mach technique of photochemistry allows surface milling and is ground to more accurate depth and to bigger
RqValue.
Although in order to obtain desired overvoltage, it is desirable to the surface roughness of the increase of low nickel-content stainless steel, mistake
The roughness of degree may cause unacceptable etching characteristic.Based on following instance, up to 5.0 microns of surface roughness RqValue
Still can be acceptable.In some instances, it may be preferred to it is up to about 2.5 microns of value.However, it is possible to it is necessary that by
The cathodic protection of negative electrode offer is maintained in the normal operation of electrolyzer, or breaks in the supply or is provided in the case of closing and replaced
For the salvo of property.
The low nickel-content stainless steel cathode that surface is modified can substitute existing conventional carbon steel negative electrode, advantageously provide simultaneously
More preferable durability, cost and performance.Can successfully by the carbon steel support plate of such cathode weld to standard to be used as routine
The substitute of carbon steel cathodes is used in industrial electrolysis.Welding can be by filler wire (such as welding rod), protective gas, standby
Purging and the various combination of welding parameter (including electric current, voltage and speed) are completed.Therefore, for the electrolysis of renovation
Tank and new electrolyzer system need not all carry out main electrolyzer design and change.In addition, perhaps it is possible to send out this
Bright negative electrode is merged into the design (for example, bipolarity type) in future.
Alternately, if industrial electrolysis is made up completely of appropriate stainless steel and therefore for example negative electrode is soldered to
On the support plate being made of stainless steel, then the electrolyzer can not have to cathodic protection and therefore may not be needed to use cathodic protection
Unit.
Other advantages of the present invention include the energy-conservation obtained from lower cathode overpotential.Also, with preferably certain
In the case of the corrosion resistance of a little grades, it is believed that the electrolyzer of thinner negative electrode embodiment per unit volume produces more
Product and/or size and cost is allowed to reduce for identical output level.It is still possible that due to by more coarse finish
Caused " anchorage effect " and the failure mechanism related to corrosion of carbon steel is avoided, for tack and durability, this
The negative electrode that class surface is modified will be more compatible with electrolysis enhancing coating.Also, even if there is no significant advantage, once coating is
Wear away or fail in addition, it is contemplated that the stainless steel base that the surface of bottom is modified will continue to provide normal operation and substantive
It is upper to retain the longer time than conventional carbon steel substrates, so as to extend the useful life of such coated cathode.
Following examples have been included to illustrate certain aspects of the invention, but are not necessarily to be construed as carrying out in any way
Limitation.
Embodiment
Micro-groove is tested：
Test a series of cathode material sample in the micro-groove of laboratory in a static condition, but in other respects with
Those undergone in commercial chlorate electrolyser are similar.Micro-groove construction use a kind of cathode material sample as groove negative electrode and
Using a kind of adjustedAs groove anode.Two electrodes are all flat sheets.Active testing surface area is 2cm2And
And the gap between them is 5.8mm.Electrolyte is the NaClO that concentration is 450/115/5gpl3/NaCl/Na2Cr2O7It is water-soluble
Liquid.These electrodes are immersed in the electrolyte under 80 DEG C of test temperatures.It is different from commercial electrolyte device, it is electrolysed in test process
Liquid is without circulating and not supplying persistently salt solution raw material.
Wherein indicate, various cathode material samples are that surface is modified, and are measured before being assembled into micro-groove
Their roughness.Then fresh electrolyte is added, is heated to test temperature, and carries out polarization test, polarization test
It is related to while tank voltage is recorded, makes applied current density from 0.5kA/m2Until 6kA/m2Tiltedly become.Then stop surveying
Examination, and check the signs of corrosion of sample electrode.
Surface roughness R is determined using three rich surface roughometer (Mitutoyo Surftest) SJ210q.To each
Cathode material sample carries out the sampling of six subsurface roughness in 2.5 to 6 inches of sampling length in random position, and right
The maximum deviation of each sampling determination and center line.The R reportedqBe this six deviations square arithmetic mean of instantaneous value square
Root.
