CN112158920B - Anode material suitable for external cold water treatment, preparation method and treatment process - Google Patents

Anode material suitable for external cold water treatment, preparation method and treatment process Download PDF

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CN112158920B
CN112158920B CN202010967736.1A CN202010967736A CN112158920B CN 112158920 B CN112158920 B CN 112158920B CN 202010967736 A CN202010967736 A CN 202010967736A CN 112158920 B CN112158920 B CN 112158920B
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cold water
external cold
titanium substrate
solution
layer
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CN112158920A (en
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祝海峰
郑丰
毛臻炫
龙英云
姚传涛
谢保鸡
路思佳
李晓良
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Tianshengqiao Bureau of Extra High Voltage Power Transmission Co
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Tianshengqiao Bureau of Extra High Voltage Power Transmission Co
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • 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
    • 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
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C02F2201/46185—Recycling the cathodic or anodic feed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention discloses an anode material suitable for external cold water treatment, which comprises a substrate layer, a middle layer and a catalytic oxidation layer from inside to outside, wherein the substrate layer is a treated titanium layer, the middle layer is a TiN layer loaded by ion sputtering, and the catalytic oxidation layer is IrO doped with La, Sb, carbon nanodots and dodecyl dimethyl betaine2‑RuO2And (3) a layer. The anode material suitable for treating the external cold water solves the problems that the salt concentration and the organic matter concentration of the external cold water are increased due to the addition of chemical substances, the service life and the treatment efficiency of a reverse osmosis membrane are greatly shortened, the concentrated water quantity is increased, and the water quality effect after purification is not ideal in the prior art. The invention also discloses a method for preparing the anode material suitable for external cold water treatment and a treatment method suitable for external cold water treatment.

Description

Anode material suitable for external cold water treatment, preparation method and treatment process
Technical Field
The invention belongs to the technical field of water treatment, and relates to an anode material suitable for external cold water treatment, a preparation method of the anode material and a treatment process suitable for external cold water treatment.
Background
The converter valve is one of core equipment of high-voltage direct-current transmission, and a large amount of heat is generated in the operation process of the converter valve, so that a valve cooling water system is required to cool the converter valve. Generally, a valve cooling water system is composed of an in-valve cooling water system (closed) and an out-valve cooling water system (open), wherein the in-valve cooling water system adopts deionized water as a medium and is responsible for discharging heat generated by a valve component to the outside of a valve hall so as to ensure that a thyristor of the converter valve component operates within a controllable temperature range; the water cooling system outside the valve generally uses softened water to continuously cool the pipeline of the water cooling system inside the valve through a cooling tower, so that the water cooling temperature inside the valve is reduced, and the continuous cooling capacity of the water cooling system inside the valve is ensured.
Because the external cold water system is an open type, along with the phenomena of wind blowing, evaporation, impurity introduction and the like, salt and organic matters in the external cold water are greatly concentrated, so that series problems of corrosion, scaling, bacterial and algae breeding and the like of the external cold water system of the valve are caused, the heat exchange efficiency is reduced, the accidents of locking, tripping and stopping operation are caused due to overhigh water temperature of the internal cold water, equipment is damaged, and the production is influenced. Therefore, the improvement of the water quality condition of the external cooling water system plays an important role in the long-term stable operation of the valve cooling water system.
At present, the water quality of external cold water is stabilized by adopting modes such as adding medicaments (mostly organic phosphine medicaments), ion exchange and the like. However, the operation brings new pollution to external cold water, so that the quality of external drainage water does not reach the standard, and even a great deal of algae in the water body is bred. In recent years, the reverse osmosis technology is applied to the treatment of external cold water, the water quality condition of the external cold water is effectively improved in the normative use process, namely, the water is subjected to filtration, softening and reverse osmosis, and then passes through an external cold water circulating system, but the salt concentration and the organic matter concentration of the external cold water are increased due to the addition of excessive chemical substances including inorganic salt, water treatment agents and the like, the service life and the treatment efficiency of the reverse osmosis membrane are greatly shortened, the concentrated water quantity is increased, and the purified water quality effect is not ideal. Therefore, a new green method is needed to treat the external cold water, reduce the addition of chemical substances and discharge capacity, and reduce the environmental pressure while saving water.
