CN116986684A - Coating electrode for electrochemical water treatment electrode inversion and preparation method thereof - Google Patents
Coating electrode for electrochemical water treatment electrode inversion and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 230000002093 peripheral effect Effects 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000007750 plasma spraying Methods 0.000 claims description 5
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
- C25F1/08—Refractory metals
-
- 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
- C02F2001/46142—Catalytic coating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Thermal Sciences (AREA)
- Ceramic Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application discloses a coating electrode for electrochemical water treatment anode pouring and a preparation method thereof, comprising the following steps: titanium matrix, tiN 0.3 An intermediate layer, a surface active layer, the TiN 0.3 The middle layer is sprayed and arranged on the peripheral wall of the titanium matrixThe surface active layer is arranged on the TiN 0.3 And an intermediate layer. Through the mode, the coating electrode for the electrochemical water treatment anode and the preparation method thereof are disclosed by the application, and TiN is introduced 0.3 The intermediate layer improves the binding force between the coating and the matrix and the corrosion resistance of the matrix, so that the electrode has better stability, longer service life and better catalytic activity, improves the reverse descaling effect, improves the softening efficiency and reduces the energy consumption.
Description
Technical Field
The application relates to the technical field of electrode materials in the electrochemical industry, in particular to a coating electrode for electrochemical water treatment and a preparation method thereof.
Background
The circulating cooling water system has very wide application in industry, and has the problems of corrosion, scaling, biological slime and the like in the long-term operation process. The scale inhibitor is mainly added to inhibit system scaling in industry, but the method has the problems of large dosage of chemical reagent, easy secondary pollution and the like.
The electrochemical method is an environment-friendly technology and has good industrial application value in the treatment of circulating cooling water. When the electrochemical technology is adopted to treat the high-hardness circulating water, ca < 2+ >, mg < 2+ > and other hardness ions in the wastewater can be enriched in the cathode, and are combined with HCO < 3+ > in the water and OH < - > generated by the cathodic hydrogen evolution reaction to generate insoluble CaCO < 3 > -and Mg (OH) 2 scale layers which are covered on the surface of the electrode, so that the electrochemical reaction is hindered.
In order to solve the structural problems caused by the electrochemical method, the conventional treatment mode adopted at present is a mechanical scraping method, a scraper is required to be installed between a cathode and an anode to periodically scrape the scale on the cathode, but the installation of the mechanical scraper needs to occupy a larger space, the polar distance between the cathode and the anode is increased, so that the hardness removal efficiency is reduced, and the energy consumption is increased.
The reverse electrode is another descaling method available at present, and the basic principle is that in the reverse electrode process, the polarity of an electrode is reversed, the original cathode is switched to an anode, and the anode electrolyzes water to generate O2 and H+ and form an acidic atmosphere on the surface of the electrode. As h+ continues to accumulate on the electrode surface, the electrode surface pH gradually decreases, causing dissolution of scale near the electrode surface first. Subsequently, the outer scale layer is separated off successively due to insufficient adhesion
Compared with mechanical scraping descaling, the reverse electrode descaling avoids the installation of a mechanical scraper, and the electrodeposition reactor has the advantages of small electrode spacing, high softening efficiency, low energy consumption and the like, but the service life of the electrode can be obviously shortened due to frequent reverse electrode, so that the reverse electrode descaling has certain limitation in industrial popularization.
Currently, shape-stable electrodes (dimensionally stable anodes, DSA) are electrocatalytic electrodes made of titanium as a substrate, coated with metal oxides on the surface. DSA electrodes commonly used in industry are mainly ruthenium-based electrodes and iridium-based electrodes. The ruthenium electrode has high chlorine separation activity, strong corrosion resistance and relatively low cost, but has short service life under high current density. In contrast, the iridium electrode lifetime can be improved by 20 times, and thus, the iridium electrode has wide application in many fields. However, such conventional DSA electrodes are generally used only as anodes, and the polarity is not changed during operation, and if the reverse polarity operation is performed, insulating TiO2 and dissolution of the active layer are generated between the coating layer and the substrate of the DSA electrode, so that the active coating layer is separated, and the electrode is rapidly failed. In addition, noble iridium is expensive, which can greatly increase the production cost of the electrode and water treatment.
