CN112142168B - Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method - Google Patents

Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method Download PDF

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CN112142168B
CN112142168B CN202010984888.2A CN202010984888A CN112142168B CN 112142168 B CN112142168 B CN 112142168B CN 202010984888 A CN202010984888 A CN 202010984888A CN 112142168 B CN112142168 B CN 112142168B
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cold water
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CN112142168A (en
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祝海峰
郑丰
李标俊
王林
向权舟
刘思远
陈小平
王行梁
李晓良
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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
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
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    • 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

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Abstract

The invention discloses an anode material for improving the membrane pollution of a cold water system outside a converter valve, which comprises a substrate layer, a middle layer and a catalytic oxidation layer from inside to outside, wherein the substrate layer is processed porous titanium suboxide, the middle layer is a multi-walled carbon nanotube-naphthol film, and the catalytic surface layer is Ce-doped RuS2/RuO2Composite nanoparticles. The anode material for the external cooling water system can not only remove membrane pollutants in the water, but also maintain the stability of electrochemical reaction. The invention also discloses an electrochemical method for improving the membrane pollution of the converter valve external cold water system.

Description

Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method
Technical Field
The invention belongs to the technical field of water treatment, relates to an anode material for improving the membrane pollution of a converter valve external cold water system, and also relates to an electrochemical method for improving the membrane pollution of the converter valve external cold water system.
Background
In the field of high-voltage direct-current transmission engineering, a converter valve is a core component for realizing alternating current and direct current conversion of a converter station. In the normal operation process, the converter valve bears large current and high voltage, and a large amount of heat is generated, so that a valve cooling water system is required to cool the converter valve. The efficient and reliable valve cooling water system is the key for ensuring the safe and reliable operation of the converter valve. The valve cooling water system mainly comprises an inner valve cooling water system (closed) and an outer valve cooling water system (open), and the inner valve cooling water system and the outer valve cooling water system cooperate to continuously cool the converter valve. The water cooling system outside the valve continuously cools the pipeline of the water cooling system inside the valve through the cooling tower, indirectly controls the heat dissipation of the converter valve and is vital to the safe operation of the converter valve.
The water replenishing source of the valve external cold water system comprises surface water, underground water, reclaimed water and the like. Generally, the external cold water contains more organic pollutants, the hardness of the supplemented water is higher, and the influence of the water quality conditions of a water supplementing area is larger. If the external cold water is improperly supplemented, the long-term circulating operation can increase the scaling risk of an external cold water system and influence the heat exchange efficiency of the system. At present, the treatment process for supplementing external cold water comprises the following steps: the method comprises the steps of filtering and softening water supplement, performing reverse osmosis on the water supplement, then performing an external cold water circulating system on the water supplement, generally performing softening treatment on the external cold water supplement by adopting ion exchange resin, and further performing deep purification on the softened water supplement by using a reverse osmosis system in some converter stations. The water quality condition after reverse osmosis treatment can be obviously improved, but with the long-term operation of a reverse osmosis system, the pollution and blockage phenomena of the reverse osmosis membrane can occur, so that the series problems of low water yield of the reverse osmosis system, short membrane service life and the like can be caused. The main reasons are that calcium ions, magnesium ions, macromolecular organic matters, microorganisms and the like in the water supplement block membrane pores, so that the reverse osmosis membrane is polluted, the water yield of the membrane is reduced, and even if softening treatment of the water supplement is carried out in the early stage, the pressure of a reverse osmosis system is still large. Therefore, the pollution of a reverse osmosis membrane of a cold water system outside the converter valve is relieved, and the method plays an important role in long-term stable operation of a valve cooling water system.
In the electrochemical water treatment technology, an anode is the core of the electrochemical water treatment technology, and the performance of an anode material directly influences the treatment effect of an electrochemical process. Aiming at the complex condition of the current external cold water replenishing, the development of a high-efficiency electrochemical anode material and an electrochemical treatment method suitable for controlling the pollution of a reverse osmosis membrane of an external cold water system is very important.
Disclosure of Invention
The invention aims to provide an anode material for improving membrane pollution of a cold water system outside a converter valve, which can not only remove membrane pollutants in water effectively, but also keep the stability of electrochemical reaction.
Another object of the present invention is to provide an electrochemical method for improving the membrane fouling of cold water systems outside converter valves.
The technical scheme adopted by the invention is that the anode material for improving the membrane pollution of the cold water system outside the converter valve comprises a substrate layer, a middle layer and a catalytic oxidation layer from inside to outside, the substrate layer is processed porous titanium suboxide, the middle layer is a multi-walled carbon nanotube-naphthol membrane, and the catalytic surface layer is Ce-doped RuS2/RuO2Composite nanoparticles.
The second technical scheme adopted by the invention is an electrochemical method for improving the membrane pollution of a cold water system outside a converter valve, which specifically comprises the following steps: the method is characterized in that the external cold water replenishing water sequentially enters an external cold circulation system through filtering, softening and reverse osmosis treatment, a bypass is added between the softening and the reverse osmosis for electrochemical treatment, namely, part of the softened replenishing water is directly subjected to reverse osmosis, and the other part of the softened replenishing water is subjected to the electrochemical treatment and then subjected to the reverse osmosis, the anode of the electrochemical treatment is the anode material, and the cathode is a stainless steel plate conductive material with the same area and size as the anode.
The second aspect of the present invention is also characterized in that,
the current density range during electrochemical treatment is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
The preparation method of the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a porous titanium suboxide substrate in a reduction state, namely a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film middle layer on the material A by adopting a coating method to obtain a material B;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system.
The step 1 specifically comprises the following steps: step 1.1, preparing a porous titanium suboxide substrate and cutting
Adding TiO into the mixture2Dispersing the powder in an isopropanol solution with a certain concentration, drying to obtain a mixture, then using a 3-6 wt% polyethylene oxide solution as a binder to press and form the mixture, then sintering for 24 hours in a 1100-1400K nitrogen atmosphere, then preserving heat for 3-5 hours at the temperature of 1100-1400K nitrogen atmosphere, then naturally cooling to normal temperature to prepare porous monolithic titanium dioxide, using the porous monolithic titanium dioxide as an electrode substrate, and then cutting into a required shape and size according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, performing ultrasonic treatment at room temperature for 30-180 min to perform alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the titanium suboxide substrate
Soaking the substrate treated in the step 1.2 in an 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 substrate with ultrapure water for several times to remove an oxide film, and naturally drying for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of the oxygen is 5-15%, and the pressure is not less than 0.5bar, heating to 150-350 ℃ from room temperature, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
The matrix treated by the step 1.4 is controlled at 15-30 mA-cm-2And under the current density, electrochemically reducing for 15-30 min to form a reduced porous titanium suboxide matrix which is marked as material A.