The unmodified cathode material sample tested includes：
- the R with 2.16 μm of measurementq'sMild steel (is expressed as " mild steel ") in accompanying drawing and table
- 2D the mill finishes with supplier and the R of the measurement with 0.26 μmq420A grade stainless steels
(SS420A) (it is expressed as in accompanying drawing and table " SS420A-0.26 μm ")
- bright the mill finish with supplier and the R of the measurement with 0.06 μmq430 grade stainless steels
(SS430) (it is expressed as in accompanying drawing and table " SS430-0.06 μm ")
(pay attention to：Two kinds of stainless steel samples are respectively provided with similar low nickel-content, i.e.,<0.25wt%, and comprising a certain amount of
Mn, S, P, Si, Cu and Mo.SS420A grades have by weight 0.25% and 12.83% C and Cr contents, and also have
There is micro Al.SS430 grades have by weight 0.04%, 16.64% and 0.03% C, Cr and N content.)
By taking SS420A and SS430 samples similar to above and subjecting them to the alumina powder using 120 mesh
End artificial blasting craft come prepare surface modification cathode material sample.The sample that the surface tested is modified includes：
- processing is grit blasted to measured surface roughness Rq(it is expressed as 1.73 μm of SS420A in accompanying drawing and table
“SS420-1.73μm”)
- processing is grit blasted to multiple surface roughness R in from 0.86 μm to 4.62 μ msqA series of SS430
Sample (is expressed as " SS430-0.86 μm " to " SS430-4.62 μm ") in accompanying drawing and table according to its surface roughness
In addition, with a range of RuO2Load capacity prepares RuO2Coating, surface modification SS430 cathode material samples
Product.Cathode material sample is by initially carrying out sandblasting to 430 stainless steel samples as above and then using RuCl3Solution is carried out
Internal coat, it is obtained then to carry out heat treatment step.Definitely, oil removing is carried out to sample, is rinsed and then in room temperature
It is lower to be etched 5 minutes with 10% HCl solution.After rinsing and dry again, using a kind of RuCl3In organic solvent molten
Liquid.By the sample drying of coating, and heat treatment 20 minutes is then carried out at about 420 DEG C.More than once apply coating and
It is heat-treated for obtaining bigger load capacity.
Prepared and test RuO2Coating, surface modification sample is summarized in table 1 below：
Table 1.RuO2Coating, surface modification sample
| Sample ID | Rq(μm) | RuO2Carrying capacity (g/m2) |
| RuO2#1 | 1.6 | 2.77 |
| RuO2#2 | 1.55 | 4.33 |
| RuO2#3 | 1.45 | 5.54 |
| RuO2#4 | 1.45 | 6.1 |
Then assembling includes the micro-groove of each in these cathode material samples, and is subjected at 80 DEG C
From 0.5kA/m2To 6kA/m2Current density range in polarization test.
Table 2 summarizes the cathode sample being modified for the mild steel sample, SS420A-0.26 μm of sample and surface of routine
The SS420-1.73 μm of data obtained.Table 2 shows the experiment of each cathode sample under the multiple current densities tested
The miniature tank voltage in room.As is apparent from this data, the groove with unmodified SS420A-0.26 μm of negative electrode is substantially than tool
Have and run under the bigger tank voltage of the groove of conventional mild steel negative electrode or overvoltage.However, the SS420-1.73 μ being modified with surface
The groove of m negative electrodes is run under than the groove of the mild steel negative electrode with routine slightly or even slightly lower tank voltage.Definitely, in 4kA/m2
Under, the unmodified SS420A-0.26 μm of cathode can voltage ratio high 150mV of mild steel tank voltage, and the SS420-1.73 μ that surface is modified
The small 25mV of m cathode can voltage ratio mild steel tank voltages.
