CN106115861A - Electrolysis unit and the method producing electrolysis water - Google Patents
Electrolysis unit and the method producing electrolysis water Download PDFInfo
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- CN106115861A CN106115861A CN201610520877.2A CN201610520877A CN106115861A CN 106115861 A CN106115861 A CN 106115861A CN 201610520877 A CN201610520877 A CN 201610520877A CN 106115861 A CN106115861 A CN 106115861A
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- electrode
- water
- coating
- lanthanum
- platinum
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a kind of electrolysis unit and the method for production electrolysis water.The electrolysis unit of the present invention includes housing, barrier film, the first electrode and the second electrode；Described housing is divided into the first tank house and the second tank house, described first electrode and described second electrode and is separately positioned in described first tank house and described second tank house by described barrier film；Described electrode includes stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing lanthanum；Gross weight based on the platinum coating containing lanthanum, the described platinum coating containing lanthanum contains the lanthanum of 0.1～5wt%.The present invention forms coating of titanium dioxide and platinum coating on stainless steel substrate, and adds lanthanum element, so further ensures the stability in use of electrode.
Description
Technical field
The present invention relates to a kind of electrolysis unit and the method for production electrolysis water, the electrolysis especially with good stability is aquatic
Become device and the method producing electrolysis water.
Background technology
Electrolytic water generating device can generate electrolysis water, mainly includes alkaline water, slightly acidic water, strong oxidized water etc..Electrode
Being all the nucleus equipment of electrolytic water generating device with separation film, there is close relationship with the quality of electrolysis water in them.
CN205099424U disclose a kind of electrode can scale removal electrolytic water device, it include by electrolytic cell housing, anode and
The electrolysis bath that negative electrode is constituted, electrolytic cell housing is provided with anode, negative electrode, and anode, negative electrode connect to fall polar circuit by wire respectively,
The polar circuit that falls connects control circuit and electrolyzer power source by wire respectively, and electrolytic cell housing is provided with ultrasonic transducer, super
Acoustic wave transducer connects transducer driving circuit by wire, and transducer driving circuit connects control circuit by wire.This electricity
Solution water device can reduce electrode surface incrustation scale and generate shield electrode, but can not prevent electrode from oozing out harmful metal ion.
In order to prevent the electrode of electrolytic water generating device from oozing out harmful metal ion, platinum Ti electrode is generally used to generate dress as electrolysis water
The anode put.But, platinum Ti electrode is expensive, and this causes the production cost of electrolytic water generating device to remain high, and seriously makes
About its popularization and application.Accordingly, it would be desirable to cheap electrode is to substitute platinum Ti electrode.
CN202440350U discloses a kind of device for tap water electrolytic separation, by ion exchange membrane, titanium alloy sun
Pole, stainless steel cathode, tank house, upper end cover, bottom end cover are constituted, and ion exchange membrane is arranged on Ti-alloy anode and stainless steel cathode
Between, Ti-alloy anode is arranged on the side of tank house, and stainless steel cathode is arranged on the opposite side of tank house, and tank house is fixed on
Between upper end cover and bottom end cover.This patent documentation has ruthenium iridium metals layer in the surface burn-back of Ti-alloy anode, instead of and closes at titanium
On gold anode, the platinum of plating, has saved cost, but its price is the highest.And for example, CN104562078A discloses one
Electrode for electrolysis, this electrode for electrolysis includes conductive substrate and active coating, and described conductive substrate closes for comprising titanium or titanium
The base material of gold, described active coating includes at least primer coating and face coat, and described primer coating comprises titanium oxide, iridium oxygen
Compound and ru oxide, described face coat comprise the one in iridium oxide, ru oxide, titanium oxide and palladium, platinum or
The metal of two kinds of elements or oxide.The electrode for electrolysis of this patent documentation have employed duplex coating, compare comprise only ruthenium, iridium,
The signal layer coating of titanium, its electrode activity is more preferable, and the chlorine evolution potential of electrode is low, and oxygen evolution potential is high, and the service life of electrode is longer,
Electrolysis stability is more preferable.But, this patent documentation still uses titanium or titanium alloy as base material, causes the cost of electrode still
Higher.
Therefore, at present in the urgent need to a kind of electrolysis unit, its production cost is relatively low, and in the electrolysis water produced substantially
Without Cr VI.
Summary of the invention
An object of the present invention is to provide a kind of electrolysis unit, and its production cost is relatively low.The present invention's is further
Purpose is to provide a kind of electrolysis unit, is substantially free of Cr VI in the electrolysis water of its production, and stability in use is good.
Further object is that and provide a kind of method producing electrolysis water, it can reduce production cost, long
Time stably obtains and is substantially free of chromic electrolysis water.
Inventors herein have recognized that following technical scheme can realize above-mentioned purpose.