The step 2 specifically comprises the following steps: 2.1 preparation of modified multiwall carbon nanotubes
Heating and refluxing 2.0-4.0 g of multi-walled carbon nano-tube in 4mol/L HCl for 3-6H, cooling to room temperature, repeatedly washing with deionized water, performing suction filtration, drying, and adding 98% of H with the volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 10-40 min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 10-40 min, performing suction filtration again, drying in a drying box at 40-80 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 20-50 mL of ethylene glycol and 5-10 g of citric acid, stirring and esterifying for 0.5-2 hours in a water bath kettle at the water temperature of 40-80 ℃, adding 0.1-0.5% of naphthol, fully stirring to prepare a poly (ethylene citrate) oligomer, weighing 1.0-5.0 g of modified multi-wall carbon nanotube powder MWCNTs, adding the modified multi-wall carbon nanotube powder MWCNTs into the prepared poly (ethylene citrate) oligomer, alternately treating for 2-6 hours at intervals of 10-40 min by using a magnetic stirrer and an ultrasonic cleaner to obtain a uniformly dispersed suspension of the CNTMWCNTs taking the citric acid/ethylene glycol oligomer as a matrix liquid, and sealing and storing by using a preservative film;
and 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium oxide matrix material A to form a layer of film, putting the film into an oven for dry heat treatment for 15-30 min, taking out the film for cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid, keeping the drying time of the last time for 40-80 min, cooling along with the temperature of the oven, taking out the film and putting the film into a dryer, and preparing the material B with the multi-walled carbon nanotube-naphthol film intermediate layer.
The step 3 specifically comprises the following steps: step 3.1, preparation of precursor solution
Weighing 0.1-1 mmol/L ruthenium chloride trihydrate, 1-5 mmol/L thiourea and proper amount of Ce (NO)3)3Dissolving in a methanol solution, stirring and carrying out ultrasonic treatment for 15-60 min, adding 0.1-1 ml of hydrazine hydrate solution after complete dissolution, and carrying out ultrasonic treatment on the solution for 15-60 min;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 6-12 hours at 150-200 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing with ultrapure water and ethanol for 3-6 times respectively to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And annealing the material B loaded with the precursor solution for 0.5-2 h under argon-hydrogen mixed gas, wherein the annealing temperature is 400-600 ℃, the heating rate is 3-8 ℃/min, and the gas flow rate is 20-50 sccm, so as to obtain the anode material for external cold water treatment.
Ruthenium chloride trihydrate in the precursor solution: the molar ratio of Ce =100:1 to 200: 1.
During annealing, the material B loaded with the precursor solution is placed in a small magnetic boat, and is well sealed by aluminum foil paper and then placed in the middle of the tube furnace.
The proportion of hydrogen in the argon-hydrogen mixed gas is 3-6%.
The invention has the beneficial effects that:
the anode material prepared by the invention can not only remove membrane pollutants in the water with high efficiency, but also keep the stability of electrochemical reaction, and continuously and efficiently play a role in the electrochemical treatment process. Therefore, a bypass mode is adopted, the electrochemical treatment capacity is adjusted through a bypass ratio to control the concentration of active chlorine, one part of softened effluent directly enters the reverse osmosis system, the other part of the softened effluent flows through the electrochemical module in the bypass and then enters the reverse osmosis system after being pretreated by the electrochemical module, the organic matters in water are further removed through electrocatalytic oxidation by the anode material in electrochemistry, and the existing electric field effect can inactivate bacteria, so that the breeding of microorganisms in water is effectively inhibited.
Drawings
FIG. 1 is a flow chart of an electrochemical method of the present invention for ameliorating membrane fouling in a cold water system outside a converter valve;
FIG. 2 is an SEM photograph of an electrode prepared in example 1 of the present invention;
FIG. 3 is an accelerated life test analysis chart of an electrode according to example 1 of the present invention;
FIG. 4 is a surface water replenishing LC-OCD map of a converter station in embodiment 2 of the present invention;
FIG. 5 shows the main water quality index changes before and after electrochemical operation in example 2 of the present invention;
FIG. 6 is a comparative graph of a reverse osmosis membrane cleaning cycle with an electroless chemical module in example 3 of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The anode material for improving the membrane pollution of a cold water system outside a converter valve comprises a substrate layer, a middle layer and a catalytic oxidation layer from inside to outside, wherein the substrate layer is treated porous titanium suboxide, the middle layer is a multi-wall carbon nano tube-naphthol membrane, and the catalytic surface layer is Ce-doped RuS2/RuO2Composite nanoparticles.