The tank voltage for the SS420 samples that table 2. is tested is to current density
After test, these cathode samples are checked.It is found that two kinds of SS420 samples have all substantially been corroded.
Table 3 summarizes the data obtained with blasting treatment to a series of SS430 samples of a variety of surface roughnesses, and
And by them compared with comparative unmodified SS430 and mild steel cathode sample.Show in the multiple electricity tested
The laboratory micro-groove electricity of every kind of cathode sample under current density.
The tank voltage for the SS430 samples that table 3. is tested is to current density
Fig. 1 compares SS430 cathode samples, the comparative unmodified SS430- that several representational surface is modified
The micro-groove voltage versus current density curve map of 0.06 μm of sample and conventional mild steel sample.(provide one and run through mild steel sample
Data line as eyes guide.) as shown in Figure 1, there is the groove of unmodified SS430-0.06 μm of negative electrode also in reality
Run in matter under the overvoltage bigger than the groove with conventional mild steel negative electrode.The SS430 samples being modified as surface, with surface
R of the roughness increase until about 1.70 μmq, overvoltage generally improves.It is less than with surface roughness or is about 1.15 μm
The micro-groove of SS430 negative electrodes with the operating voltage lower than the groove with unmodified SS430-0.06 μm of negative electrode, but unlike
Groove with conventional mild steel negative electrode is so low.However, with the micro- of the SS430 negative electrodes that surface roughness is about 1.70 μm or bigger
Type groove is with the operating voltage similar or lower with the groove with conventional mild steel negative electrode.However, surface roughness increases to 1.81 μ
M does not reduce operative cell voltage significantly further apparently (not shown in Fig. 1, but referring to table 3).Definitely, in 4kA/m2Under,
The unmodified high about 230mV of SS430-0.06 μm of cathode can voltage ratio mild steel tank voltage, and SS430-1.81 μm of negative electrode tank voltage
About 70mV smaller than mild steel tank voltage.
Fig. 2 depict SS430 cathode samples become with surface roughness under several representational current densities
Observed miniature tank voltage.Definitely, depict in 2kA/m2、3kA/m2And 4kA/m2Under miniature tank voltage.As it is pre-
Phase, miniature tank voltage increases with used current density.And primitively, miniature tank voltage subtracts with surface roughness
It is small.Unexpectedly, however, the miniature tank voltage under each current density apparently reaches at about 1.8 μm of surface roughness
To their minimum.
Fig. 3 compares a variety of RuO2SS430 cathode samples and the micro-groove of conventional mild steel sample of coating, surface modification
Voltage versus current density curve map.As seen in Figure 3, each with RuO2The groove of coating, surface modification SS430 negative electrodes exists
Run under tank voltage substantially lower than the groove with conventional mild steel negative electrode.However, based on the test carried out, RuO2It is negative
Carrying capacity does not significantly affect tank voltage.In 4kA/m2Under, RuO2Coating, surface modification SS430 negative electrodes tank voltage is substantially
Less than mild steel negative electrode tank voltage, i.e., low about 240-280mV.
Testing all above SS430 and RuO2After the sample of coating, on any not in these samples
It was observed that visible corrosion.