The present invention provides a kind of electrolysis unit, and it includes housing, barrier film, the first electrode and the second electrode；Described barrier film
Described housing is divided into the first tank house and the second tank house, described first electrode and described second electrode be separately positioned on
In described first tank house and described second tank house；
The first described electrode includes stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing lanthanum；Described
Nickel coating is arranged on the outer surface of stainless steel substrate, and its thickness is 5～25 microns；Described coating of titanium dioxide is arranged on nickel plating
The outer surface of layer, its thickness is 5～10 microns；The described platinum coating containing lanthanum is arranged on the outer surface of coating of titanium dioxide, its
Thickness is 3～10 microns；Gross weight based on the platinum coating containing lanthanum, the described platinum coating containing lanthanum contains 0.1～5wt%
Lanthanum.
According to device of the present invention, it is preferable that the thickness of described nickel coating is 10～20 microns；Described dioxy
The thickness changing titanium coating is 6～8 microns；The thickness of the described platinum coating containing lanthanum is 5～8 microns；Based on the platinum coating containing lanthanum
Gross weight, the described platinum coating containing lanthanum contains the lanthanum of 0.5～3wt%.
According to device of the present invention, it is preferable that described second electrode includes base material and cover layer, described base material choosing
From rustless steel, titanium or titanium alloy, described cover layer selected from platinum, iridium, palladium, tantalum one or more.
According to device of the present invention, it is preferable that described barrier film is the continuous poriferous plasma membrane with water penetration, its hole
Footpath is 15～190nm.
According to device of the present invention, it is preferable that the bottom of described first tank house is provided with the first water inlet, described
The top of the first tank house is provided with the first outlet；The bottom of described second tank house is provided with the second water inlet, and described
The top of two tank houses is provided with the second outlet.
According to device of the present invention, it is preferable that described electrolysis unit is electrolytic water generating device.
The present invention also provides for the method utilizing above-mentioned electrolysis unit to produce electrolysis water, and it includes being electrolysed water conservancy project sequence: to first
Tank house supplies the first water, supplies the second water to the second tank house, and the first electrode and the second electrode are applied voltage, thus
Form electrolysis water.
According to method of the present invention, it is preferable that the described water that the first water is chloride ion-containing, described the second
Water is tap water.
According to method of the present invention, it is preferable that in described electrolysis water conservancy project sequence, the differential water pressures of barrier film both sides is ±
Within 5.5kPa.
According to method of the present invention, it is preferable that described method also includes the preparation section of the first electrode:
(1) stainless steel substrate is used the sand papering of 80～110 mesh, by the stainless steel substrate after polishing at 30～45 DEG C
Lower alkaline degreaser soaks and carries out oil removing, and etch activation obtains pretreating substrates in 60～80 seconds the most in an acidic solution；
(2) using described pretreating substrates as negative electrode, rustless steel as anode, with comprise nickel compound solution for plating
Liquid, electronickelling on described pretreating substrates, thus form the electrode containing nickel coating；
(3) the described electrode containing nickel coating is placed in the mixed solution of ammonium hexa-fluorotitanate and boric acid formation, in 35～55
Soak at DEG C to take out after 10～50 hours and dry, then under inert gas shielding, at 500～700 DEG C heat treatment 50～80
Minute, obtain the electrode containing coating of titanium dioxide after natural cooling；Wherein, the hexafluorotitanic acid ammonium concentration in described mixed solution is
0.2～0.35mol/L and boric acid concentration be 0.2～0.35mol/L；
(4) it is anode using the described electrode containing coating of titanium dioxide as negative electrode, platinum guaze, to comprise lanthanum compound and platinum
The solution of compound is electroplate liquid, forms the platinum coating containing lanthanum, thus obtain first on the described electrode containing coating of titanium dioxide
Electrode；Wherein, described lanthanum compound is selected from Lanthanum (III) nitrate or lanthanum chloride；Described platinum compounds selected from dinitroso two ammino platinum or
Chloroplatinic acid.
In the electrolysis unit of the present invention, the base material of the first electrode is stainless steel, will be just relative to titanium or titanium alloy
The most many.The present invention forms coating of titanium dioxide and platinum coating on stainless steel substrate, and adds lanthanum element, this ensure that
The stability in use of electrode, such as, ensure during using for a long time that the Cr VI in rustless steel does not penetrates into electrolysis water
In.
Accompanying drawing explanation
Fig. 1 is the electrolysis unit of embodiment 1, wherein:
1-housing, 2-barrier film, 21-the first tank house, 22-the second tank house, 31-the first electrode, 32-the second electrode, 41-
First water inlet, 42-the second water inlet, 51-the first outlet, 52-the second outlet.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, " rustless steel " represents in atmosphere or can support erosion-resisting steel alloy in chemical attack medium,
Include but not limited to martensite type rustless steel, ferrite type rustless steel, Austenitic rustless steel, martensite type rustless steel, ferrum element
Body-Austenitic rustless steel.Can contain chromium in the rustless steel of the present invention, its content can be more than 12%.In addition to chromium, this
The rustless steel of invention can add the elements such as nickel, molybdenum that steel can be made to be passivated.
