CN113800606B - Coating titanium anode for treatment of circulating cooling water, preparation method and application - Google Patents

Coating titanium anode for treatment of circulating cooling water, preparation method and application Download PDF

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CN113800606B
CN113800606B CN202110999012.XA CN202110999012A CN113800606B CN 113800606 B CN113800606 B CN 113800606B CN 202110999012 A CN202110999012 A CN 202110999012A CN 113800606 B CN113800606 B CN 113800606B
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coating
tio
titanium
ruo
iro
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CN113800606A (en
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庞海丽
周利君
王建坤
冯庆
贾波
杨莹
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Xidian University
Xian Taijin Industrial Electrochemical Technology Co Ltd
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Xian Taijin Industrial Electrochemical Technology Co Ltd
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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
    • C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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

Abstract

The invention belongs to the technical field of anode materials in electrochemical industry, and discloses a coating titanium anode for circulating cooling water treatment, a preparation method and application thereof, wherein the coating titanium anode for circulating cooling water treatment is sequentially provided with a titanium substrate, an intermediate layer, a transition layer and a surface active layer; the intermediate layer is TiC; the transition layer is TiO2‑Co3O4-C; the surface active layer is made of TiO2、RuO2、IrO2、SnO2、CeO2、Co3O4And C. The titanium anode prepared by the invention has low tank pressure and low power consumption in the process of treating circulating cooling water. The titanium anode prepared by the method reduces the loading amount of noble metal and effectively controls the electrode cost. The potential difference of the oxygen and the chlorine of the titanium anode prepared by the method is more than 200mV, so that the dechlorination efficiency in the electrolytic process and the effective chlorine content in the electrolyte are improved, and the service life of the electrode is also prolonged.