Another a series of ferrite cathode material sample is obtained, surface modification is carried out to it, and as described above real
Test in the micro-groove of room and tested and/or such as following carry out corrosion test described below.These samples include following herein
：
- 430 grades of stainless steels, consisting of：By weight 0.042% C, 0.36% Si, 0.48% Mn,
0.031% P, 0.0015% S, 16.13% Cr, 0.15% Ni, 0.041% N, remaining is Fe, and is being carried out
R with 2.13 μm of measurement after sandblastingq(being expressed as in Fig. 4 " SS430 ")
- 430D level stainless steels, consisting of：By weight 0.005% C, 0.1% Si, 0.11% Mn,
0.025% P, 0.002% S, 16.39% Cr, 0.29% Ti, remaining is Fe, and has 2.1 after sandblasting is carried out
μm measurement Rq(being expressed as in Fig. 4 " SS430D ")
- 432 grades of stainless steels, consisting of：By weight 0.004% C, 0.1% Si, 0.08% Mn, 0.022%
P, 0.001% S, 17.20% Cr, 0% Ni, 0.18% Ti, 0.01% N, 0.48% Mo, 0.02%
Cu, remaining is Fe, and the R with 1.89 μm of measurement after sandblasting is carried outq(being expressed as in Fig. 4 " 432 ")
- 436S level stainless steels, consisting of：By weight 0.005% C, 0.1% Si, 0.09% Mn,
0.022% P, 0.002% S, 17.2% Cr, 0.23% Ti, 0.011% N, remaining is Fe, and is being sprayed
R with 2.09 μm of measurement after sandq(being expressed as in Fig. 4 " SS436S ")
- LDX2205 level stainless steels, consisting of：By weight 0.018% C, 0.38% Si, 1.54% Mn,
0.023% P, 0.001% S, 22.50% Cr, 5.70% Ni, 0.017% N, 3.10% Mo, remaining is Fe,
And the R with 1.73 μm of measurement after sandblasting is carried outq(being expressed as " LDX2205 ", but not shown in FIG. 4)
A kind of-the stainless steel of first doping level, consisting of：By weight 0.004% C, 0.12% Si,
0.10% Mn, 0.024% P, 0.001% S, 14.4% Cr, 0.11% Sn, 0.20% combination Nb+Ti,
0.010% N, remaining is Fe, and the R with 2.35 μm of measurement after sandblasting is carried outq(be expressed as in Fig. 4 " doping-
1”)
A kind of-the stainless steel of second doping level, consisting of：By weight 0.005% C, 0.07% Si,
0.06% Mn, 0.020% P, 0.001% S, 16.4% Cr, 0.31% Sn, 0.22% combination Nb+Ti,
0.010% N, remaining is Fe, and the R with 2.14 μm of measurement after sandblasting is carried outq(be expressed as in Fig. 4 " doping-
2”)
The ferrite cathode sample and Fig. 1 for the doping that Fig. 4 compares the ferrite of these surfaces modification and surface is modified
The micro-groove voltage versus current density curve map of conventional mild steel sample.(432 samples are not tested and therefore it is not
Occur in Fig. 4.And only obtain 4kA/m on LDX2205 samples2Under voltage, therefore it does not appear in Fig. 4 yet
In.LDX2205 this voltage is 3.18 volts.) in the case of all measurements, surface be modified sample result be comparable to or
It is better than conventional mild steel sample.
In order to obtain and corrode relevant additional information, also it is subjected to the above-mentioned sample including conventional mild steel sample
Corrosion test, wherein single sample is exposed to corrosive, circulation from pilot-scale chlorate reactor
" hypochlorite " electrolyte.(it is somebody's turn to do " hypochlorite " and includes a kind of about 4g/L HClO and NaClO solution, the solution is about
Circulated at 70 DEG C with 60L/h flow velocity, and from 4kA/m2Current density under obtain in the reactor that runs.) these samples
The area of product is about 80mm × 35mm and thickness is about 3mm, and they are lasted up into 5 hours exposed to the electrolyte
A period of time.The weight loss for being then based on thus these samples caused by secondary exposure (is recorded as to determine corrosion rate
Per unit area and the weight loss of time).Table 4 summarizes some observed corrosion rates.
Corrosion rate observed by table 4.
The corrosion rate for all samples tested is considered as acceptable.(notice the measured of LDX2205 samples
Corrosion rate it is very low.Although correct, other tests show that crevice corrosion should be paid close attention to, because it may significantly much.)
These examples show that the negative electrode of the ferritic stainless steel based on SS430, SS430D, SS436 and doping can fit
Locality carries out surface modification, so as to while acceptable corrosion resistance is remained on, provided in chlorate electrolyser with
As conventional mild steel cathode type or preferably overvoltage performance.