The invention discloses an electrochemical method for improving the membrane pollution of a converter valve external cold water system, which has the flow shown in figure 1 and specifically comprises the following steps: the method comprises the steps that external cold water replenishing water sequentially enters an external cold circulation system through filtering, softening and reverse osmosis treatment, a bypass is added between softening and reverse osmosis for electrochemical treatment, namely, part of softened replenishing water is directly subjected to reverse osmosis, part of softened replenishing water is subjected to electrochemical treatment and then subjected to reverse osmosis, an anode subjected to electrochemical treatment is the prepared anode material, a cathode is a stainless steel plate conductive material with the same area and size as the anode, and the current density range during electrochemical treatment is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
The method for preparing the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a reduced porous titanium suboxide substrate, namely a material A, which specifically comprises the following steps:
step 1.1, preparing a porous titanium suboxide matrix and cutting
Adding TiO into the mixture2Dispersing the powder in an isopropanol solution with a certain concentration, drying to obtain a mixture, then using a 3-6 wt% polyethylene oxide solution as a binder to press and form the mixture, then sintering for 24 hours in a 1100-1400K nitrogen atmosphere, then preserving heat for 3-5 hours at the temperature of 1100-1400K nitrogen atmosphere, then naturally cooling to normal temperature to prepare porous monolithic titanium dioxide, using the porous monolithic titanium dioxide as an electrode substrate, and then cutting into a required shape and size according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, performing ultrasonic treatment at room temperature for 30-180 min to perform alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the Titania substrate
Soaking the substrate treated in the step 1.2 in an 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 substrate with ultrapure water for several times to remove an oxide film, and naturally drying for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of oxygen is 5-15%, the pressure is not less than 0.5bar, heating the substrate from room temperature to 150-350 ℃, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
The matrix treated by the step 1.4 is controlled at 15-30 mA-cm-2Carrying out electrochemical reduction for 15-30 min under the current density to form a reduced porous titanium dioxide substrate, and marking as a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film intermediate layer on the material A by adopting a coating method to obtain a material B, which specifically comprises the following steps:
2.1 preparation of modified multiwall carbon nanotubes
Taking 2.0-4.0 g of multi-walled carbon nano-tube at 4mol/LHeating and refluxing the HCl solution for 3-6H, cooling to room temperature, repeatedly washing and filtering the HCl solution by deionized water, drying the HCl solution, and adding 98% of H according to the volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 10-40 min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 10-40 min, performing suction filtration again, drying in a drying box at 40-80 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 20-50 mL of ethylene glycol and 5-10 g of citric acid, stirring and esterifying for 0.5-2 hours in a water bath kettle at the water temperature of 40-80 ℃, adding 0.1-0.5% of naphthol, fully stirring to prepare a poly (ethylene citrate) oligomer, weighing 1.0-5.0 g of modified multi-wall carbon nanotube powder MWCNTs, adding the modified multi-wall carbon nanotube powder MWCNTs into the prepared poly (ethylene citrate) oligomer, alternately treating for 2-6 hours at intervals of 10-40 min by using a magnetic stirrer and an ultrasonic cleaner to obtain a uniformly dispersed suspension of the CNTMWCNTs taking the citric acid/ethylene glycol oligomer as a matrix liquid, and sealing and storing by using a preservative film;
step 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium dioxide matrix material A, coating a layer of film, putting the film into an oven for dry heat treatment for 15-30 min, taking out and cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as the matrix liquid, keeping the last drying time for 40-80 min, cooling along with the furnace temperature, taking out and putting into a dryer, and preparing a material B with a multiwalled carbon nanotube-naphthol film middle layer;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system, which specifically comprises the following steps:
step 3.1, preparation of precursor solution
Weighing 0.1-1 mmol/L ruthenium chloride trihydrate, 1-5 mmol/L thiourea and proper amount of Ce (NO)3)3Dissolving in methanol solution, stirring and carrying out ultrasonic treatment for 15-60 min, adding 0.1-1 ml of hydrazine hydrate solution after complete dissolution, carrying out ultrasonic treatment for 15-60 min, and carrying out trihydrate in precursor solutionRuthenium chloride: the molar ratio of Ce =100:1 to 200: 1;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 6-12 hours at 150-200 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing with ultrapure water and ethanol for 3-6 times respectively to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, sealing the boat with an aluminum foil paper completely, placing the boat in the middle of a tube furnace, and annealing for 0.5-2 h in argon-hydrogen mixed gas at the annealing temperature of 400-600 ℃, the heating rate of 3-8 ℃/min and the gas flow rate of 20-50 sccm to obtain the anode material for external cold water treatment, wherein the proportion of hydrogen in the argon-hydrogen mixed gas is 3-6%.
The anode material prepared by the invention can realize the efficient removal or degradation of scaling ions, pollutants and the like in water, improve the stability of the electrochemical process and realize the continuous and efficient exertion of the electrode. According to the invention, the bypass is led out from the softening link and embedded into the electrochemical module, so that scale forming ions, organic matters and microorganisms in the replenishing water are removed, the pollution of a subsequent reverse osmosis membrane is reduced, the service life of the reverse osmosis system is prolonged and the treatment efficiency of the reverse osmosis system is improved.
According to the filtering process, one or more combinations of sand filtration, carbon filtration, multi-medium filtration, security filters and the like can be adopted according to specific water quality, sodium chloride is required to be added in a softening link to replace Ca and Mg ions in water so as to primarily reduce the hardness, a large amount of chloride ions exist in softened effluent, active chlorine can be generated under the electrochemical action, the reverse osmosis membrane can be damaged by too much active chlorine, and microorganisms on the reverse osmosis membrane can not be inhibited by too little active chlorine. In electrochemical reactions, there are three reactions: (1) forming hydroxide precipitate in the cathode alkaline region by the scaling ions of Ca, Mg and the like in the water; (2) the anode material in the electrochemical module further removes organic matters in the water through electrocatalytic oxidation; (3) the existing electric field can inactivate bacteria and effectively inhibit the breeding of microorganisms in water. The comprehensive effects of the three components can relieve the pollution of the reverse osmosis membrane.
Example 1
The preparation method of the anode material comprises the following specific steps:
step 1 preparation of novel anode:
1. pretreating the titanium substrate to obtain a reduced porous titanium suboxide substrate
1.1 preparing a porous titanium dioxide matrix and cutting:
firstly, pre-treating the TiO2Dispersing the powder in isopropanol solution with certain concentration to reduce TiO2The capillary force of the powder is then dried. The mixture was then press-formed using about 5wt% polyethylene oxide solution as a binder. And then sintered for 24 hours in a nitrogen atmosphere of 1323K. Then the mixture is kept at the temperature of 1323K nitrogen atmosphere for 4 hours to the normal temperature. A porous monolithic titanium suboxide is produced. Cutting the electrode substrate as an electrode substrate into a required shape and size according to requirements;
1.2 degreasing of titanium suboxide substrate:
putting the matrix treated in the step 1.1 into NaOH with the mass fraction of 3%, performing ultrasonic treatment at room temperature for a certain time for alkali treatment, controlling the ultrasonic time at 60min, washing the soaked matrix with pure water for several times, and naturally airing for later use;
1.3 etching of titanium suboxide substrate:
soaking the substrate treated in the step 1.2 in an oxalic acid solution with the mass fraction of 5% for etching, keeping the temperature at 90 ℃ during soaking, soaking for 60min, cleaning the soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4 heat treatment of titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the oxygen concentration is 10% and the pressure is more than or equal to 0.5bar, heating the substrate to 200 ℃ from room temperature, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of titanium suboxide substrate:
subjecting the substrate treated in step 1.4 to a treatment at 20mA cm-2Carrying out electrochemical reduction for 30min under the current density to form a high-conductivity reduced porous titanium suboxide matrix material A;
2. forming a middle layer of a multi-walled carbon nano-tube-naphthol film on the material A by adopting a coating method
2.1 preparation of modified Multi-walled carbon nanotubes
Heating and refluxing multi-walled carbon nanotubes 3.0g in HCl 4mol/L for 4H, cooling to room temperature, repeatedly washing with deionized water, vacuum-filtering, drying, and adding 98% H at a volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 20min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 20min, performing suction filtration again, drying in a drying box at 60 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs.