China patent (publication number: CN105712500B) relates to a descaling device and a descaling method for external cold water of a cooling system of a direct-current converter valve, belongs to the technical field of external cold water treatment, and adopts an electrochemical technology to remove scale-causing ions of the external cold water, so that the problem of scaling of a cooling tower in an external cooling system can be effectively solved. The method proves that the electrochemical technology has the characteristics of convenience and rapidness in operation, environmental friendliness and high descaling efficiency, can improve the concentration rate of external cold water to a certain extent, reduces external drainage, saves water resources, and finally achieves the aims of water saving and emission reduction.
However, the core of electrochemical water treatment is the anode used, and the external cooling water contains more salt ions (such as chloride ions, etc.), so the water treatment process should ensure the high-performance stable operation of the anode to achieve the continuous and efficient extraction of scaling ions in water. Aiming at the problems of large dosage of traditional Chinese medicine for controlling external cold water, more external concentrated water, poor water quality treatment effect and the like, the development of a green technology suitable for efficiently treating the external cold water is very important.
Disclosure of Invention
The invention aims to provide an anode material suitable for treating external cold water, and solves the problems that the salt concentration and the organic matter concentration of the external cold water are increased due to the addition of chemical substances, the service life and the treatment efficiency of a reverse osmosis membrane are greatly shortened, the concentrated water amount is increased, and the water quality effect after purification is not ideal in the prior art.
A second object of the present invention is to provide a method for preparing an anode material suitable for external cold water treatment.
The third purpose of the invention is to provide a treatment method suitable for external cold water treatment.
The technical scheme adopted by the invention is that the anode material is suitable for external cold water treatment, the anode material comprises a substrate layer, an intermediate layer and a catalytic oxidation layer from inside to outside, the substrate layer is a treated titanium layer, the intermediate layer is a TiN layer loaded by ion sputtering, and catalytic oxidation is carried outThe layer is IrO doped with La, Sb, carbon nanodots and dodecyl dimethyl betaine2-RuO2And (3) a layer.
The second technical scheme adopted by the invention is that the method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment.
The second aspect of the present invention is also characterized in that,
the step 1 specifically comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, keeping the temperature of the solution at 90-99 ℃ during soaking, controlling the soaking time at 60-180 min, washing the soaked titanium substrate with ultrapure water for several times, and naturally drying for later use;
step 1.3, etching of the titanium substrate
And (3) soaking the titanium substrate treated in the step (1.2) in oxalic acid solution with the mass fraction of 3-15% for etching, keeping the temperature at 90-99 ℃ during soaking, soaking for 60-180 min, cleaning the titanium substrate with ultrapure water for several times after soaking to obtain a material A with uniform pitted surface, and naturally airing for later use.
The step 2 specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A treated in the step 1 in an arc ion plating machine for 5-10 min, wherein the vacuum pressure in the arc ion plating machine is kept at 18-22V, and the bias voltage is-750-900V;
step 2.2, preparation of TiN layer
And (3) plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 10-30 min in an arc ion plating machine with the vacuum chamber pressure kept at 0.2-0.4 pa, the arc pressure at 18-22V and the matrix bias at-240-260V to obtain a material B.
The step 3 specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the solution to be loaded on the material B in the step 2.2, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 50-120 ℃, and naturally cooling to room temperature after drying;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 400-550 ℃ from room temperature for 15-45 min at the heating rate of 1-8 ℃/min, cooling the material B to room temperature, continuing to perform the step 3.1-3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
The solution to be loaded is H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a mixed solution of absolute ethyl alcohol, n-butyl alcohol, isopropanol and a carbon nano-dot solution.