In the present invention, so-called the outer surface of B " A be arranged on ", is not that proper A is fully wrapped around by B, A, B
Between there may be overlapped, intersect, interpenetrative relation.
<electrolysis unit>
The electrolysis unit of the present invention includes housing, barrier film, the first electrode and the second electrode；Described barrier film is by described shell
Body is divided into the first tank house and the second tank house, described first electrode and described second electrode and is separately positioned on described first electricity
Solve in room and described second tank house.The electrolysis unit of the present invention can also include current adjustment unit and power supply.
The housing of the present invention can use the material of acid-fast alkali-proof to make, and its shape can be rectangular box or irregular
Shape, it can be one-body molded or be welded by different baffle plates.The housing of the present invention can be two cell structures, three Room knots
Structure and many cell structures, preferably two cell structures.Described housing is divided into the first tank house and the second electricity by the barrier film of the present invention
Solve room.If barrier film is a piece of, then it is two cell structures；If barrier film is two panels, then it is three cell structures；If barrier film is for more than two
Sheet, then be many cell structures.In the case of barrier film is more than two panels, medial compartment can be formed between barrier film, be used for accommodating electrolysis
Liquid.
In the present invention, described barrier film can be dielectric film, such as cation exchange membrane or anion exchange membrane,
Depending on concrete demand.The dielectric film of the present invention can use polyelectrolyte membrane.The cation that macromolecule is formed
The example of exchange membrane includes but not limited to NAFION112, NAFION115, NAFION117 of E.I.Du Pont Company, Asahi Glass strain formula meeting
The GORE-SELECT and the ACIPLEX of Asahi Kasei Corporation of FLEMION, W.L.Gore&Associates company of society；
The example of the anion exchange membrane that macromolecule is formed includes but not limited to the heterogeneous membrane of Shanghai Water-Treatment Material Co., Ltd., Shanghai
3362BW and the AHA of ASTOM company of Japan.
In the present invention, described barrier film preferably has the continuous poriferous plasma membrane of water penetration.The aperture of multiple aperture plasma membrane can
Think 15～190nm, preferably 50～185nm, more preferably 105～180nm.Use the multiple aperture plasma membrane in above-mentioned aperture, permissible
The differential water pressures of barrier film both sides is controlled within ± 5.5kPa, thus avoid the deterioration of barrier film, extend barrier film service life.This
Bright multiple aperture plasma membrane can have in face and irregular hole in solid.The continuous poriferous plasma membrane of the present invention can be selected from Porous
The porous ceramic films such as glass-film, Porous pellumina, Porous oxidation titanium film, it is also possible to selected from Porous polyethylene film,
The Porous polymeric films such as Porous polypropylene screen, chloridizing high molecule multiple aperture plasma membrane, fluoropolymer multiple aperture plasma membrane.The present invention's
The example of multiple aperture plasma membrane includes but not limited to Y-9201T, Y9211T barrier film of Japan Tang Qian membranous system company (Yuasa).This
Bright multiple aperture plasma membrane can be the stacked film formed by the multiple aperture plasma membrane of different pore size.So it is more beneficial for the migration of ion, and
Reduce stress concentration effect.
In the present invention, the first electrode includes stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing lanthanum.
Nickel coating is arranged on the outer surface of stainless steel substrate, and its thickness is 5～25 microns, preferably 10～20 microns, and more preferably 15
～20 microns；Coating of titanium dioxide is arranged on the outer surface of nickel coating, and its thickness is 5～10 microns, preferably 6～8 microns, more
It is preferably 7～8 microns.Platinum coating containing lanthanum is arranged on the outer surface of coating of titanium dioxide, and its thickness is 3～10 microns, preferably
It is 5～8 microns, more preferably 6～7 microns.Gross weight based on the platinum coating containing lanthanum, the platinum coating containing lanthanum contain 0.1～
5wt%, be preferably 0.5～3wt%, more preferably 1～2wt%, the lanthanum of most preferably 1.2～1.5wt%.Present invention
People is it was unexpectedly observed that increase nickel coating and coating of titanium dioxide on stainless steel substrate, and increases a small amount of lanthanum unit in platinum coating
Element, can significantly more increase the stability in use of stainless steel substrate so that main material is that stainless electrode can be made
It is applied to electrolysis unit for anode；And the Cr VI that can ensure that in rustless steel during using for a long time does not penetrates into
In electrolysis water.