Therefore, it is important to find a coating material and a preparation process which can not only keep stable performance and electrocatalytic activity under the reverse working condition, but also reduce cost and electricity consumption.
Disclosure of Invention
In order to solve the technical problems, the application adopts a technical scheme that:
provided is a coated electrode for electrochemical water treatment reversal, comprising: titanium matrix, tiN 0.3 An intermediate layer, a surface active layer, the TiN 0.3 The middle layer is sprayed and arranged on the peripheral wall of the titanium matrix, and the surface active layer is arranged on the TiN 0.3 An intermediate layer;
the preparation steps of the coated electrode comprise:
(1) Pretreatment of a titanium matrix: cutting industrial pure titanium into small titanium plates after rolling and sand blasting treatment, and cleaning and airing the titanium plates by absolute ethyl alcohol and/or deionized water after alkali cleaning and oil removal and oxalic acid etching treatment to obtain a titanium matrix;
（2）TiN 0.3 and (3) preparing and treating an intermediate layer: drying Ti powder at 50-70deg.C for 2-3 hr, and plasma spraying according to N 2 The molar ratio of the titanium alloy to Ti is (3-5): 10 and preset spraying parameters to spray the dried titanium powder on the pretreated titanium substrate to form TiN on the titanium substrate 0.3 An intermediate layer; wherein, the spraying parameters include: the arc voltage is 60-70V, the arc current is 400-500A, the powder feeding gas flow is 3-5L/min, the gun distance is 50-100mm, the moving speed of the spray gun is 4-6m/min, the gas flow of plasma gas is 60-70L/min, the plasma gas is nitrogen or nitrogen-argon mixed gas, wherein the flow ratio of nitrogen to argon in the nitrogen-argon mixed gas is 1:1, a step of;
(3) Surface active layer treatment
(3.1) configuring the Ru-Ir-Ti coating solution such that Ru: ir: the molar ratio of Ti is 3:4:3;
(3.1.1) preparing a mixed solution of n-butanol and isopropanol in a volume ratio of 3:1, and then dissolving ruthenium trichloride in the mixed solution;
(3.1.2) after the ruthenium trichloride is completely dissolved, adding n-butanol solution of chloroiridic acid, and finally adding the prepared tetrabutyl titanate solution while stirring, so as to uniformly mix the tetrabutyl titanate solution to prepare the required Ru-Ir-Ti coating solution for later use;
(3.2) uniformly coating the prepared Ru-Ir-Ti coating solution on the coating solution with TiN 0.3 The titanium plate surface of the middle layer is placed in a drying oven, dried for 10min at 100-120 ℃, then the dried titanium plate is placed in a thermal oxidation furnace at 450 ℃ for thermal decomposition reaction, and after heat preservation for 10min, the titanium plate is taken out of the furnace and air-cooled; continuously brushing Ru-Ir-Ti coating solution on the cooled titanium plate, and drying the titanium plate for a plurality of times;
(3.3) after the coating solution of the last layer is coated and dried, the titanium plate is annealed at 450 ℃ for 60min, thus preparing the titanium plate which sequentially contains Ti base material and TiN from inside to outside 0.3 、RuO 2 -IrO 2 -TiO 2 And (3) a coated electrode.
In a preferred embodiment of the application, the commercially pure titanium is of the TA1 scale.
In a preferred embodiment of the present application, the step of alkaline washing the oil comprises: immersing the small plates in 10-15% sodium hydroxide solution, heating the solution to 60-80 ℃ and immersing the small plates for 1-2h.
In a preferred embodiment of the present application, the step of oxalic acid etching comprises: heating oxalic acid with the mass fraction of 10% -15% to 92-100 ℃, and then placing the alkaline washed platelets into the oxalic acid for 2-3h.
The beneficial effects of the application are as follows: by introducing TiN 0.3 The intermediate layer improves the binding force between the coating and the matrix and the corrosion resistance of the matrix, so that the electrode has better stability, longer service life and better catalytic activity, improves the reverse descaling effect, improves the softening efficiency and reduces the energy consumption.