Adding H into the solvent to be loaded, wherein the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol are used as the solvent, the volume ratio of the absolute ethyl alcohol to the n-butyl alcohol to the isopropanol is 1:1:1, and then the solvent is added with the H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.25 to 0.5mol/L, RuCl3In a concentration of 0.5 to1mol/L, NaF of 0.001-0.002 mol/L, dodecyl dimethyl betaine of 0.05-0.1 g/L, SbCl3Has a concentration of 0.05 to 0.1mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.01-0.05 mol/L, and the content of the carbon nano-dot solution is as follows: the carbon nano-dot solution is 5-15 mL in 100mL of solution to be loaded, and the adding volume of absolute ethyl alcohol, n-butyl alcohol and isopropanol is 1:1: 1.
The third technical scheme adopted by the invention is as follows: the treatment process suitable for external cold water treatment specifically comprises the following steps: adding a bypass between filtration and softening for electrochemical treatment, so that part of the filtered water supplement is directly softened, part of the filtered water supplement is softened after electrochemical treatment, adding a bypass between reverse osmosis and an external cold water circulating system for electrochemical treatment, namely, part of the filtered water supplement is directly treated by the external cold water circulating system, and part of the filtered water supplement is treated by the external cold water circulating system after electrochemical treatment, wherein the anode material adopted by the electrochemical treatment is the prepared anode material, the cathode is a conductive material, and the current density range is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
The invention has the beneficial effects that:
(1) the anode material has long service life, and meanwhile, the removal efficiency of scale forming ions in the external cold water can reach 37.4 percent, so that the scale forming risk of the external cold water is relieved, the cost of electrochemical treatment is further reduced, the chemical addition and discharge capacity are reduced, and the environmental pressure is reduced while water is saved.
(2) According to the invention, after the electrochemical module is embedded in front of the water replenishing treatment part of the softening module of the converter valve external cold water circulation system, the removal rate of the scale forming ions in the water replenishing reaches 13.4%, the backwashing period of the cation exchange resin of the subsequent softening module is prolonged, the membrane life of the subsequent reverse osmosis system is prolonged, and the treatment effect is improved. An electrochemical module is embedded in a cold water circulating system outside the converter valve, so that scaling ions in circulating water are removed secondarily, the quality of the circulating water is improved, scaling risk is reduced, concentration multiple is improved, and discharge of waste water is reduced.
Drawings
FIG. 1 is a schematic diagram of a treatment process of the present invention suitable for use in external cold water treatment;
FIG. 2 is an SEM image of the electrode morphology prepared from the anode material suitable for external cold water treatment according to the invention;
FIG. 3 is a graph showing the enhanced life of an electrode in the method for preparing an anode material suitable for external cold water treatment according to the present invention;
FIG. 4 is a graph showing the trend of scaling ions in water with electrochemical parameters when water is supplemented by electrochemical treatment;
FIG. 5 is a graph of the removal effect of hardness in a simulated external cold water circulation system;
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The anode material is suitable for external cold water treatment, and comprises a substrate layer, an intermediate layer and a catalytic oxidation layer from inside to outside, wherein the substrate layer is a treated titanium layer, the intermediate layer is a TiN layer loaded by ion sputtering, and the catalytic oxidation layer is IrO doped with La, Sb, carbon nanodots and dodecyl dimethyl betaine2-RuO2And (3) a layer.