Middle experimental tank test：
With undergone in the chlorate electrolyser of commercialization those under the same conditions, in one bigger pilot-scale electricity
A kind of be modified in chemical tank to surface SS430 negative electrodes (having the composition similar to Fig. 4 SS430 samples), a kind of surface changes
- 2 type cathodes (there is the composition similar to -2 samples of Fig. 4 doping) of the doping of property and a kind of conventionalMild steel negative electrode is compared test.Experimental tank uses effective area as 19 square inches of planar cathode in these,
The commercially available anode of identical (has RuO2The DSA of coating), and a kind of water for including sodium chlorate, sodium chloride and sodium dichromate
Solution and the NaClO having3/NaCl/Na2Cr2O7Concentration is 450/110/5gpl electrolyte.Electrolyte is with 0.8 liter/peace
The speed of training hour flows through the groove, and is controlled as pH 6.0.In test process, temperature is in the scope from 80 DEG C to 90 DEG C
Interior change and current density is from 2kA/m2To 4kA/m2.Pilot scale tank voltage is recorded in test process, and is also monitored by the groove
Oxygen concentration in caused tail gas.Oxygen is undesirable accessory substance in such electrolysis.Higher oxygen in tail gas
Concentration shows lower current efficiency (that is, consuming more energy to produce same amount of sodium chlorate).In addition, when with also producing
Hydrogen mixing when, higher oxygen concentration causes security concern.(many factors including two kinds of electrode materials may
Influence oxygen concentration.Although this is not the direct instruction of electrode corrosion, with regard to electrode selection for, it be one to be considered it is non-
Normal important criteria.)
The negative electrode tested again includes the R with 2.16 μm of measurementqIt is conventional comparativeMild steel
Negative electrode, processing has been grit blasted to the R of 1.54 μm of measurementqSS430 negative electrodes and be grit blasted processing to 1.91 μm of measurement
RqDoping -2 type stainless steel cathodes.
Initially, those (90 DEG C and 4kA/m used during being electrolysed with normal production are passed through2) compared to reduce temperature and
Current density (80 DEG C and 2kA/m2) under operation adjust all grooves.In the process of 1-6 days, temperature and current density are increased
Big 90 DEG C and 4kA/m that institute's normal use is electrolysed to production2Value.It is stabilized simultaneously in tank voltage, continue under these settings
Operation.During regulation, tank voltage drifts about upwards within the time in or so two to the three initial weeks of operation.This is a kind of normal
Effect, and be byCaused by the regulation of anode and cathodic polarization.Fig. 5 is compared after tank voltage has been stablized
Pilot scale aluminum pot working voltage under normal operation is to days running.(in Fig. 5, show from the 12nd day and later voltage.
Pay attention to：The mild steel negative electrode by contrast compared with property has carried out the other preconditioning of up to 12 days.) as in Fig. 5 it will be evident that having table
The groove for the SS430 negative electrodes that face is modified has the tank voltage for being markedly inferior to comparative groove.After the regulation of 12 days, based on surface
The groove of modified SS430 negative electrodes is run under 3.18 volts, and the oxygen concentration in tail gas is low 1.7%.It is worth noting
Ground, the groove of -2 serial negative electrodes of the doping being modified with surface is with the lower groove electricity of even surface improved SS430 negative electrodes
Pressure, and its superior property retention is more than the days running of 85 days.
In order to obtain the finger of the corrosion resistance for the SS430 negative electrodes that experimental tank service condition lower surface is modified in these are normal
Show, the electrolyte of the about 1200ml from the groove is filtered by 934-AH glass microfibre filter papers.Do not see in filter paper
To discoloration, this shows do not have signs of corrosion in the electrolytic solution after middle experimental tank is run 20 days under normal operating conditions.