In the present invention, the second electrode includes base material and cover layer.Described base material is selected from rustless steel, titanium or titanium alloy,
Described cover layer selected from platinum, iridium, palladium, tantalum one or more.As preferably, described base material is selected from rustless steel, described
Cover layer selected from platinum, iridium one or both.According to a specific embodiment of the present invention, the second electrode is rustless steel electricity
Pole, so can reduce cost.
In the present invention, the bottom of described first tank house is provided with the first water inlet, the top of described first tank house
It is provided with the first outlet；The bottom of described second tank house is provided with the second water inlet, and the top of described second tank house sets
It is equipped with the second outlet.First water inlet is for being connected with the first water inlet pipe, for the first water is imported the first tank house；The
One outlet and the first outlet pipe connect, and derive for the electrolysis water that will produce.Second water inlet is for the second water inlet pipe even
Connect, for the second water is imported the second tank house；Second outlet and the second outlet pipe connect, for the electrolysis water that will produce
Derive.First water inlet pipe and the second water inlet pipe all can be provided with flow control valve, for controlling flow velocity and the hydraulic pressure of water.The
One outlet pipe and the second outlet pipe the most all can be provided with flow control valve, for controlling flow velocity and the hydraulic pressure of water.According to this
One detailed description of the invention of invention, the first water inlet and the second water inlet and the connection of water inlet pipe, be used for importing chloride from
The tap water of son.
The electrolysis unit of the present invention can also include current adjustment unit and power supply.Power supply is for the first electrode and second
Electrode applies voltage, and current adjustment unit is for adjusting the size of current of electrolytic process.
<electrolysis water producing method>
The electrolysis water producing method of the present invention utilizes above-mentioned electrolysis unit to realize.The method of the present invention includes being electrolysed water conservancy project
Sequence, it is also possible to include the preparation section of the first electrode.Electrolysis water conservancy project sequence includes: supply the first water to the first tank house, to the
Two tank houses supply the second water, the first electrode and the second electrode are applied voltage, thus forms electrolysis water.
In the present invention, the first described water can be the water of chloride ion-containing, such as, contain the electrolyte of NaCl, contain
The tap water etc. of hypochlorous acid or derivatives thereof.Described the second water can be tap water, such as, contain hypochlorous acid or it derives
The tap water of thing.Common tap water all contains chloride ion, and some metal cations, therefore, the first of the present invention
Water can be identical with the second water, is tap water.By controlling flow control valve to control to the first tank house supply first
Plant flow velocity and the hydraulic pressure of water, and control to supply to the second tank house flow velocity and the hydraulic pressure of the second water, thus regulate and control barrier film both sides
Differential water pressures.When using multiple aperture plasma membrane, can be by the differential water pressures of barrier film both sides ± 5.5kPa within, preferably ± 3kPa with
In, within more preferably ± 1kPa.So can avoid the deterioration of multiple aperture plasma membrane, improve stability in use.
Turn on the power and the first electrode and the second electrode are applied voltage, by regulation current adjustment unit, can be by voltage
Control 3～5V, preferably 3.5～5V, more preferably 4～5V；Electric current can be controlled 15～30A, preferably 20～
28A, more preferably 22～25V.
Electrolysis water during, anion by barrier film to anode migrate, cation by barrier film to cathodic migration, thus
Form rich anion-containing electrolysis water (acid water) at the first tank house, and form the electrolysis rich in cation at the second tank house
Water (alkaline water).Rich anion-containing electrolysis water is derived by the first outlet and by the first outlet pipe；Electricity rich in cation
Xie Shui derives by the second outlet and by the second outlet pipe.
The preparation section of first electrode of the present invention comprises the steps:
(1) stainless steel substrate is used the sand papering of 80～110 mesh, by the stainless steel substrate after polishing at 30～45 DEG C
Lower alkaline degreaser soaks and carries out oil removing, and etch activation obtains pretreating substrates in 60～80 seconds the most in an acidic solution；
(2) using described pretreating substrates as negative electrode, rustless steel as anode, with comprise nickel compound solution for plating
Liquid, electronickelling on described pretreating substrates, thus form the electrode containing nickel coating；
(3) the described electrode containing nickel coating is placed in the mixed solution of ammonium hexa-fluorotitanate and boric acid formation, in 35～55
Soak at DEG C to take out after 10～50 hours and dry, then under inert gas shielding, at 500～700 DEG C heat treatment 50～80
Minute, obtain the electrode containing coating of titanium dioxide after natural cooling；Wherein, the hexafluorotitanic acid ammonium concentration in described mixed solution is
0.2～0.35mol/L and boric acid concentration be 0.2～0.35mol/L；
(4) it is anode using the described electrode containing coating of titanium dioxide as negative electrode, platinum guaze, to comprise lanthanum compound and platinum
The solution of compound is electroplate liquid, forms the platinum coating containing lanthanum, thus obtain first on the described electrode containing coating of titanium dioxide
Electrode；Wherein, described lanthanum compound is selected from Lanthanum (III) nitrate or lanthanum chloride；Described platinum compounds selected from dinitroso two ammino platinum or
Chloroplatinic acid.