Description

Coating titanium anode for treatment of circulating cooling water, preparation method and application
Technical Field
The invention belongs to the technical field of anode materials in the electrochemical industry, and particularly relates to a coated titanium anode for circulating cooling water treatment, a preparation method and application.
Background
At present: with the rapid development of economy, the water shortage phenomenon in China is more and more prominent, and especially the problem is further excited by the increasing trend of the demand of industrial water. The circulating cooling water is a large item of industrial water and is widely applied to various modern industrial productions of power plants, textiles, metallurgy, heating furnaces, central air-conditioning systems and the like. However, circulating water has serious problems such as corrosion, microorganism slime, scaling and the like, and particularly, the concentration multiple is increased after the circulating water is continuously recycled, so that scaling, equipment corrosion and microorganism mass propagation in the pipeline are aggravated. In order to solve the above problems, various researches have been conducted for a long time, and currently, common circulating water treatment technologies mainly include chemical methods, physical methods, and biological methods. The chemical method is to add various medicaments for scale prevention, corrosion prevention, sterilization and algae removal, but can bring secondary pollution to the environment; the physical method adopts methods such as magnetization, static electricity, ultrasound and the like to carry out antiseptic sterilization, but the energy consumption is large, and the equipment is easy to age; the biological method is to purify water by degrading pollutants in water by using microorganisms as self nutrition and energy, but the method has poor descaling effect and long water treatment time, and is not suitable for a circulating cooling water system. Therefore, the electrochemical technology is most widely applied to the circulating cooling water treatment system at the present stage through the continuous research of experts at home and abroad.
The electrochemical circulating water treatment technology is Cl which is corrosive to pipes in a solution under the action of externally-applied direct current-Can generate active chlorine (such as ClO) with strong bactericidal property by electrolysis-And HClO), Ca2+、Mg2+Formation of CaCO in cathode region by isocationic ions3And MgCO3The bacteria are precipitated, and are restricted in proliferation or dead due to cell rupture and metabolic process disorder under the action of an electric field, and the effects of corrosion prevention, sterilization and scale inhibition are achieved. The anode material is a key material of an electrochemical circulating water treatment system, and sterilization and dechlorination reactions are carried out in an anode area, so that the anode material has important influence on the overall performance of the water treatment system. The electrocatalytic activity and stability of the anode material are two main performance indexes for finally evaluating the anode, and the anode material used at present is mainly superior to other electrode materials (graphite, lead anode and the like)Lead-based alloy anodes) have better electrocatalytic activity and stability.
The DSA electrode is divided into a chlorine evolution type anode and an oxygen evolution type anode according to the reaction types of the anode surface under different electrolyte conditions. The distribution range of the content of the chloride ions in the circulating cooling water is wide (300-20000 mg/L), the surface of the anode mainly has a chlorine evolution reaction, and the oxygen evolution reaction is accompanied, especially the oxygen evolution reaction is more obvious under the condition of low content of the chloride ions, so that the anode material is required to have higher oxygen-chlorine potential difference. The most common chlorine evolution type DSA is Ti/RuO2+IrO2+TiO2The coated electrode has low chlorine evolution potential and high catalytic activity, and is generally applied to the chlor-alkali industry with high chloride ion content. However, in the circulating water treatment industry, because the content of chloride ions is relatively low, the chlorine evolution potential of the coating electrode is low, but the oxygen evolution potential is also low, the oxygen-chlorine potential difference is small, and the surface of the electrode is accompanied by oxygen evolution side reaction to a great extent, so that the chlorine removal and sterilization efficiency of the anode is influenced, and the service life of the electrode is shortened. Research shows that IrO2Because of its high oxygen evolution potential, is introduced into the RuO2-TiO2The oxygen-chlorine potential difference can be improved after the coating is coated, but the price is higher than that of RuO2Much higher, so the cost of the electrode is relatively high. Secondly, the concomitant progress of the oxygen evolution reaction greatly shortens the service life of the coating, mainly due to the formation of insulating TiO between the coating and the substrate2And dissolution of the active layer. In addition, the conductivity is also an important index influencing the performance of the electrode, the conductivity of the metal oxide is poor, and the electric energy consumption can be increased in the electrode reaction process. Therefore, a coating material and a preparation process which can improve the electrocatalytic activity and stability of the electrode and reduce the cost and the power consumption are sought, and the problem to be solved in the circulating cooling water treatment industry at present is urgently needed.
Through the above analysis, the problems and defects of the prior art are as follows: the prior coating electrode has small oxygen-chlorine potential difference, poor chlorine removal and sterilization efficiency, short service life of the electrode, and high coating cost and power consumption.
The difficulty in solving the above problems and defects is: (1) side reactions exist on the surface of the electrode, and the accompanying oxygen evolution reaction is inevitable; (2) the active components in the coating are often all noble metal oxides; (3) the conductivity of the titanium substrate and the oxide coating is poor.
The significance for solving the problems and the defects is as follows: (1) doping a certain amount of base metal elements in the coating to increase the potential difference of oxygen evolution and chlorine evolution reactions, so that the oxygen evolution reaction is difficult to occur, thereby not only improving the removal rate of the anode chloride ions, but also prolonging the service life of the electrode; (2) the adoption of the intermediate layer and the gradient coating process can not only protect the titanium substrate and improve the binding force between the coating layers, but also effectively reduce the use amount of noble metal and reduce the coating cost; (3) the electrode conductivity is improved by doping a certain amount of conductive elements, so that the practical application power consumption can be reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a coating titanium anode for circulating cooling water treatment, a preparation method and application.
The invention is realized in such a way that the coating titanium anode for the treatment of the circulating cooling water is sequentially provided with a titanium substrate, an intermediate layer, a transition layer and a surface active layer;
the intermediate layer is TiC;
the transition layer is TiO2-Co3O4-C；