The SS430 negative electrodes evaluation being modified on surface again, continue to carry out test under normally production electrolytic condition and hold
It is continuous to amount to 46 days, cathodic protection be present during this time.Hereafter, experimental tank in this is made to be subjected to power failure test.This test
The corrosion resistance in the case where electrolyzer occurs and closes is have rated, cathodic protection is not present during this time.The test bag
Include and cut off the electricity supply three times, every time the period of five minutes, wherein there is the normal operation period of five minutes between cutting off twice.
Again, take electrolyte sample and filtered by filter paper.Specifically, it was observed that the sign of cathodic corrosion.However, with mild steel
The difference observed on negative electrode, the corrosion pattern on SS430 negative electrodes are local (such as spot corrosion) and not in whole surface
On.Therefore the improvement better than mild steel is indicated, and the coating in the major part on expectable SS430 surfaces will be unaffected.
The instruction of the corrosion resistance of -2 negative electrodes of the doping that surface is modified is in a similar manner by from wherein experimental tank
Electrolyte is filtered and checks residue and change colour to obtain.Again, after normal middle experimental tank service condition and also
After having power failure test, electrolyte sample is taken.In this case, experimental tank normal operation 137 days in this, while still
Remain 3.21 volts of obvious low tank voltage.Then an electrolyte sample is taken, and the groove is subjected to power failure survey
Examination, takes thereafter another electrolyte sample.Again, discoloration is not seen in filter paper, this shows the normal pilot scale at 137 days
Do not have signs of corrosion in the electrolytic solution after groove operation.And signs of corrosion again, has been seen after an interruption of the power supply, but
Again, the corrosion pattern on -2 negative electrodes of doping is local that discoloration on filter paper is moderate, and indicates better than mild steel
Improve.
This example confirms the significantly improved mistake of the groove of the SS430 being modified comprising surface and -2 serial negative electrodes of doping
Voltage and improved corrosion resistance.
All above United States Patent (USP)s for referring in this manual, U.S. Patent application, foreign patent, foreign patent application
And non-patent publications are combined herein by quoting with its full text.
Although key element, embodiment and the application of the present invention has been shown and described, it will of course be appreciated that this
Invention is not limited to this, because in the case of the spirit and scope without departing from present disclosure, in particular according to foregoing teachings,
One of ordinary skill in the art can make a variety of modifications.For example, although previous description and example is for chlorate electricity
Solve device, but the present invention may can be used for chlor-alkali production, hydrogen electrolysis, desalinization or for requiring active, inexpensive on the contrary
, other electrochemistry in industry application of the chemical production of cathode electrode material resistant to chemical etching is (for example, by carbon dioxide conversion
For liquid fuel and industrial chemicals) in.Such modification should be taken into account in the authority and scope of additional claims in this.
Claims (20)
1. a kind of chlorate electrolyser, it includes negative electrode, and the negative electrode includes stainless steel electrode, and the stainless steel electrode includes small
In by weight 6% nickel, and the surface roughness R of the stainless steel electrodeqBetween 1.0 microns and 5.0 microns.
2. chlorate electrolyser as claimed in claim 1, wherein the feature of the stainless steel electrode is surface roughness RqIt is less than
2.5 micron.
3. chlorate electrolyser as claimed in claim 1, wherein the stainless steel is ferritic stainless steel.
4. chlorate electrolyser as claimed in claim 3, wherein the stainless steel is selected from 430,430D, 432 and 436S etc.
The ferritic stainless steel of level.
5. chlorate electrolyser as claimed in claim 1, adulterated wherein the stainless steel includes to be selected from the stabilisation of the following group
Thing：Cu, Mo, N, Nb, Sn, Ti, V and W.
6. chlorate electrolyser as claimed in claim 3, wherein the ferritic stainless steel includes Mo dopants.
7. chlorate electrolyser as claimed in claim 3, wherein the ferritic stainless steel includes Sn dopants.
8. chlorate electrolyser as claimed in claim 3, wherein the ferritic stainless steel includes Ti dopants.
9. chlorate electrolyser as claimed in claim 3, wherein the ferritic stainless steel includes V dopants.