2.2 preparation of intermediate layer of multiwalled carbon nanotube-Naphthol film
30 mL of ethylene glycol and 8.4 g of citric acid are mixed, stirred and esterified for 1 hour at 70 ℃ in a water bath kettle, and then 0.1% of naphthol is added and stirred fully. 2.0g of activated MWCNTs was weighed out and added to the prepared poly (ethylene citrate) oligomer. Alternately treating for 3 hours by a magnetic stirrer and an ultrasonic cleaner at intervals of 20min to obtain MWCNTs uniformly dispersed suspension taking citric acid/glycol ester oligomers as matrix liquid, and sealing and storing by a preservative film.
And 2.3, setting the temperature of the oven to 160 ℃, cleaning a watch glass, a crucible, the base material A and the like, and then putting the washed watch glass, the crucible, the base material A and the like into the oven for drying. Dipping a small amount of solution by using a watercolor brush, uniformly coating a layer of film on the reduced porous titanium oxide substrate material A, and putting the film into an oven for dry heat treatment for 15-30 min. After being taken out and cooled, the coating with the ester solution is repeated and dried. And (3) the last drying lasts for 60min, and the material A is taken out after being cooled along with the furnace temperature and is placed into a dryer to prepare a material B attached with a multi-walled carbon nano tube-naphthol film middle layer.
3. Preparation of catalytically active coatings
3.1 preparation of precursor solution
0.1mmol/L of ruthenium chloride trihydrate, 1mmol/L of thiourea and an appropriate amount of Ce (NO)3)3Dissolved in a methanol solution, wherein ruthenium chloride trihydrate: and (3) stirring and ultrasonically treating the rare earth element Ce for 300min until the rare earth element Ce is completely dissolved, adding 0.5ml of hydrazine hydrate solution, and ultrasonically treating the solution for 30 min.
3.2 preparation of active coatings by hydrothermal method
And (3) obliquely placing the material B in a polytetrafluoroethylene inner container, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, and placing in the middle of an oven. And (3) reacting for 6 hours at 150 ℃, naturally cooling after the reaction is finished, taking out the material B, and rinsing with ultrapure water and ethanol for 3-6 times respectively.
3.3 annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, and placing the material B in the middle of the tube furnace after the material B is completely covered by an aluminum foil paper to prevent uneven heating during annealing. The sample is annealed for 0.5h under argon-hydrogen mixed gas (the proportion of hydrogen is 3%), the annealing temperature is 400 ℃, the heating rate is 3 ℃/min, and the gas flow rate is 20 sccm. Thus, the anode material C suitable for external cold water treatment is obtained.
As can be seen from FIG. 2, the prepared electrode has a rough surface and a large specific surface area, which is beneficial to increasing the number of electrode reaction sites. The prepared novel electrode and the commonly used Ti/RuO2The electrodes are respectively arranged at 3 mol/L H2SO4The enhanced life test is carried out in the solution, the temperature of the solution is controlled at 25 ℃, and the current density range is controlled at 500 mA/cm2The resulting voltage-time curve is shown in fig. 3. The voltage-time curves of both electrodes have a voltage stabilization period, then a voltage slow rising period, and finally a voltage accelerated rising until the final voltage reaches 10V. Ti/RuO2The accelerated life of the electrode is 505.5 hours, while the accelerated life of the prepared electrode can be prolonged to 875.0 hours, which is 1.73 times of that of an unmodified electrode, and the stability is greatly improved.
Example 2
The preparation method of the anode material comprises the following specific steps:
step 1 preparation of novel anode:
1. pretreating the titanium substrate to obtain a reduced porous titanium suboxide substrate
1.1 preparing a porous titanium protoxide substrate and cutting:
firstly, pre-treating the TiO2Dispersing the powder in isopropanol solution with certain concentration to reduce TiO2Drying the powder under the action of capillary force. The mixture was then press-formed using about 5wt% polyethylene oxide solution as a binder. And then sintered for 24 hours in a nitrogen atmosphere of 1323K. Then the mixture is kept at the temperature of 1323K nitrogen atmosphere for 4 hours to the normal temperature. A porous monolithic titanium suboxide is produced. Cutting the electrode substrate as an electrode substrate into a required shape and size according to requirements;
1.2 degreasing of titanium suboxide substrate:
putting the matrix treated in the step 1.1 into NaOH with the mass fraction of 5%, performing ultrasonic treatment at room temperature for a certain time for alkali treatment, controlling the ultrasonic time to be 90 min, washing the soaked matrix with pure water for a plurality of times, and naturally airing for later use;
1.3 etching of titanium suboxide substrate:
soaking the substrate treated in the step 1.2 in an oxalic acid solution with the mass fraction of 5% for etching, keeping the soaking temperature at 95 ℃ for 120min, cleaning the soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4 heat treatment of titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of oxygen is 10% and the pressure is more than or equal to 0.5bar, heating to 250 ℃ from room temperature, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of titanium suboxide substrate:
subjecting the substrate treated in step 1.4 to a treatment at 25mA cm-2Carrying out electrochemical reduction for 25min under the current density to form a high-conductivity reduced-state porous titanium dioxide base material A;
2. forming a multi-walled carbon nano-tube-naphthol film interlayer on the material A by adopting a coating method
2.1 preparation of modified Multi-walled carbon nanotubes
Heating and refluxing multi-walled carbon nanotubes 3.0g in HCl 4mol/L for 4H, cooling to room temperature, repeatedly washing with deionized water, vacuum-filtering, drying, and adding 98% H at a volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 20min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 20min, performing suction filtration again, drying in a drying box at 60 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs.
2.2 preparation of intermediate layer of multiwalled carbon nanotube-Naphthol film
30 mL of ethylene glycol and 8.4 g of citric acid are mixed, stirred and esterified for 1 hour at 70 ℃ in a water bath kettle, and then 0.1% of naphthol is added and stirred fully. 2.0g of activated MWCNTs was weighed into the prepared poly (ethylene citrate) oligomer. Treating with magnetic stirrer and ultrasonic cleaner at 20min interval for 3 hr to obtain MWCNTs suspension with citric acid/glycol oligomer as matrix liquid, and sealing with preservative film.
And 2.3, setting the temperature of the oven to 160 ℃, cleaning a watch glass, a crucible, the base material A and the like, and then putting the washed watch glass, the crucible, the base material A and the like into the oven for drying. Dipping a small amount of solution by using a watercolor brush, uniformly coating a layer of film on the reduced porous titanium oxide substrate material A, and putting the film into an oven for dry heat treatment for 15-30 min. After being taken out and cooled, the coating with the ester solution is repeated and dried. And (3) the last drying lasts for 60min, and the material A is taken out after being cooled along with the furnace temperature and is placed into a dryer to prepare a material B attached with a multi-walled carbon nano tube-naphthol film middle layer.