In the step (1) of the present invention, the bruting process of stainless steel substrate can use sand papering, it would however also be possible to employ thin
Sand is polished.When using sand papering, the sand paper of 80～110 mesh can be used, it is preferred to use the sand paper of 90～100 mesh.
In the step (1) of the present invention, soak to remove surface by the alkaline degreaser of the stainless steel substrate after polishing
Oily matter.Soaking temperature can control at 30～45 DEG C, preferably 35～40 DEG C.Soak time is not particularly limited, with
The oily matter on stainless steel substrate surface is removed and is totally limited.The alkaline degreaser of the present invention can be containing 10～35g/L phosphorus
Acid trisodium and the aqueous solution of 5～13g/L sodium silicate, be preferably containing 15～30g/L tertiary sodium phosphates and the water of 6～11g/L sodium silicate
Solution, more preferably containing 20～25g/L tertiary sodium phosphates and the aqueous solution of 8～10g/L sodium silicate.The acid solution of the present invention includes
10～20wt% nitric acid, 30～40wt% hydrochloric acid and 45～55wt% water, preferably include 12～18wt% nitric acid, 32～38wt%
Hydrochloric acid and 46～52wt% water, more preferably include 15～17wt% nitric acid, 33～35wt% hydrochloric acid and 49～51wt% water.Its
In, the percentage by weight of nitric acid is with HNO3Calculating, the percentage by weight of hydrochloric acid calculates with HCl.According to the present invention one is concrete
Embodiment, the acid solution of the present invention is made up of 10～20wt% nitric acid, 30～40wt% hydrochloric acid and 45～55wt% water.
In the step (1) of the present invention, the etch in an acidic solution of the stainless steel substrate after oil removal treatment is activated, etch
Activation temperature can at room temperature be carried out.Etch soak time can control at 60～80 seconds, preferably 65～75 seconds.Etch is lived
The purpose changed is easily to adhere to the solution intending forming nickel coating so that stainless steel surfaces.
In the step (2) of the present invention, outside stainless steel substrate, form the nickel coating with microcellular structure, thus promote
The generation of nanometer titanium dioxide coating, and then improve the anticorrosive of electrode and oxidation resistance." solution " of the present invention represents
The mixture that plated material is formed with solvent.Above-mentioned solvent can be water.
In the step (2) of the present invention, electronickelling can use those electroplate liquids known in the art.According to the present invention's
One embodiment, the electroplate liquid in this step can include nickel sulfate solution, boric acid solution, sodium alkyl sulfate solution and chlorination
Nickel solution.According to another implementation of the invention, the electroplate liquid in this step is by nickel sulfate solution, boric acid solution, alkyl
Metabisulfite solution and nickel chloride solution composition.In the present invention, the concentration of nickel sulfate solution can be 300～500g/L, preferably
It is 350～460g/L, more preferably 420～450g/L；The concentration of boric acid solution can be 30～42g/L, be preferably 32～
40g/L, more preferably 35～38g/L；The concentration of sodium alkyl sulfate solution is 5～25g/L, is preferably 8～20g/L, more preferably
It is 10～15g/L；The concentration of nickel chloride solution can be 0.5～1g/L, be preferably 0.6～0.8g/L, more preferably 0.65～
0.75g/L.Comprising plated material nickel sulfate in electroplate liquid, it can be added in the way of seven water nickel sulfate.The present invention's
Alkyl sodium sulfate can be selected from sodium hexadecyl sulfate, sodium tetradecyl sulfate, sodium lauryl sulphate, positive sodium decyl sulfate,
N-octyl sodium sulfate etc.；It is preferably sodium lauryl sulphate or n-octyl sodium sulfate.
In the step (2) of the present invention, its plating conditions is: cathode-current density is 5～10A/dm2, preferably 6～
8A/dm2；Electroplating temperature is 40～60 DEG C, preferably 50～55 DEG C；Electroplating time 1～10 minutes, preferably 2～5 minutes.
In the step (3) of the present invention, hexafluorotitanic acid ammonium concentration can be 0.2～0.35mol/L, preferably 0.25～
0.3mol/L；Boric acid concentration can be 0.2～0.35mol/L, preferably 0.25～0.3mol/L.In the present invention, temperature is soaked
Degree is preferably 38～52 DEG C, more preferably 40～45 DEG C；Soak time is preferably 15～30 hours, and more preferably 20～25 is little
Time.In order to ensure that coating of titanium dioxide is evenly distributed on the nickel coating of stainless steel substrate, above-mentioned heat treatment can be at indifferent gas
Carry out under body protection.Noble gas can be selected from nitrogen, argon and helium etc..The temperature of heat treatment is preferably 550～650 DEG C,
More preferably 580～600 DEG C；Heat treatment time is preferably 55～75 minutes, more preferably 60～70 minutes.After heat treatment
Stainless steel substrate naturally cools to room temperature, obtains the electrode containing coating of titanium dioxide.So obtain containing coating of titanium dioxide more
For dense uniform.