10. chlorate electrolyser as claimed in claim 1, wherein the stainless steel is two phase stainless steel.
11. chlorate electrolyser as claimed in claim 10, wherein the stainless steel be selected from S31803, S32101, S32205,
The two phase stainless steel of S32304, S82441, S82011 and S82122 grade.
12. chlorate electrolyser as claimed in claim 1, wherein the stainless steel is included less than by weight 0.03%
Carbon.
13. chlorate electrolyser as claimed in claim 12, wherein the stainless steel is included less than by weight 0.005%
Carbon.
14. chlorate electrolyser as claimed in claim 1, wherein the stainless steel includes the phosphorus less than by weight 0.03%
And the sulphur less than by weight 0.003%.
15. chlorate electrolyser as claimed in claim 1, the negative electrode is included and is applied on the stainless steel electrode of low nickel-content
Electrolysis enhancing coating.
16. chlorate electrolyser as claimed in claim 1, wherein the chlorate electrolyser is sodium chlorate electrolyzer.
17. chlorate electrolyser as claimed in claim 1, wherein the negative electrode is soldered to made of carbon steel or stainless steel
On support plate.
18. chlorate electrolyser as claimed in claim 17, wherein the negative electrode is soldered to the support plate being made of stainless steel
On, and the electrolyzer does not include cathodic protection unit.
A kind of 19. mistake that industrial electrolysis negative electrode is reduced while the corrosion resistance of negative electrode is being kept during saline electrolysis
The method of voltage, methods described are included the surface coarsening of the stainless steel cathode of the nickel comprising less than by weight 6% to 1.0
Surface roughness R between micron and 5.0 micronsq。
20. method as claimed in claim 19, wherein the roughening is carried out including the cathode surface described in alumina powder foot couple
Sandblasting.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US201261637244P | 2012-04-23 | 2012-04-23 | |
| US61/637,244 | 2012-04-23 | ||
| PCT/CA2013/050289 WO2013159219A1 (en) | 2012-04-23 | 2013-04-15 | Surface modified stainless steel cathode for electrolyser |
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| RU2017101726A (en) * | 2014-06-24 | 2018-07-24 | Кеметикс Инк. | NON-SEPARATED CELL FOR NARROW ELECTROLYSIS |
| WO2016010782A1 (en) | 2014-07-16 | 2016-01-21 | Chemetics Inc. | Method of welding ferritic stainless steel to carbon steel using a filler material made of duplex stainless stell; corresponding welded article |
| FI128294B (en) * | 2015-01-27 | 2020-02-28 | Outokumpu Oy | Method for manufacturing a plate material for electrochemical process |
| US10622643B2 (en) * | 2015-09-25 | 2020-04-14 | Nippon Steel Corporation | Carbon separator for solid polymer fuel cell, solid polymer fuel cell, and solid polymer fuel cell stack |
| FR3053363B1 (en) * | 2016-06-30 | 2021-04-09 | Herakles | ELECTROLYTIC SYSTEM FOR THE SYNTHESIS OF SODIUM PERCHLORATE WITH ANODE WITH EXTERNAL SURFACE IN DIAMOND DOPED WITH BORON |
| JPWO2021014940A1 (en) * | 2019-07-23 | 2021-01-28 | ||
| US11769639B2 (en) | 2022-02-22 | 2023-09-26 | Imam Abdulrahman Bin Faisal University | Molybdenum doped carbon nanotube and graphene nanocomposite electrodes |
| CN115972102B (en) * | 2022-12-19 | 2023-09-12 | 江苏亿安腾特种电极新材料科技有限公司 | Regenerated titanium anode and preparation method thereof |
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|---|---|---|---|---|