3. Preparation of the catalytically active coating
3.1 preparation of precursor solution
0.5mmol/L of ruthenium chloride trihydrate, 3mmol/L of thiourea and an appropriate amount of Ce (NO)3)3Dissolved in methanol solution, wherein ruthenium chloride trihydrate: the rare earth element Ce molar ratio is =100:1, stirring and ultrasonic treatment are carried out for 45min, 0.5ml of hydrate is added after complete dissolutionHydrazine solution, and then the solution is subjected to ultrasonic treatment for 45 min.
3.2 preparation of active coatings by hydrothermal method
And (3) obliquely placing the material B in a polytetrafluoroethylene inner container, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, and placing in the middle of an oven. Reacting for 9 hours at 180 ℃, naturally cooling after the reaction is finished, taking out the material B, and rinsing with ultrapure water and ethanol for 5 times respectively.
3.3 annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, and placing the material B in the middle of the tube furnace after the material B is completely sealed by aluminum foil paper to prevent uneven heating during annealing. The sample is annealed for 1h under argon-hydrogen mixed gas (the proportion of hydrogen is 5%), the annealing temperature is 500 ℃, the heating rate is 5 ℃/min, and the gas flow rate is 30 sccm. Thus, the anode material C suitable for external cold water treatment is obtained.
The electrode prepared by the method is used as an anode of an electrochemical module, the electrochemical module is used for preprocessing the surface water replenishing water of a certain converter station, an LC-OCD (liquid chromatography-optical stability detector) diagram of the surface water replenishing water of the certain converter station is shown in figure 4, and as can be seen from the LC-OCD diagram of figure 4, the proportion of macromolecular organic substances (Biopolymers, Humics and the like) in the replenishing water is large (the total proportion is 67.2%), the water quality easily causes reverse osmosis membrane pollution, and in addition, the replenishing water also contains a large amount of calcium and magnesium ions. The change in the main indicators before and after the electrochemical treatment after the introduction of the electrochemical module is shown in fig. 5. The average values of the total hardness, the hardness and the alkalinity of the softened effluent are respectively 58.5mg/L, 31.3mg/L and 24.5mg/L, after electrochemical pretreatment, the average values are respectively reduced to 26.1mg/L, 13.6mg/L and 10.7mg/L, and the removal rates are respectively 55.38%, 56.55% and 56.32%. In addition, the electrochemical treatment has a removal rate of 73.2% for soluble organic carbon DOC in the external cold water and a removal rate of 90% or more for microorganisms such as bacteria and algae. The electrochemical treatment not only effectively removes calcium and magnesium ions in the water, but also removes organic matters and microorganisms in the water, and lightens the working pressure of a subsequent reverse osmosis system. And the membrane pollution of the reverse osmosis system is relieved to a certain extent.
Example 3
The preparation method of the anode material comprises the following specific steps:
step 1 preparation of a novel anode:
1. pretreating the titanium substrate to obtain a reduced porous titanium suboxide substrate
1.1 preparing a porous titanium dioxide matrix and cutting:
firstly, pre-treating the TiO2Dispersing the powder in isopropanol solution with certain concentration to reduce TiO2Drying the powder under the action of capillary force. The mixture was then press-formed using about 5wt% polyethylene oxide solution as a binder. And then sintered for 24 hours in a nitrogen atmosphere of 1323K. Then the mixture is kept at the temperature of 1323K nitrogen atmosphere for 4 hours to the normal temperature. A porous monolithic titanium suboxide is produced. Cutting the electrode substrate as an electrode substrate into a required shape and size according to requirements;
1.2 degreasing of titanium suboxide substrate:
putting the matrix treated in the step 1.1 into NaOH with the mass fraction of 15%, performing ultrasonic treatment at room temperature for a certain time for alkali treatment, controlling the ultrasonic time to be 30-180 min, washing the soaked matrix with pure water for several times, and naturally airing for later use;
1.3 etching of the titanium suboxide substrate:
soaking the substrate treated in the step 1.2 in an oxalic acid solution with the mass fraction of 15% for etching, keeping the temperature at 99 ℃ during soaking, soaking for 180min, cleaning the soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4 heat treatment of titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the oxygen concentration is 15% and the pressure is more than or equal to 0.5bar, heating the substrate from room temperature to 350 ℃, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of titanium suboxide substrate:
subjecting the substrate treated in step 1.4 to a treatment at 30mA cm-2Carrying out electrochemical reduction for 30min under the current density to form a high-conductivity reduced porous titanium suboxide matrix material A;
2. forming a multi-walled carbon nano-tube-naphthol film interlayer on the material A by adopting a coating method
2.1 preparation of modified Multi-walled carbon nanotubes
Heating and refluxing multi-walled carbon nanotubes 3.0g in HCl 4mol/L for 4H, cooling to room temperature, repeatedly washing with deionized water, vacuum-filtering, drying, and adding 98% H at a volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 20min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 20min, performing suction filtration again, drying in a drying box at 60 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs.
2.2 preparation of intermediate layer of multiwalled carbon nanotube-Naphthol film
30 mL of ethylene glycol and 8.4 g of citric acid are mixed, stirred and esterified for 1 hour at 70 ℃ in a water bath kettle, and then 0.1% of naphthol is added and stirred fully. 2.0g of activated MWCNTs was weighed into the prepared poly (ethylene citrate) oligomer. Treating with magnetic stirrer and ultrasonic cleaner at 20min interval for 3 hr to obtain MWCNTs suspension with citric acid/glycol oligomer as matrix liquid, and sealing with preservative film.
And 2.3, setting the temperature of the oven to 160 ℃, cleaning a watch glass, a crucible, the base material A and the like, and then putting the washed watch glass, the crucible, the base material A and the like into the oven for drying. Dipping a small amount of solution by using a watercolor painting brush, uniformly coating a layer of film on the reduced porous titanium oxide substrate material A, and putting the film into an oven for dry heat treatment for 15-30 min. After being taken out and cooled, the coating with the ester solution is repeated and dried. And (3) the last drying time lasts for 60min, the material A is cooled along with the furnace temperature and then taken out and put into a dryer, and the material B attached with the multiwalled carbon nanotube-naphthol film middle layer is prepared.
3. Preparation of catalytically active coatings
3.1 preparation of precursor solution
1mmol/L of ruthenium chloride trihydrate, 5mmol/L of thiourea and a proper amount of Ce (NO)3)3Dissolved in a methanol solution, wherein ruthenium chloride trihydrate: the rare earth element Ce molar ratio =100:1, stirring and ultrasonic treating for 60min, adding 1ml hydrazine hydrate solution after completely dissolving, and adding the solutionAnd (5) carrying out ultrasonic treatment for 60 min.