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, keeping the temperature of the solution at 90-99 ℃ during soaking, controlling the soaking time at 60-180 min, washing the soaked titanium substrate with ultrapure water for several times, and naturally drying for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 3-15% for etching, keeping the temperature at 90-99 ℃ during soaking, soaking for 60-180 min, cleaning the soaked titanium substrate with ultrapure water for several times to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A treated in the step 1 in an arc ion plating machine for 5-10 min, wherein the vacuum pressure in the arc ion plating machine is kept at 18-22V, and the bias voltage is-750-900V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 10-30 min in an arc ion plating machine with the vacuum chamber pressure kept at 0.2-0.4 pa, the arc pressure at 18-22V and the matrix bias at-240-260V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the material B in the step 2.2 with the solution to be loaded, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 50-120 ℃, naturally cooling to room temperature after drying, taking absolute ethyl alcohol, n-butyl alcohol and isopropanol as solvents in the solution to be loaded, wherein the volume ratio of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1:1, and then adding H into the solvents2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.25 to 0.5mol/L, RuCl3The concentration of (A) is 0.001-0.002 mol/L, the concentration of (B) is 0.5-1 mol/L, NaF, and the concentration of dodecyl dimethyl betaine is 0.05-0.1g/L，SbCl3The concentration of (A) is 0.05-0.1 mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.01-0.05 mol/L, and the content of the carbon nano-dot solution is as follows: 5-15 mL of carbon nano-dot solution is contained in 100mL of solution to be loaded;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 400-550 ℃ from room temperature for 15-45 min at the heating rate of 1-8 ℃/min, cooling the material B to room temperature, continuing to perform the step 3.1-3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
The invention is suitable for the treatment process of external cold water treatment, the flow of which is shown in figure 1, and the process specifically comprises the following steps: adding a bypass between filtration and softening for electrochemical treatment, so that part of the filtered water supplement is directly softened, part of the filtered water supplement is softened after electrochemical treatment, adding a bypass between reverse osmosis and an external cold water circulating system for electrochemical treatment, namely, part of the filtered water supplement is directly treated by the external cold water circulating system, and part of the filtered water supplement is treated by the external cold water circulating system after electrochemical treatment, wherein the anode material adopted by the electrochemical treatment is the prepared anode material, the cathode is a conductive material, and the current density range is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
The invention embeds the electrochemical processing module in the circulating cooling process of the external cold water of the converter valve, thereby reducing the scaling ions (such as Ca) in the external cold water2+、Mg2+Etc.) and comprehensively relieving the pressure of the subsequent treatment module by catalytic oxidation of the anode;
as shown in FIG. 1, the electrochemical module is embedded in a bypass mode before the softening module, so that the removal rate of the scaling ions in the supplemented water can reach 13.4%, and the backwashing period of the cation exchange resin of the softening module is also relieved; meanwhile, the anode has catalytic oxidation capacity and can degrade organic matters in the water supplement, and the combined action of the anode and the water supplement can relieve the treatment pressure of a subsequent reverse osmosis module, delay the service life of the membrane and improve the reverse osmosis treatment efficiency;
an electrochemical module is embedded in an external cold water circulating system in a bypass mode, so that scaling ions in external cold water are removed for the second time, the scaling risk of circulating water is reduced, meanwhile, the concentration multiple can be increased from 2-3 times to 4-5 times, and the discharge amount of sewage is reduced;
wherein the anode in the electrochemical module is made of an anode material suitable for external cold water treatment, the cathode is made of a conductive material such as stainless steel, and the like, and the current density range is 1-20 mA/cm2The pH range is 6-9, the treatment temperature is 15-45 ℃, and the treatment capacity is 600-800L/h.
The filtering links of the invention comprise sand filtering, carbon filtering, multi-medium filtering and the like; the softening step adopts cation exchange resin, and sodium chloride is added to remove Ca in water2+、Mg2+The ions are displaced out to reduce the total hardness in the water. Reverse osmosis relieving is to carry out final treatment on the replenishing water through a reverse osmosis membrane so as to further improve the water quality.
Example 1
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 5%, keeping the temperature of the solution at 98 ℃ during soaking, controlling the soaking time at 120min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 5% for etching, wherein the soaking temperature is kept at 98 ℃, the soaking time is 120min, cleaning the titanium substrate after the soaking with ultrapure water for a plurality of times to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 8min, wherein the vacuum pressure in the arc ion plating machine is kept at 20V, and the bias voltage is-800V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 20min in an arc ion plating machine with the vacuum chamber pressure kept at 0.3pa, the arc pressure at 20V and the matrix bias voltage at-255V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprising the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the solution to be loaded on the material B in the step 2.2, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 75 ℃, naturally cooling to room temperature after drying, and the solution to be loaded is H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a mixed solution of absolute ethyl alcohol, n-butanol, isopropanol and a carbon nanodot solution, wherein H is2IrCl6·6H2The concentration of O is 0.35mol/L, RuCl3Has a concentration of 0.001mol/L of 0.6mol/L, NaF, a concentration of dodecyl dimethyl betaine of 0.06g/L, and SbCl3Has a concentration of 0.06mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.03mol/L, and the content of the carbon nano-dot solution is as follows: adding 8mL of carbon nanodot solution into 100mL of solution to be loaded, and adding anhydrous ethanol, n-butanol and isopropanolThe volume is 1:1: 1.