In the step (4) of the present invention, the electroplate liquid of the present invention is the solution comprising lanthanum compound and platinum compounds.This
Bright " solution " represents the mixture that plated material is formed with solvent.The solvent of the present invention can be water.Above-mentioned lanthanum compound is
Water miscible lanthanum salt, can be selected from Lanthanum (III) nitrate or lanthanum chloride, preferably Lanthanum (III) nitrate.Above-mentioned platinum compounds is water miscible platinum salt,
Dinitroso two ammino platinum (NH can be selected from3)2Pt(NO2)2·H2O, chloroplatinic acid H2PtCl6·6H2O etc., preferably dinitroso
Two ammino platinum.
According to a specific embodiment of the present invention, described electroplate liquid includes following component:
Detailed description of the invention according to another preferred, described electroplate liquid is made up of following component:
According to the preferred embodiments of the disclosure, described electroplate liquid includes following component:
Preferred embodiment according to another preferred, described electroplate liquid is made up of said components.
According to the detailed description of the invention that the present invention is further preferred, described electroplate liquid includes following component:
The most further preferred detailed description of the invention, described electroplate liquid is by said components group
Become.
The step (4) of the present invention can be carried out in the electroplating device that this area is conventional, repeats no more here.In the present invention
Step (4) in, cathode-current density can be 1～3A/dm2, be preferably 1.5～2A/dm2；Cathode and anode spacing can be 0.6
～1.5cm, preferably 0.8～1.0cm；Tank voltage can be 2～5V, be preferably 3～3.5V；The pH value of electroplate liquid can be
9.5～11.5,10～11 it are preferably；Electroplating temperature is 80～95 DEG C, is preferably 85～90 DEG C；Electroplating time can be 10～50
Hour, be preferably 20～30 hours.
<mensuration of the content of 6-valence Cr ions in water>
(1) content of 6-valence Cr ions in the diphenyl carbazide spectrophotometry detection water of GB7467-1987 is used；
(2) using the content of 6-valence Cr ions in water with ion chromatography, concrete steps see that " ion-chromatographic determination is drunk
Cr VI in water ", Hu Zhongyang etc., the 14th national chromatography of ions symposium collection of thesis, on JIUYUE 17th, 2012.
The preparation section of preparation example 1-the first electrode C1
(1) stainless steel substrate is used the sand papering of 100 mesh, the stainless steel substrate after polishing is used alkalescence at 35 DEG C
Degreaser soaks and carries out oil removing.Alkaline degreaser is containing 22g/L tertiary sodium phosphate and the aqueous solution of 9g/L sodium silicate.After oil removing
Stainless steel substrate etch in an acidic solution obtains pretreating substrates after activating 70 seconds.Acid solution be 17wt% nitric acid,
The solution that 33wt% hydrochloric acid and 50wt% water are formed.
(2) using described pretreating substrates as negative electrode, stainless steel substrate is as anode, with following solution as electroplate liquid,
Electronickelling on described pretreating substrates, thus form the electrode containing nickel coating:
Plating conditions is: cathode-current density is 8A/dm2, electroplating temperature is 50 DEG C, electroplating time 2 minutes.
(3) what the described electrode containing nickel coating was placed in 0.25mol/L ammonium hexa-fluorotitanate and 0.25mol/L boric acid formed is mixed
Close in solution, take out after soaking 25 hours at 40 DEG C and dry, the most under nitrogen protection, at 600 DEG C heat treatment 60 minutes,
The electrode containing coating of titanium dioxide is obtained after natural cooling.
(4) it is anode using the electrode containing coating of titanium dioxide as negative electrode, platinum guaze, with following solution as electroplate liquid, is containing
The formation platinum coating containing lanthanum on first electrode of coating of titanium dioxide:
Plating conditions is as follows: cathode-current density is 2A/dm2, cathode and anode spacing is 1cm, and tank voltage is 3V, electroplate liquid
PH value is 10, and electroplating temperature is 85 DEG C, and electroplating time is 20 hours.
The first electrode C1 is prepared by preparation example 1.This electrode is by stainless steel substrate, nickel coating, coating of titanium dioxide
Form with the platinum coating containing lanthanum.After testing, the thickness of nickel coating is 25 microns, and the thickness of coating of titanium dioxide is 7 microns, containing lanthanum
The thickness of platinum coating be 6 microns, wherein contain the lanthanum of 1.5wt%.