3.2 preparation of active coatings by hydrothermal method
And (3) obliquely placing the material B in a polytetrafluoroethylene inner container, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, and placing in the middle of an oven. Reacting at 200 deg.C for 12 hr, naturally cooling, taking out material B, and rinsing with ultrapure water and ethanol respectively for 6 times.
3.3 annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, and placing the material B in the middle of the tube furnace after the material B is completely sealed by aluminum foil paper to prevent uneven heating during annealing. The sample is annealed for 2h under argon-hydrogen mixed gas (the proportion of hydrogen is 6 percent), the annealing temperature is 600 ℃, the heating rate is 8 ℃/min, and the gas flow rate is 50 sccm. Thus, the anode material C suitable for external cold water treatment is obtained.
Under the condition of the same water quality, the cleaning period change of the reverse osmosis membrane is compared with that under the condition of no electrochemical module. In the electrochemical reaction, the prepared anode material is used as an anode, stainless steel is used as a cathode, 5 groups are arranged in parallel, the distance between polar plates is 2 cm, and the current density is 8 mA/cm2The water treatment amount is 600L/h, the electrochemical treatment time is 90 min, the pH value is 8.5, and the treatment temperature is 25 ℃. Electrochemical pretreatment further removed impurities from the water, the membrane life increased, and the cleaning interval decreased, as shown in figure 6.
Example 4
The preparation method of the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a reduced porous titanium suboxide substrate, namely a material A, which specifically comprises the following steps:
step 1.1, preparing a porous titanium suboxide substrate and cutting
Adding TiO into the mixture2Dispersing the powder in isopropanol solution with certain concentration, drying to obtain mixture, pressing with 3wt% polyethylene oxide solution as binder, sintering at 1100K under nitrogen atmosphere for 24 hr, maintaining at 1100K under nitrogen atmosphere for 3 hr, and naturally dryingCooling to normal temperature to prepare porous monolithic titanium dioxide, taking the porous monolithic titanium dioxide as an electrode substrate, and cutting the electrode substrate into required shapes and sizes according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate treated in the step 1.1 into NaOH with the mass fraction of 3%, performing ultrasonic treatment for 30min at room temperature for alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the titanium suboxide substrate
Soaking the 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 soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of oxygen is 5% and the pressure is more than or equal to 0.5bar, heating the substrate from room temperature to 150 ℃, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
Subjecting the substrate treated in step 1.4 to a treatment at 15mA cm-2Carrying out electrochemical reduction for 15min under the current density to form a reduced porous titanium dioxide substrate which is marked as a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film middle layer on the material A by adopting a coating method to obtain a material B, which specifically comprises the following steps:
2.1 preparation of modified multiwall carbon nanotubes
Heating and refluxing 2.0g of multi-walled carbon nano-tube in 4mol/L HCl for 3H, cooling to room temperature, repeatedly washing with deionized water, filtering, drying, and adding 98% of H with volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 10min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 10min, performing suction filtration, drying in a drying box at 40 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 20mL of ethylene glycol and 5g of citric acid, stirring and esterifying for 0.5 hour at the water temperature of 40 ℃ in a water bath kettle, adding 0.1% of naphthol, fully stirring to prepare a polyethylene citrate oligomer, weighing 1.0g of modified multi-wall carbon nanotube powder MWCNTs, adding the modified multi-wall carbon nanotube powder MWCNTs into the prepared polyethylene citrate oligomer, alternately treating for 2 hours at intervals of 10min by using a magnetic stirrer and an ultrasonic cleaner to obtain a suspension with uniformly dispersed MWCNTs by using citric acid/ethylene glycol ester oligomer as a matrix liquid, and sealing and storing by using a preservative film;
step 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium dioxide matrix material A, coating a layer of film, putting the film into an oven for dry heat treatment for 15min, taking out and cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid, keeping the last drying time for 40min, cooling along with the oven temperature, taking out and putting into a dryer, and preparing a material B with a carbon nanotube-naphthol film middle layer;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system, which specifically comprises the following steps:
step 3.1, preparation of precursor solution
0.1mmol/L of ruthenium chloride trihydrate, 1mmol/L of thiourea and an appropriate amount of Ce (NO)3)3Dissolving in methanol solution, stirring and ultrasonic treating for 15min, adding 0.1ml hydrazine hydrate solution after complete dissolution, and then ultrasonic treating the solution for 15min, wherein the content of ruthenium chloride trihydrate in the precursor solution: ce molar ratio =100: 1;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 6 hours at 150 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing with ultrapure water and ethanol for 3 times respectively to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, sealing the boat with aluminum foil paper, placing the boat in the middle of a tube furnace, and annealing for 0.5h under argon-hydrogen mixed gas at the annealing temperature of 400 ℃, the heating rate of 3 ℃/min and the gas flow rate of 20sccm to obtain the anode material for external cold water treatment, wherein the hydrogen proportion in the argon-hydrogen mixed gas is 3%.