Step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 500 ℃ from the room temperature for 20min at the heating rate of 5 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material with clear water for several times after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
FIG. 3 is a graph comparing the lifetime of a modified electrode and that of an unmodified electrode, the electrodes being prepared at 3mol/L H2SO4In the solution, the temperature of the solution is controlled at 25 ℃, and the current density range is controlled at 500mA/cm2The service life of the undoped electrode is 703h, and the service life of the electrode is prolonged to 1018h after the electrode is doped and modified by La, Sb, carbon nanodots and dodecyl dimethyl betaine.
Example 2
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of a titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 5%, keeping the temperature of the solution at 98 ℃ during soaking, controlling the soaking time at 120min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 5% for etching, keeping the soaking temperature at 98 ℃, soaking for 120min, cleaning the titanium substrate with ultrapure water for a plurality of times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 8min, wherein the vacuum pressure in the arc ion plating machine is kept at 20V, and the bias voltage is-800V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 20min in an arc ion plating machine with the vacuum chamber pressure kept at 0.3pa, the arc pressure at 20V and the matrix bias voltage at-255V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the material B in the step 2.2 with the solution to be loaded, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 75 ℃, naturally cooling to room temperature after drying, taking absolute ethyl alcohol, n-butyl alcohol and isopropanol as solvents in the solution to be loaded, wherein the volume ratio of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1:1, and then adding H into the solvent2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.25 to 0.5mol/L, RuCl3The concentration of (A) is 0.001-0.002 mol/L, the concentration of dodecyl dimethyl betaine is 0.05-0.1 g/L, and SbCl is 0.5-1 mol/L, NaF3Has a concentration of 0.05 to 0.1mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.01-0.05 mol/L, and the content of the carbon nano-dot solution is as follows: 5-15 mL of carbon nano-dot solution is contained in 100mL of solution to be loaded;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 500 ℃ from the room temperature for 20min at the heating rate of 5 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
FIG. 4 is a graph showing the effect of removing hardness in the make-up water after the electrochemical module is embedded in a simulated circulation manner by using a dynamic simulation device for circulating cooling water, wherein the removal rate of hardness in the make-up water reaches 13.4% before the electrochemical module is embedded in the softening module, the total hardness of water in the simulated make-up water is 90mg/L, the total quantity of make-up water is 160L, the flow rate is 300L/h, the electrochemical treatment time is 30min, and the current density is 10mA/cm2The pH was 8.4 and the treatment temperature was 25 ℃.
FIG. 5 is a diagram showing the effect of removing hardness from the external cold water circulation system after the electrochemical module is inserted into the external cold water circulation system in a simulated circulation manner by using a dynamic simulation device for circulating cooling water, wherein the removal rate of hardness from the external cold water reaches 37.4%, the total hardness of the simulated external cold water is 40mg/L, the circulation water amount is 630L/h, the electrochemical treatment time is 60min, and the current density is 10mA/cm2The pH range is 8.5, the treatment temperature is 25 DEG C
Example 3
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 5%, keeping the temperature of the solution at 98 ℃ during soaking, controlling the soaking time at 120min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 5% for etching, keeping the soaking temperature at 98 ℃, soaking for 120min, cleaning the titanium substrate with ultrapure water for a plurality of times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 8min, wherein the vacuum pressure in the arc ion plating machine is kept at 20V, and the bias voltage is-800V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 20min in an arc ion plating machine with the vacuum chamber pressure kept at 0.3pa, the arc pressure at 20V and the matrix bias voltage at-255V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the solution to be loaded on the material B in the step 2.2, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 75 ℃, naturally cooling to room temperature after drying, and the solution to be loaded is H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a mixed solution of absolute ethyl alcohol, n-butanol, isopropanol and a carbon nanodot solution, wherein H is2IrCl6·6H2The concentration of O is 0.35mol/L, RuCl3Has a concentration of 0.001mol/L of 0.6mol/L, NaF, a concentration of dodecyl dimethyl betaine of 0.06g/L, and SbCl3Has a concentration of 0.06mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.03mol/L, and the content of the carbon nano-dot solution is as follows: 100mL of the solution to be loaded contains 8mL of the carbon nanodot solution, and the adding volume of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1: 1.