Drawings
For a clearer description of the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the description below are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art, wherein:
FIG. 1 is a schematic view showing the structure of a coated electrode for electrochemical water treatment according to a preferred embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a coated electrode for electrochemical water treatment according to a preferred embodiment of the present application;
FIG. 3 shows the TiN-containing composition of the present application 0.3 SEM images of the surface active layer of the interlayer electrode (500 x left, 5000 x right);
FIG. 4 shows the TiN intermediate layer (left) and TiN in the application 0.3 SEM contrast of middle layer (right);
FIG. 5 shows TiN intermediate layer (a) and TiN in the application 0.3 XRD pattern of the intermediate layer (b);
FIG. 6 is a diagram of a conventional embodiment of the present applicationElectrode (a) and TiN-containing electrode 0.3 Life span of the intermediate layer electrode (b) versus graph.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Referring to fig. 1-6, an embodiment of the present application includes:
the coating electrode for the electrochemical water treatment inverting electrode structurally comprises the following components: titanium matrix, tiN 0.3 An intermediate layer, a surface active layer, the TiN 0.3 The middle layer is sprayed and arranged on the peripheral wall of the titanium matrix, and the surface active layer is arranged on the TiN 0.3 And an intermediate layer.
When pure Ti is used as an anode matrix, a non-conductive oxide film TiO is easy to generate on the surface 2 The anode process is prevented from being carried out on the electrode, in addition, the pure Ti has large internal resistance and high electrode potential, which not only inhibits the catalytic activity of the electrode, but also increases the reactive loss of the electrode, so TiN is introduced 0.3 An intermediate layer.
TiN 0.3 Has the characteristics similar to valve metal, and increases TiN with porous loose structure on the surface 0.3 An intermediate layer of TiN 0.3 The middle layer is not only a substrate of the surface active layer catalyst, but also an upper protective barrier of the titanium substrate, so that the titanium substrate can be protected, the physical and chemical properties of the surface catalytic layer can be improved, passivation and dissolution reactions can be inhibited, the binding force between the coating layers can be improved, the binding strength can be enhanced, the conductivity is stronger, the stability of the electrode can be remarkably improved, the effect of effectively slowing down the damage of the electrode to prolong the service life can be achieved, the use amount of noble metal can be effectively reduced, and the cost of the coating can be reduced.
The preparation method of the coating electrode for the electrochemical water treatment anode comprises the following specific steps:
(1) Titanium matrix pretreatment
The industrial pure titanium is cut into small plates after rolling and sand blasting treatment, and is cleaned and dried by absolute ethyl alcohol and/or deionized water after alkali washing oil removal and oxalic acid etching treatment to obtain a titanium matrix.
Further preferably, the commercially pure titanium is of the TA1 scale.
Further preferably, the step of alkaline washing to remove oil comprises: immersing the small plates in 10-15% sodium hydroxide solution, heating the solution to 60-80 ℃ and immersing the small plates for 1-2h.
Further preferably, the step of oxalic acid etching includes: heating oxalic acid with the mass fraction of 10% -15% to 95 ℃, and then placing the alkaline washed platelets into the oxalic acid for 2-3h.
（2）TiN 0.3 Intermediate layer preparation treatment
Drying Ti powder at 50-70deg.C for 2-3 hr, and then adding N 2 The molar ratio of the titanium alloy to Ti is (3-5): 10, spraying the dried titanium powder on the pretreated titanium substrate by adopting plasma spraying equipment to form TiN on the titanium substrate 0.3 An intermediate layer. The plasma spraying equipment can directly adopt the existing equipment to spray titanium powder, and the application does not relate to the improvement of the plasma spraying equipment.
Wherein, the spraying parameters include: the arc voltage is 60-70V, the arc current is 400-500A, the powder feeding air flow is 3-5L/min, the gun distance is 50-100mm, the moving speed of the spray gun is 4-6m/min, the plasma gas is nitrogen or nitrogen-argon mixed gas, and the flow ratio of nitrogen to argon is 1:1, and the air flow of the plasma gas is 60-70L/min.