The preparation section of preparation example 2-the first electrode C2
By 0.63g/L, the Lanthanum (III) nitrate consumption of preparation example 1 is replaced with 0.5g/L, and remaining condition is identical with preparation example 1, preparation
Obtain the first electrode C2.This electrode is made up of stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing lanthanum.Through inspection
Surveying, the thickness of nickel coating is 25 microns, and the thickness of coating of titanium dioxide is 7 microns, and the thickness of the platinum coating containing lanthanum is 6 microns,
Wherein contain the lanthanum of 1.2wt%.
Embodiment 1
Fig. 1 shows a kind of electrolysis unit of the present invention.As seen from the figure, this device includes housing 1, barrier film the 2, first electrode
31 and second electrode 32；Housing 2 is divided into the first tank house 21 and the second tank house 22, the first electrode 31 and second by barrier film 1
Electrode 32 is separately positioned in the first tank house 21 and the second tank house 22.This device also includes current adjustment unit (not shown)
With power supply (not shown).Power supply is for applying voltage to the first electrode 31 and the second electrode 32, and current adjustment unit is used for adjusting
Electric current.First electrode 31 uses the first electrode C1 that preparation example 1 obtains；Barrier film 2 is the continuous poriferous plasma membrane with water penetration, hole
Footpath 150nm, for example with the Y-9201T barrier film of Japan Tang Qian membranous system company (Yuasa).
The bottom of the first tank house 21 is provided with the first water inlet 41, and its top is provided with the first outlet 51；Second electricity
The bottom solving room 22 is provided with the second water inlet 42, and its top is provided with the second outlet 52.First water inlet 41 enters with first
Water pipe (not shown) connects, for the first water imports the first tank house 21；First outlet 51 (is not schemed with the first outlet pipe
Show) connect, derive for the electrolysis water that will produce.Second water inlet 42 is connected with the second water inlet pipe (not shown), for by the
Two kinds of water import the second tank house 22；Second outlet 52 is connected with the second outlet pipe (not shown), for the electrolysis that will produce
Water is derived.First water inlet pipe and the second water inlet pipe are provided with flow control valve, for controlling flow velocity and the hydraulic pressure of water.First
Outlet pipe and the second outlet pipe are provided with flow control valve, for controlling flow velocity and the hydraulic pressure of water.
When using said apparatus, first-selected first water inlet 41 that passes through is supplied from water to the first tank house 21, and passes through
Second water inlet 42 is supplied from water to the second tank house 22, and regulation flow control valve is so that the differential water pressures of barrier film 2 both sides is
Within ± 5kPa；First electrode 31 and the second electrode 32 are applied voltage, and voltage is 5V, and electric current is 25A；The acidic electrolysis produced
Water is derived from the first outlet 51, and the electrolyzed alkaline water of generation is derived from the second outlet 52.
Use the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.At continued electrolysis
After water carries out 3500 hours, in the water generated, still it is not detected by Cr VI.
Embodiment 2
In addition to the first electrode 31 is replaced with the first electrode C2 that preparation example 2 obtains, other conditions and embodiment 1 phase
With.
Use the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.At continued electrolysis
After water carries out 3500 hours, in the water generated, still it is not detected by Cr VI.
Embodiment 3
In addition to barrier film 2 is replaced with cation exchange membrane (NAFION 117 of E.I.Du Pont Company), other conditions and reality
Execute example 1 identical.
Use the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.At continued electrolysis
After water carries out 3500 hours, in the water generated, still it is not detected by Cr VI.
Embodiment 4
In addition to barrier film 2 is replaced with anion exchange membrane (AHA of ASTOM company of Japan), other conditions and enforcement
Example 1 is identical.
Use the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.At continued electrolysis
After water carries out 3500 hours, in the water generated, still it is not detected by Cr VI.
Embodiment 5
Except barrier film 2 being replaced with the anion exchange membrane (heterogeneous membrane of Shanghai Water-Treatment Material Co., Ltd., Shanghai
Outside 3362BW), other conditions are same as in Example 1.
Use the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.At continued electrolysis
After water carries out 3500 hours, in the water generated, still it is not detected by Cr VI.
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the flesh and blood of the present invention, and this area skill
Art personnel it is contemplated that any deformation, improve, replace and each fall within the scope of the present invention.
Claims (10)
1. an electrolysis unit, it is characterised in that described electrolysis unit includes housing, barrier film, the first electrode and the second electrode；
Described housing is divided into the first tank house and the second tank house, described first electrode and described second electrode by described barrier film
It is separately positioned in described first tank house and described second tank house；
The first described electrode includes stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing lanthanum；Described nickel plating
Layer is arranged on the outer surface of stainless steel substrate, and its thickness is 5～25 microns；Described coating of titanium dioxide is arranged on nickel coating
Outer surface, its thickness is 5～10 microns；The described platinum coating containing lanthanum is arranged on the outer surface of coating of titanium dioxide, its thickness
It it is 3～10 microns；Gross weight based on the platinum coating containing lanthanum, the described platinum coating containing lanthanum contains the lanthanum of 0.1～5wt%.