Step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 500 ℃ from the room temperature for 20min at the heating rate of 5 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
And before water supplement, an electrochemical module is embedded, 33.8 percent of total hardness in water supplement is removed, the backwashing period of the cation exchange resin in the subsequent softening link is prolonged, before the electrochemical module is not embedded, the cation exchange resin in the softening link is backwashed once every 12 days, and after the electrochemical module is embedded before the softening link, the backwashing period of the cation exchange resin is increased to 21 days.
Example 4
FIG. 2 shows the SEM morphology of the prepared anode material suitable for external cold water treatment, which is specifically implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 5%, keeping the temperature of the solution at 98 ℃ during soaking, controlling the soaking time at 120min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally drying for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 5% for etching, keeping the soaking temperature at 98 ℃, soaking for 120min, cleaning the titanium substrate with ultrapure water for a plurality of times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 8min, wherein the vacuum pressure in the arc ion plating machine is kept at 20V, and the bias voltage is-800V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 20min in an arc ion plating machine with the vacuum chamber pressure kept at 0.3pa, the arc pressure at 20V and the matrix bias voltage at-255V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying the material B
Uniformly coating the solution to be loaded on the material B in the step 2.2, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 75 ℃, naturally cooling to room temperature after drying, and the solution to be loaded is H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a mixed solution of absolute ethyl alcohol, n-butanol, isopropanol and a carbon nanodot solution, wherein H is2IrCl6·6H2The concentration of O is 0.35mol/L, RuCl3Has a concentration of 0.001mol/L of 0.6mol/L, NaF, a concentration of dodecyl dimethyl betaine of 0.06g/L, and SbCl3Has a concentration of 0.06 mol-L、La(NO3)3The concentration of the carbon nano-dot solution is 0.03mol/L, and the content of the carbon nano-dot solution is as follows: 100mL of the solution to be loaded contains 8mL of the carbon nanodot solution, and the adding volume of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1: 1.
Step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 500 ℃ from the room temperature for 20min at the heating rate of 5 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
Example 5
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 12%, keeping the temperature of the solution at 94 ℃ during soaking, controlling the soaking time at 120min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 10% for etching, keeping the soaking temperature at 95 ℃ for 100min, cleaning the titanium substrate with ultrapure water for several times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 8min, wherein the vacuum pressure in the arc ion plating machine is kept at 20V, and the bias voltage is-800V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 20min in an arc ion plating machine with the vacuum chamber pressure kept at 0.3pa, the arc pressure at 20V and the matrix bias at-250V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the material B in the step 2.2 with the solution to be loaded, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 50-120 ℃, naturally cooling to room temperature after drying, taking absolute ethyl alcohol, n-butyl alcohol and isopropanol as solvents in the solution to be loaded, wherein the volume ratio of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1:1, and then adding H into the solvents2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.4mol/L, RuCl3The concentration of (a) is 0.0015mol/L and the concentration of dodecyl dimethyl betaine is 0.05-0.1 g/L, and the concentration of SbCl is 0.8mol/L, NaF3Has a concentration of 0.08mol/L, La (NO)3)3The concentration of (2) is 0.025mol/L, and the content of the carbon nano-dot solution is as follows: 100mL of solution to be loaded contains 10mL of carbon nanodot solution;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 500 ℃ from the room temperature for 30min at the heating rate of 5 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
Example 6
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 15%, keeping the temperature of the solution at 99 ℃ during soaking, controlling the soaking time at 180min, washing the soaked titanium substrate with ultrapure water for a plurality of times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 15% for etching, keeping the soaking temperature at 99 ℃, soaking for 180min, cleaning the titanium substrate with ultrapure water for several times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 10min, wherein the vacuum pressure in the arc ion plating machine is kept at 22V, and the bias voltage is-900V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 30min in an arc ion plating machine with the vacuum chamber pressure kept at 0.4pa, the arc pressure at 22V and the matrix bias voltage at-260V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