Example 5
The preparation method of the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a reduced porous titanium suboxide substrate, namely a material A, which specifically comprises the following steps:
step 1.1, preparing a porous titanium suboxide substrate and cutting
Mixing TiO with2Dispersing the powder in isopropanol solution with certain concentration, drying to obtain a mixture, then using 6wt% of polyethylene oxide solution as a binder to press and form the mixture, sintering for 24 hours in 1400K nitrogen atmosphere, then keeping the temperature for 5 hours at 1400K nitrogen atmosphere, naturally cooling to normal temperature to prepare porous monolithic titanium suboxide, using the porous monolithic titanium suboxide as an electrode substrate, and then cutting into required shapes and sizes according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate processed in the step 1.1 into NaOH with the mass fraction of 15%, performing ultrasonic treatment for 180min at room temperature for alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the titanium suboxide substrate
Soaking the substrate treated in the step 1.2 in an oxalic acid solution with the mass fraction of 15% for etching, keeping the temperature at 99 ℃ during soaking, soaking for 180min, cleaning the soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of oxygen is 15% and the pressure is more than or equal to 0.5bar, heating from room temperature to 350 ℃, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
Subjecting the substrate treated in step 1.4 to a treatment at 30mA cm-2Electrochemically reducing for 30min under the current density to form a reduced porous titanium suboxide matrix which is marked as a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film middle layer on the material A by adopting a coating method to obtain a material B, which specifically comprises the following steps:
2.1 preparation of modified Multi-walled carbon nanotubes
Heating and refluxing 4.0g of multi-walled carbon nano-tube in 4mol/L HCl for 6H, cooling to room temperature, repeatedly washing with deionized water, filtering, drying, and adding 98% of H with volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 40min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 40min, performing suction filtration again, drying in a drying box at 80 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 50mL of ethylene glycol and 10g of citric acid, stirring and esterifying for 2 hours at the water temperature of 80 ℃ in a water bath kettle, adding 0.5% of naphthol, fully stirring to prepare a poly (ethylene citrate) oligomer, weighing 5.0g of modified multi-wall carbon nanotube powder MWCNTs, adding the modified multi-wall carbon nanotube powder MWCNTs into the prepared poly (ethylene citrate) oligomer, alternately treating for 6 hours at 40min intervals by using a magnetic stirrer and an ultrasonic cleaner to obtain a suspension with uniformly dispersed MWCNTs and using a citric acid/ethylene glycol ester oligomer as a matrix liquid, and sealing and storing by using a preservative film;
step 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium dioxide matrix material A, coating a layer of film, putting the film into an oven for dry heat treatment for 30min, taking out and cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid, keeping the last drying time for 80min, cooling along with the oven temperature, taking out and putting into a dryer, and preparing a material B with a carbon nanotube-naphthol film middle layer;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system, which specifically comprises the following steps:
step 3.1, preparation of precursor solution
1mmol/L of ruthenium chloride trihydrate, 5mmol/L of thiourea and a proper amount of Ce (NO)3)3Dissolving in a methanol solution, stirring and ultrasonically treating for 60min, adding 0.1-1 ml of hydrazine hydrate solution after completely dissolving, and ultrasonically treating the solution for 60min to obtain a precursor solution containing ruthenium chloride trihydrate: ce molar ratio =200: 1;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 12 hours at 200 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing respectively for 6 times by using ultrapure water and ethanol to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, sealing the small magnetic boat with aluminum foil paper, placing the small magnetic boat in the middle of a tube furnace, and annealing for 2 hours in argon-hydrogen mixed gas at the annealing temperature of 600 ℃, the heating rate of 8 ℃/min and the gas flow rate of 50sccm to obtain the anode material for external cold water treatment, wherein the hydrogen proportion in the argon-hydrogen mixed gas is 6%.
Example 6
The preparation method of the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a reduced porous titanium suboxide substrate, namely a material A, which specifically comprises the following steps:
step 1.1, preparing a porous titanium suboxide matrix and cutting
Adding TiO into the mixture2Dispersing the powder in isopropanol solution with certain concentration, and drying to obtain the final productAfter the mixture is mixed, 5wt% of polyethylene oxide solution is used as a binder to press and form the mixture, then the mixture is sintered for 24 hours in 1300K nitrogen atmosphere, then the mixture is kept at the temperature of 1300K nitrogen atmosphere for 4 hours and then is naturally cooled to normal temperature to prepare porous monolithic titanium suboxide, the porous monolithic titanium suboxide is used as an electrode substrate, and then the porous monolithic titanium suboxide is cut into required shapes and sizes according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate treated in the step 1.1 into NaOH with the mass fraction of 10%, performing ultrasonic treatment at room temperature for 120min to perform alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the Titania substrate
Soaking the substrate treated in the step 1.2 in an oxalic acid solution with the mass fraction of 10% for etching, keeping the soaking temperature at 95 ℃ for 120min, cleaning the soaked substrate with ultrapure water for several times to remove an oxide film, and naturally airing for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the oxygen concentration is 10% and the pressure is more than or equal to 0.5bar, heating the substrate to 200 ℃ from room temperature, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
Subjecting the substrate treated in step 1.4 to a treatment at 20mA cm-2Carrying out electrochemical reduction for 20min under the current density to form a reduced porous titanium dioxide substrate which is marked as a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film middle layer on the material A by adopting a coating method to obtain a material B, which specifically comprises the following steps:
2.1 preparation of modified multiwall carbon nanotubes
Taking 3.0g of multi-wall carbon nano-tube in 4mol
Figure 886685DEST_PATH_IMAGE002
Heating and refluxing in HCl for 4h, cooling to room temperature, repeatedly washing with deionized water, vacuum filtering, and dryingThen 98% of H in a volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 25min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 25n, performing suction filtration again, drying in a 60-dry box, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 40mL of ethylene glycol and 5-10 g of citric acid, stirring and esterifying for 1.5 hours in a water bath kettle at the water temperature of 60 ℃, adding 0.3% of naphthol, fully stirring to prepare a polyethylene citrate oligomer, weighing 3g of modified multi-wall carbon nanotube powder MWCNTs, adding the MWCNTs into the prepared polyethylene citrate oligomer, alternately treating for 5 hours at intervals of 20min by using a magnetic stirrer and an ultrasonic cleaner to obtain a suspension with uniformly dispersed MWCNTs by using citric acid/ethylene glycol oligomer as a matrix liquid, and sealing and storing by using a preservative film;
step 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium dioxide matrix material A, coating a layer of film, putting the film into an oven for dry heat treatment for 20min, taking out and cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid, keeping the last drying time for 60min, cooling along with the oven temperature, taking out and putting into a dryer, and preparing a material B with a carbon nanotube-naphthol film middle layer;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system, which specifically comprises the following steps:
step 3.1, preparation of precursor solution
0.5mmol/L of ruthenium chloride trihydrate, 3mmol/L of thiourea and an appropriate amount of Ce (NO)3)3Dissolving in methanol solution, stirring and ultrasonic treating for 40min, adding 0.6ml hydrazine hydrate solution after complete dissolution, and then ultrasonic treating the solution for 40min, wherein the content of ruthenium chloride trihydrate in the precursor solution: ce molar ratio =150: 1;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 8 hours at 180 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing with ultrapure water and ethanol for 5 times respectively to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And placing the material B loaded with the precursor solution in a small magnetic boat, sealing the boat with aluminum foil paper, placing the boat in the middle of a tube furnace, and annealing for 1.5h under argon-hydrogen mixed gas, wherein the annealing temperature is 500 ℃, the heating rate is 5 ℃/min, and the gas flow rate is 30sccm, so as to obtain the anode material for external cold water treatment, wherein the hydrogen proportion in the argon-hydrogen mixed gas is 5%.

Claims (9)

1. The electrochemical method for improving the membrane pollution of the converter valve external cold water system is characterized by comprising the following specific steps: the external cold water replenishing water enters an external cold circulation system through filtering, softening and reverse osmosis treatment in sequence, a bypass is added between softening and reverse osmosis for electrochemical treatment, namely, part of the softened replenishing water is directly subjected to reverse osmosis, and the other part of the softened replenishing water is subjected to reverse osmosis after electrochemical treatment, an anode of the electrochemical treatment is respectively provided with a substrate layer, a middle layer and a catalytic oxidation layer from inside to outside, the substrate layer is treated porous titanium suboxide, the middle layer is a multiwalled carbon nanotube-naphthol film, and the catalytic surface layer is Ce-doped RuS2/RuO2The cathode is a stainless steel plate conductive material with the same area size as the anode.
2. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 1, wherein the current density range during electrochemical treatment is 1-20 mA/cm2The pH range is 6-9, and the temperature range is 15-45 ℃.
3. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 1, wherein the preparation method of the anode material is implemented according to the following steps:
step 1, pretreating a titanium suboxide substrate to obtain a porous titanium suboxide substrate in a reduction state, namely a material A;
step 2, forming a multi-walled carbon nanotube-naphthol film middle layer on the material A by adopting a coating method to obtain a material B;
and 3, loading the precursor solution on the material B by a hydrothermal method to obtain the anode material for the external cooling water system.
4. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 3, wherein the step 1 is specifically as follows:
step 1.1, preparing a porous titanium suboxide substrate and cutting
Adding TiO into the mixture2Dispersing the powder in an isopropanol solution with a certain concentration, drying to obtain a mixture, then using a 3-6 wt% polyethylene oxide solution as a binder to press and form the mixture, then sintering for 24 hours in a 1100-1400K nitrogen atmosphere, then preserving heat for 3-5 hours at the temperature of 1100-1400K nitrogen atmosphere, then naturally cooling to normal temperature to prepare porous monolithic titanium dioxide, using the porous monolithic titanium dioxide as an electrode substrate, and then cutting into a required shape and size according to requirements;
step 1.2 degreasing of titanium suboxide substrate
Putting the electrode substrate treated in the step 1.1 into NaOH with the mass fraction of 3-15%, performing ultrasonic treatment at room temperature for 30-180 min to perform alkali treatment, washing the soaked substrate with pure water for several times, and naturally airing for later use;
step 1.3, etching of the titanium suboxide substrate
Soaking the substrate treated in the step 1.2 in an 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 substrate with ultrapure water for several times to remove an oxide film, and naturally drying for later use;
1.4, carrying out heat treatment on the titanium oxide substrate:
placing the substrate treated in the step 1.3 in a pressure environment consisting of oxygen and nitrogen, wherein the concentration of oxygen is 5-15%, the pressure is not less than 0.5bar, heating the substrate from room temperature to 150-350 ℃, and then carrying out heat treatment for 30 min;
1.5 electrochemical treatment of Titania substrates
The matrix treated by the step 1.4 is controlled at 15-30 mA-cm-2And under the current density, electrochemically reducing for 15-30 min to form a reduced porous titanium suboxide matrix which is marked as material A.
5. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 4, wherein the step 2 is specifically:
2.1 preparation of modified multiwall carbon nanotubes
Heating and refluxing 2.0-4.0 g of multi-walled carbon nano-tube in 4mol/L HCl for 3-6H, cooling to room temperature, repeatedly washing with deionized water, performing suction filtration, drying, and adding 98% of H in a volume ratio of 3:12SO4And HNO3Heating and refluxing the mixed solution for 10-40 min, repeatedly washing with deionized water, performing suction filtration until the pH value is neutral, performing ultrasonic treatment for 10-40 min, performing suction filtration again, drying in a drying box at 40-80 ℃, and grinding to obtain modified multi-wall carbon nanotube powder MWCNTs;
step 2.2 preparation of intermediate layer of multiwalled carbon nanotube-naphthol film
Mixing 20-50 mL of ethylene glycol and 5-10 g of citric acid, stirring and esterifying for 0.5-2 hours in a water bath kettle at the water temperature of 40-80 ℃, adding 0.1-0.5% of naphthol, fully stirring to prepare a poly (ethylene citrate) oligomer, weighing 1.0-5.0 g of modified multi-wall carbon nanotube powder MWCNTs, adding the modified multi-wall carbon nanotube powder MWCNTs into the prepared poly (ethylene citrate) oligomer, alternately treating for 2-6 hours at intervals of 10-40 min by using a magnetic stirrer and an ultrasonic cleaner to obtain a uniformly dispersed suspension of the CNTMWCNTs taking the citric acid/ethylene glycol oligomer as a matrix liquid, and sealing and storing by using a preservative film;
and 2.3, uniformly coating the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as a matrix liquid on a reduced porous titanium dioxide matrix material A, coating a layer of film, putting the film into an oven for dry heat treatment for 15-30 min, taking out and cooling, repeatedly coating and drying the uniformly dispersed suspension of MWCNTs with citric acid/glycol ester oligomers as the matrix liquid, keeping the last drying time for 40-80 min, cooling along with the furnace temperature, taking out and putting into a dryer, and preparing a material B with a multiwalled carbon nanotube-naphthol film middle layer.
6. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 5, wherein the step 3 is specifically as follows:
step 3.1, preparation of precursor solution
Weighing 0.1-1 mmol/L ruthenium chloride trihydrate, 1-5 mmol/L thiourea and proper amount of Ce (NO)3)3Dissolving in a methanol solution, stirring and carrying out ultrasonic treatment for 15-60 min, adding 0.1-1 ml of hydrazine hydrate solution after complete dissolution, and carrying out ultrasonic treatment on the solution for 15-60 min;
step 3.2, preparing the active coating by a hydrothermal method
Placing the material B in a polytetrafluoroethylene inner container in an inclined manner, transferring the prepared precursor solution, sealing, placing into a stainless steel reaction kettle, screwing, placing in a drying oven, reacting for 6-12 hours at 150-200 ℃, taking out the material B after the reaction is finished and naturally cooling, and rinsing with ultrapure water and ethanol for 3-6 times respectively to obtain the material B loaded with the precursor solution;
step 3.3, annealing treatment
And annealing the material B loaded with the precursor solution for 0.5-2 h under argon-hydrogen mixed gas, wherein the annealing temperature is 400-600 ℃, the heating rate is 3-8 ℃/min, and the gas flow rate is 20-50 sccm, so as to obtain the anode material for external cold water treatment.
7. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 6, wherein the ratio of ruthenium chloride trihydrate: the molar ratio of Ce =100:1 to 200: 1.
8. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve as claimed in claim 6, wherein during the annealing, the material B loaded with the precursor solution is placed in a small magnetic boat, and is placed in the middle of the tube furnace after being sealed completely by aluminum foil paper.
9. The electrochemical method for improving the membrane pollution of the cold water system outside the converter valve according to claim 6, wherein the proportion of hydrogen in the argon-hydrogen mixed gas is 3-6%.
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