| CN1508291A (en) * | 2002-12-18 | 2004-06-30 | 吴建国 | Method for preparing perchlorate by electrolysis of chlorate |
| JP2009200008A (en) * | 2008-02-25 | 2009-09-03 | Nisshin Steel Co Ltd | Electrode material, its manufacturing method, and electrode of dye-sensitized solar cell |
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| KR100361548B1 (en) * | 1999-04-19 | 2002-11-21 | 스미토모 긴조쿠 고교 가부시키가이샤 | Stainless steel product for producing polymer electrode fuel cell |
| JP2000328205A (en) * | 1999-05-24 | 2000-11-28 | Sumitomo Metal Ind Ltd | Ferritic stainless steel for conductive electric parts and fuel cell |
| JP3397168B2 (en) * | 1999-04-19 | 2003-04-14 | 住友金属工業株式会社 | Ferritic stainless steel and polymer electrolyte fuel cell for polymer electrolyte fuel cell separator |
| US20030116431A1 (en) * | 2001-12-19 | 2003-06-26 | Akzo Nobel N.V. | Electrode |
| US7807028B2 (en) * | 2005-03-09 | 2010-10-05 | Xstrata Queensland Limited | Stainless steel electrolytic plates |
| ITMI20052298A1 (en) * | 2005-11-30 | 2007-06-01 | De Nora Elettrodi Spa | SYSTEM FOR THE ELECTROLYTIC PRODUCTION OF CHLORATO SODICO |
| CA2588906A1 (en) * | 2007-05-15 | 2008-11-15 | Hydro Quebec | Fe3al(ru) nanocrystalline alloys and use thereof in nanocrystalline form or not for the production of electrodes for the synthesis of sodium chlorate |
| EP2085501A1 (en) * | 2008-01-31 | 2009-08-05 | Casale Chemicals S.A. | High performance cathodes for water electrolysers |
| JP5366609B2 (en) * | 2009-03-26 | 2013-12-11 | 新日鐵住金ステンレス株式会社 | Alloy-saving duplex stainless steel material with good corrosion resistance and its manufacturing method |
| CA2671211A1 (en) * | 2009-07-08 | 2011-01-08 | Hydro-Quebec | Highly energy efficient bipolar electrodes and use thereof for the synthesis of sodium chlorate |
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- 2013-04-15 US US14/396,305 patent/US20150090586A1/en not_active Abandoned
- 2013-04-15 MY MYPI2014703042A patent/MY168646A/en unknown
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- 2013-04-15 JP JP2015506055A patent/JP6189932B2/en not_active Expired - Fee Related
- 2013-04-15 BR BR112014026603A patent/BR112014026603A2/en not_active IP Right Cessation
- 2013-04-15 KR KR1020147029359A patent/KR20150013130A/en not_active Application Discontinuation
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- 2013-04-15 EP EP13781847.2A patent/EP2841625A4/en not_active Withdrawn
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- 2013-04-15 WO PCT/CA2013/050289 patent/WO2013159219A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508291A (en) * | 2002-12-18 | 2004-06-30 | 吴建国 | Method for preparing perchlorate by electrolysis of chlorate |
| JP2009200008A (en) * | 2008-02-25 | 2009-09-03 | Nisshin Steel Co Ltd | Electrode material, its manufacturing method, and electrode of dye-sensitized solar cell |
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| US20180105943A1 (en) | 2018-04-19 |
| IN2014DN09171A (en) | 2015-07-10 |
| EP2841625A4 (en) | 2015-08-05 |
| WO2013159219A1 (en) | 2013-10-31 |
| PH12014502355A1 (en) | 2015-01-12 |
| EA029024B1 (en) | 2018-01-31 |
| EA201491931A1 (en) | 2015-01-30 |
| AU2013252464A1 (en) | 2014-10-16 |
| KR20150013130A (en) | 2015-02-04 |
| BR112014026603A2 (en) | 2017-06-27 |
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| CA2870097A1 (en) | 2013-10-31 |
| AU2013252464B2 (en) | 2017-09-28 |
| CN104271809A (en) | 2015-01-07 |
| NZ700607A (en) | 2016-08-26 |
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