Uniformly coating the material B in the step 2.2 with the solution to be loaded, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 120 ℃, naturally cooling to room temperature after drying, taking absolute ethyl alcohol, n-butyl alcohol and isopropanol as solvents in the solution to be loaded, wherein the volume ratio of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1:1, and then adding H into the solvent2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.5mol/L, RuCl3Has a concentration of 1mol/L, NaF of 0.002mol/L, a concentration of dodecyl dimethyl betaine of 0.1g/L, and SbCl3Has a concentration of 0.1mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.05mol/L, and the content of the carbon nano-dot solution is as follows: 100mL of solution to be loaded contains 15mL of carbon nanodot solution;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 550 ℃ from room temperature for 45min at the heating rate of 8 ℃/min, cooling the material B to room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
Example 7
The method for preparing the anode material suitable for external cold water treatment is implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface, which comprises the following steps:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 3%, keeping the temperature of the solution at 90 ℃ during soaking, controlling the soaking time at 60min, washing the soaked titanium substrate with ultrapure water for several times, and naturally airing for later use;
step 1.3, etching of the titanium substrate
Soaking the titanium substrate treated in the step 1.2 in oxalic acid solution with the mass fraction of 3% for etching, keeping the temperature at 90 ℃ during soaking, soaking for 60min, cleaning the titanium substrate with ultrapure water for a plurality of times after soaking to obtain a material A with uniform pitted surface, and naturally drying for later use;
step 2, carrying out thermal decomposition oxidation loading on the material A to obtain an anode material B suitable for external cold water treatment, which specifically comprises the following steps:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 5min, wherein the vacuum pressure in the arc ion plating machine is kept at 18V, and the bias voltage is-750V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 10min in an arc ion plating machine with the vacuum chamber pressure kept at 0.2pa, the arc pressure at 18V and the matrix bias voltage at-240V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, and specifically comprises the following steps:
step 3.1, coating and drying of the material B
The solution to be loaded is applied homogeneously in step 2.2And (2) drying the coated material B in an oven at the temperature of 50 ℃, naturally cooling to room temperature after drying, adding H into the solvent when absolute ethyl alcohol, n-butyl alcohol and isopropanol are used as solvents and the volume ratio of the absolute ethyl alcohol, the n-butyl alcohol and the isopropanol is 1:1:1 in the loading solution, and adding the H into the solvent2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La(NO3)3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.25mol/L, RuCl3Has a concentration of 0.001mol/L of 0.5mol/L, NaF, a concentration of 0.05g/L of dodecyl dimethyl betaine, and SbCl3Has a concentration of 0.05mol/L, La (NO)3)3The concentration of the carbon nano-dot solution is 0.01mol/L, and the content of the carbon nano-dot solution is as follows: 100mL of solution to be loaded contains 5mL of carbon nanodot solution;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 400 ℃ from the room temperature for 15min at the heating rate of 1 ℃/min, cooling the material B to the room temperature, continuing to perform the step 3.1 to 3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.

Claims (5)

1. The method for preparing the anode material suitable for the external cold water treatment is characterized in that the anode material comprises a substrate layer, an intermediate layer and a catalytic oxidation layer from inside to outside, the substrate layer is a treated titanium layer, the intermediate layer is a TiN layer loaded by ion sputtering, and the catalytic oxidation layer is IrO doped with La, Sb, carbon nanodots and dodecyl dimethyl betaine2-RuO2The layer is specifically implemented according to the following steps:
step 1, pretreating a titanium substrate layer to obtain a material A with a uniform pitted surface on the surface;
step 2, specifically:
step 2.1, cleaning of Material A
Cleaning the material A processed in the step 1 in an arc ion plating machine for 5-10 min, wherein the vacuum pressure in the arc ion plating machine is kept at 18-22V, and the bias voltage is-750V to-900V;
step 2.2, preparation of TiN layer
Plating a TiN layer on the material A cleaned in the step 2.1 by adopting an ion sputtering method, and depositing for 10-30 min in an arc ion plating machine with the vacuum chamber pressure kept at 0.2-0.4 pa, the arc pressure 18-22V and the matrix bias voltage of-240-260V to obtain a material B;
and 3, loading the loading solution on the material B by a thermal oxidation decomposition method to obtain a material C, namely the anode material suitable for external cold water treatment, wherein the loading solution is H2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La（NO3）3And a mixed solution of absolute ethyl alcohol, n-butyl alcohol, isopropanol and a carbon nano-dot solution.