Device the most according to claim 1, it is characterised in that: the thickness of described nickel coating is 10～20 microns；Described
The thickness of coating of titanium dioxide be 6～8 microns；The thickness of the described platinum coating containing lanthanum is 5～8 microns；Based on containing lanthanum
The gross weight of platinum coating, the described platinum coating containing lanthanum contains the lanthanum of 0.5～3wt%.
Device the most according to claim 1, it is characterised in that: described second electrode includes base material and cover layer, described
Base material selected from rustless steel, titanium or titanium alloy, described cover layer selected from platinum, iridium, palladium, tantalum one or more.
Device the most according to claim 1, it is characterised in that: described barrier film is the continuous poriferous matter with water penetration
Film, its aperture is 15～190nm.
Device the most according to claim 1, it is characterised in that: the bottom of described first tank house is provided with the first water inlet
Mouthful, the top of described first tank house is provided with the first outlet；The bottom of described second tank house is provided with the second water inlet,
The top of described second tank house is provided with the second outlet.
Device the most according to claim 1, it is characterised in that: described electrolysis unit is electrolytic water generating device.
7. utilize the method that the device described in any one of claim 1～6 produces electrolysis water, it is characterised in that described method
Including electrolysis water conservancy project sequence: supply the first water to the first tank house, supply the second water to the second tank house, to the first electrode and
Second electrode applies voltage, thus forms electrolysis water.
Method the most according to claim 7, it is characterised in that: the described water that the first water is chloride ion-containing, described
The second water is tap water.
Method the most according to claim 7, it is characterised in that in described electrolysis water conservancy project sequence, the differential water pressures of barrier film both sides
For within ± 5.5kPa.
Method the most according to claim 7, it is characterised in that described method also includes the preparation section of the first electrode:
(1) stainless steel substrate is used the sand papering of 80～110 mesh, the stainless steel substrate after polishing is used at 30～45 DEG C
Alkaline degreaser soaks and carries out oil removing, and etch activation obtains pretreating substrates in 60～80 seconds the most in an acidic solution；
(2) using described pretreating substrates as negative electrode, rustless steel as anode, with comprise nickel compound solution as electroplate liquid,
Electronickelling on described pretreating substrates, thus form the electrode containing nickel coating；
(3) the described electrode containing nickel coating is placed in the mixed solution of ammonium hexa-fluorotitanate and boric acid formation, at 35～55 DEG C
Take out after soaking 10～50 hours and dry, then under inert gas shielding, at 500～700 DEG C heat treatment 50～80 minutes,
The electrode containing coating of titanium dioxide is obtained after natural cooling；Wherein, the hexafluorotitanic acid ammonium concentration in described mixed solution be 0.2～
0.35mol/L and boric acid concentration are 0.2～0.35mol/L；
(4) it is anode using the described electrode containing coating of titanium dioxide as negative electrode, platinum guaze, to comprise lanthanum compound and platinum compounds
Solution be electroplate liquid, the described electrode containing coating of titanium dioxide is formed containing the platinum coating of lanthanum, thus obtains the first electrode；
Wherein, described lanthanum compound is selected from Lanthanum (III) nitrate or lanthanum chloride；Described platinum compounds is selected from dinitroso two ammino platinum or chlorine platinum
Acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132069A (en) * | 2007-09-22 | 2008-02-27 | 太原理工大学 | Method for manufacturing carbon-carrying platinum-ruthenium alloy electrode doped with rare earth elements of La series |
| CN101423270A (en) * | 2008-10-09 | 2009-05-06 | 张学东 | Electric pole material of high efficiency electrocatalysis high-grade oxidation technology |
| CN103088363A (en) * | 2012-12-13 | 2013-05-08 | 苏州新区化工节能设备厂 | Preparation method of stainless steel electrolysis electrode with titanium dioxide coating layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132069A (en) * | 2007-09-22 | 2008-02-27 | 太原理工大学 | Method for manufacturing carbon-carrying platinum-ruthenium alloy electrode doped with rare earth elements of La series |
| CN101423270A (en) * | 2008-10-09 | 2009-05-06 | 张学东 | Electric pole material of high efficiency electrocatalysis high-grade oxidation technology |
| CN103088363A (en) * | 2012-12-13 | 2013-05-08 | 苏州新区化工节能设备厂 | Preparation method of stainless steel electrolysis electrode with titanium dioxide coating layer |
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