Ti powder and N 2 The synthesis reaction is rapidly completed by heating in a plasma flame stream: ti+3/20N 2 =TiN 0.3 TiN under the action of air flow 0.3 Rapidly spraying the TiN on the titanium substrate due to the high splashing speed 0.3 Impact on the titanium matrix to be spread out and combined with the titanium matrix to form a coating, a large amount of TiN 0.3 The droplets continuously strike the titanium matrix, spread and solidify, and are covered layer by layer, thereby forming TiN with certain thickness 0.3 And (3) coating.
TiN X Refers to the holding ofOn the premise that the TiN face-centered cubic crystal structure is unchanged, a certain amount of Ti atoms or N atoms of TiN with vacancy defects exist in the crystal structure. TiN has a relatively wide range of metering compositions, and the N content X can vary from 0.26 to 1.16 without changing its face-centered cubic structure. When the content X of N is less than 1, that is, when N vacancy defects are present in the TiN crystal structure, a series of effects are exerted on the properties thereof, and the properties thereof are changed as the value of X is decreased.
(3) Surface active layer treatment: the coating is doped with a certain amount of Ru element to increase the potential difference between oxygen evolution and chlorine evolution, so that the oxygen evolution reaction is difficult to occur, the removal rate of anode chloride ions can be improved, and the service life of the electrode can be prolonged.
(3.1) preparing Ru-Ir-Ti coating solution, wherein Ru: ir: the molar ratio of Ti is 3:4:3.
(3.1.1) A mixed solution was prepared by mixing n-butanol and isopropanol in a volume ratio of 3:1, and ruthenium trichloride (RuCl) 3 ·3H 2 O) is dissolved in the mixed solution.
(3.1.2) after the ruthenium trichloride is completely dissolved, chloroiridic acid (H) is added 2 IrCl 6 ·xH 2 And O) n-butanol solution, and finally adding the prepared tetrabutyl titanate solution while stirring, so as to uniformly mix the tetrabutyl titanate solution to prepare the required Ru-Ir-Ti coating solution for later use.
(3.2) uniformly coating the prepared Ru-Ir-Ti coating solution with TiN using a soft brush 0.3 And (3) placing the titanium plate on the surface of the middle layer in a drying oven, drying at 100-120 ℃ for 10min, placing the dried titanium plate in a thermal oxidation furnace at 450 ℃ for thermal decomposition reaction, keeping the temperature for 10min, discharging, air-cooling, and continuing to carry out Ru-Ir-Ti coating solution coating and drying treatment, thus repeating 7-13 times. By adopting the gradient brushing process, the coating structure can be obviously improved.
(3.3) after the final coating solution is coated and dried, annealing the titanium plate at 450 ℃ for 60min, thereby preparing the titanium plate containing Ti substrate and TiN from inside to outside 0.3 、RuO 2 -IrO 2 -TiO 2 And (3) a coated electrode.
As shown in FIG. 4, the surface of the intermediate layer of the electrode having only the TiN structure is relatively dense (left image), and contains TiN 0.3 The surface (right) of the electrode intermediate layer of the structure is loose, so that the surface active layer can be coated in the next step more conveniently, the binding force between the coating and the matrix and the corrosion resistance of the matrix are increased, and the electrode intermediate layer has better stability.
As shown in fig. 6, curve a represents a conventional anode, and curve b represents a coated titanium anode prepared by the present application, it can be seen that the reinforcement life of the coated anode prepared by the present application is effectively improved.
The application relates to a coating electrode for electrochemical water treatment and a preparation method thereof, which has the beneficial effects that:
1. by introducing TiN 0.3 The intermediate layer has good protection effect on the matrix, has good repeatability, can effectively delay the passivation speed of the titanium matrix, prolongs the service life of the electrode, and simultaneously ensures that the electrode has good catalytic activity;
2. by introducing an interlayer TiN 0.3 The binding force between the coating and the matrix and the corrosion resistance of the matrix are improved, the stability is better, the corrosion actions of anodic electrolysis and electric/chemical dissolution in the medium can be resisted, frequent replacement is avoided, and the requirement of continuous production is better met;
3. by introducing an interlayer TiN 0.3 The produced electrode has better catalytic activity, wide potential window and better conductivity, can provide stable channels for electron transmission, and does not generate extra resistance energy consumption;
4. by using the coating electrode, a cathode scraping plate is not required to be additionally arranged, the operation is simple, the electrode spacing of the electrodeposition reactor is reduced, the reverse electrode descaling effect can be improved, the softening efficiency is improved, and the energy consumption is reduced;
5. the gradient preparation process not only improves the binding force among the active layers and reduces the loading amount of noble metal, but also has lower coating cost and effectively reduces the enterprise cost.