2. The method for preparing an anode material suitable for external cold water treatment according to claim 1, wherein the step 1 is specifically:
step 1.1, polishing and cleaning of titanium substrate
Mechanically polishing the titanium substrate by using abrasive paper with different meshes until the surface of the titanium substrate is smooth and bright, cleaning the polished titanium substrate by using ultrapure water for several times, and naturally airing for later use;
step 1.2 degreasing of titanium substrate
Putting the titanium substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, keeping the temperature of the solution at 90-99 ℃ during soaking, controlling the soaking time at 60-180 min, washing the soaked titanium substrate with ultrapure water for several times, and naturally drying for later use;
step 1.3, etching of the titanium substrate
And (3) soaking the titanium substrate treated in the step (1.2) in oxalic acid solution with the mass fraction of 3-15% for etching, keeping the temperature at 90-99 ℃ during soaking, soaking for 60-180 min, cleaning the titanium substrate with ultrapure water for several times after soaking to obtain a material A with uniform pitted surface, and naturally airing for later use.
3. The method for preparing an anode material suitable for external cold water treatment according to claim 1, wherein the step 3 is specifically:
step 3.1, coating and drying of the material B
Uniformly coating the load solution on the material B in the step 2.2, placing the coated material B in an oven for drying, wherein the temperature range of the oven is 50-120 ℃, and naturally cooling to room temperature after drying;
step 3.2, calcining the material B;
calcining the material B treated in the step 3.1 in heating equipment, heating the material B to 400-550 ℃ from room temperature for 15-45 min at the heating rate of 1-8 ℃/min, cooling the material B to room temperature, continuing to perform the step 3.1-3.2 on the cooled material,
and 3.3, repeating the step 3.1 and the step 3.2 for 5-10 times, and cleaning the material for several times by using clear water after the material is cooled in the last time, so that the method is suitable for the anode material treated by external cold water.
4. The method for preparing anode material suitable for external cold water treatment according to claim 3, wherein the supporting solution is prepared by taking absolute ethyl alcohol, n-butanol and isopropanol as solvent, the volume ratio of absolute ethyl alcohol, n-butanol and isopropanol is 1:1:1, and then H is added into the solvent2IrCl6·6H2O、RuCl3NaF, dodecyl dimethyl betaine, SbCl3、La（NO3）3And a carbon nanodot solution, wherein H2IrCl6·6H2The concentration of O is 0.25 to 0.5mol/L, RuCl3The concentration of (A) is 0.001-0.002 mol/L, the concentration of dodecyl dimethyl betaine is 0.05-0.1 g/L, and SbCl is 0.5-1 mol/L, NaF3Has a concentration of 0.05 to 0.1mol/L, La (NO)3）3The concentration of the carbon nano-dot solution is 0.01-0.05 mol/L, and the content of the carbon nano-dot solution is as follows: and 5-15 mL of carbon nano-dot solution is contained in 100mL of solution to be loaded.
5. The treatment process suitable for external cold water treatment is characterized by comprising the following specific steps: adding a bypass between filtration and softening for electrochemical treatment, so that part of the filtered water supplement is directly softened, part of the filtered water supplement is softened after electrochemical treatment, adding a bypass between reverse osmosis and an external cold water circulating system for electrochemical treatment, namely, part of the reverse osmosis water supplement is directly treated by the external cold water circulating system, and part of the reverse osmosis water supplement is treated by the external cold water circulating system after electrochemical treatment, wherein the anode material adopted in the electrochemical treatment is the anode material prepared in the claim 4, the cathode is a conductive material, and the current density range is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
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