The foregoing description is only illustrative of the present application and is not intended to limit the scope of the application, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present application.
Claims (4)
1. A coated electrode for electrochemical water treatment of a reversed electrode, comprising: titanium matrix, tiN 0.3 An intermediate layer, a surface active layer, the TiN 0.3 The middle layer is sprayed and arranged on the peripheral wall of the titanium matrix, and the surface active layer is arranged on the TiN 0.3 An intermediate layer;
the preparation steps of the coated electrode comprise:
(1) Pretreatment of a titanium matrix: cutting industrial pure titanium into small titanium plates after rolling and sand blasting treatment, and cleaning and airing the titanium plates by absolute ethyl alcohol and/or deionized water after alkali cleaning and oil removal and oxalic acid etching treatment to obtain a titanium matrix;
（2）TiN 0.3 and (3) preparing and treating an intermediate layer: drying Ti powder at 50-70deg.C for 2-3 hr, and spraying with plasma spraying equipment according to N 2 The molar ratio of the titanium alloy to Ti is (3-5): 10 and preset spraying parameters to spray the dried titanium powder on the pretreated titanium substrate to form TiN on the titanium substrate 0.3 An intermediate layer; wherein, the spraying parameters include: the arc voltage is 60-70V, the arc current is 400-500A, the powder feeding gas flow is 3-5L/min, the gun distance is 50-100mm, the moving speed of the spray gun is 4-6m/min, the gas flow of plasma gas is 60-70L/min, the plasma gas is one of nitrogen gas or nitrogen-argon gas mixed gas, wherein the flow ratio of the nitrogen gas to the argon gas is 1:1, a step of;
(3) Surface active layer treatment
(3.1) configuring the Ru-Ir-Ti coating solution such that Ru: ir: the molar ratio of Ti is 3:4:3;
(3.1.1) preparing a mixed solution of n-butanol and isopropanol in a volume ratio of 3:1, and then dissolving ruthenium trichloride in the mixed solution;
(3.1.2) after the ruthenium trichloride is completely dissolved, adding chloroiridic acid and n-butanol solution, and finally adding the prepared tetrabutyl titanate solution while stirring, so that the tetrabutyl titanate solution is uniformly mixed to prepare the required Ru-Ir-Ti coating solution for later use;
(3.2) uniformly coating the prepared Ru-Ir-Ti coating solution on the coating solution with TiN 0.3 The titanium plate surface of the middle layer is placed in a drying oven, dried for 10min at 100-120 ℃, then the dried titanium plate is placed in a thermal oxidation furnace at 450 ℃ for thermal decomposition reaction, and after heat preservation for 10min, the titanium plate is taken out of the furnace and air-cooled; continuously brushing Ru-Ir-Ti coating solution on the cooled titanium plate, and drying the titanium plate for a plurality of times;
(3.3) after the coating solution of the last layer is coated and dried, the titanium plate is annealed at 450 ℃ for 60min, thus preparing the titanium plate which sequentially contains Ti base material and TiN from inside to outside 0.3 、RuO 2 -IrO 2 -TiO 2 And (3) a coated electrode.
2. The coated electrode for electrochemical water treatment and its preparation method as claimed in claim 1, wherein the industrial pure titanium is TA1 grade.
3. The coated electrode for electrochemical water treatment and preparation method thereof according to claim 1, wherein the step of alkaline washing for removing oil comprises: immersing the small plates in 10-15% sodium hydroxide solution, heating the solution to 60-80 ℃ and immersing the small plates for 1-2h.
4. The coated electrode for electrochemical water treatment and preparation method thereof according to claim 1, wherein the step of oxalic acid etching comprises: heating oxalic acid with the mass fraction of 10% -15% to 92-100 ℃ for slight boiling, and then placing the alkaline washed platelets into the oxalic acid for 2-3h.
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Application publication date: 20231103 |