The surface active layer is made of TiO2、RuO2、IrO2、SnO2、CeO2、Co3O4And C, the surface active layer is [ RuO ] from inside to outside2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C，[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C。
The invention also aims to provide a preparation method of the coating titanium anode for the circulating cooling water treatment, which comprises the following steps:
step one, carrying out sand blasting treatment on a titanium substrate, and preparing the titanium substrate containing a TiC intermediate layer based on the titanium substrate subjected to sand blasting;
coating the mixed coating agent A on the titanium substrate containing the TiC interlayer obtained in the step one, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step three, repeating the step two for 1-3 times to obtain the alloy sequentially containing a TiC intermediate layer and TiO from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
coating the mixed coating agent B on the titanium base material obtained in the step three, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step five, repeating the step four for 3-7 times to obtain the alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
coating the mixed coating agent C on the titanium base material obtained in the fifth step, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step seven, repeating the step six 7-9 times to obtain the alloy sequentially containing TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step eight, coating the mixed coating agent D on the titanium base material obtained in the step seven, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step nine, repeating the step eight 1-3 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Further, in the step one, the preparing of the titanium substrate with the TiC interlayer comprises:
(1) after the titanium substrate was sand-blasted, 10 wt% Na was added2CO3Boiling in the solution, washing with alkali to remove oil, washing with acid in the boiling oxalic acid solution for at least 1h to remove oxide scale, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
(2) mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and a zeolite imidazole framework compound ZIFs-67;
(3) coating a hydrochloric acid-ethanol coating solution of 40-120 g/L malic acid on the dried titanium substrate, and drying at 60 ℃ for 15 min; and introducing nitrogen into the high-temperature furnace at 200-300 ℃ for roasting for 60-120 min, and introducing argon at 1300-2000 ℃ for roasting for 60-120 min to obtain the titanium substrate containing the TiC intermediate layer.
Further, in the second step, the mixed paint a containing the butyl titanate and the hydrochloric acid-ethanol mixed solution includes: 150g/L of butyl titanate and 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixture.
Further, in the fourth step, the mixed paint B includes: 19g/LRuCl3、4.2g/LH2IrCl6、0.3～1.5g/LSnCl4、0.3～1.5g/LCe(NO3)3150g/L of butyl titanate and 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixed solution.
Further, in the sixth step, the mixed paint C includes: 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3150g/L of butyl titanate and 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixed solution.
Further, in the step eight,the mixed paint D comprises: 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3And 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixture.
The invention also aims to provide application of the coating titanium anode for treating the circulating cooling water in the circulating cooling water treatment.
By combining all the technical schemes, the electrochemical performance test shows that the chlorine evolution potential of the coating titanium anode prepared by the method is lower than that of the traditional electrode, the oxygen-chlorine potential difference is increased, and the reinforced service life is prolonged, which shows that the coating titanium anode has advantages in the aspects of power consumption and service life; secondly, the removal rate of chloride ions and calcium ions is higher than that of the traditional titanium anode and the tank pressure is lower than that of the traditional electrode through a circulating water treatment test, which shows that the removal rate of chloride ions and calcium ions is better than that of the traditional titanium anode in the aspects of chlorine removal, sterilization, scale inhibition and power consumption reduction; in addition, the use amount of the noble metal in the preparation process provided by the invention is found to be reduced by 16.7 percent compared with the traditional preparation process through accounting, so that the enterprise cost can be greatly reduced. Therefore, the invention has the advantages and positive effects that: the invention provides a coating titanium anode for treatment of circulating cooling water, which can effectively remove chlorine, sterilize and inhibit scale, has good chemical stability, small electric energy consumption and lower coating cost, and effectively reduces enterprise cost.
The titanium anode with the gradient structure coating has the characteristics of strong TiC corrosion resistance and electrical conductivity and strong bonding force with metal titanium, and the TiC layer is introduced on the titanium substrate, so that the service life of the anode can be effectively prolonged, and the groove pressure can be reduced; SnO2Can improve the oxygen evolution potential of the electrode and reduce IrO2The amount of use of (c); CeO (CeO)2Can reduce the chlorine evolution potential and RuO of the electrode2The amount of use of (c); ZIFs-67 is used as a porous metal organic framework material with large specific surface area, and Co can be obtained by pyrolysis3O4And porous C, Co3O4Can refine oxide particles in the coating and increase the surface roughness of the coating, thereby effectively improving the utilization rate of noble metal oxide, and the porous C can improve the oxideThe conductivity of the coating; ruo in oxide coating2-IrO2The content of TiO is gradually increased from inside to outside2The content is gradually reduced from inside to outside, so that the effective utilization rate of active components is improved, the cost is reduced, and meanwhile, the gradient structure can effectively slow down the stress mutation on the bonding surface of the coating and the substrate and improve the bonding force between the coating and the substrate.
The titanium anode prepared by the invention has low tank pressure and low power consumption in the process of treating circulating cooling water. The titanium anode prepared by the method reduces the loading amount of noble metal and effectively controls the cost of the electrode. The potential difference of the oxygen and the chlorine of the titanium anode prepared by the method is more than 200mV, so that the dechlorination efficiency in the electrolytic process and the effective chlorine content in the electrolyte are improved, and the service life of the electrode is also prolonged.
The invention provides a coating titanium anode for treatment of circulating cooling water, which comprises a titanium substrate, a TiC intermediate layer and TiO2-Co3O4A C transition layer and a C, Sn, Ce and Co Co-doped active layer prepared by a gradient method. With conventional Ti/RuO2+IrO2+TiO2Comparing the anode: the addition of the TiC intermediate layer improves the binding force between the coating and the matrix and the corrosion resistance of the matrix; the introduction of the C element improves the conductivity of the coating; the addition of Sn, Ce and Co can not only improve the utilization rate of the metal oxide particles by refining the metal oxide particles, but also increase the potential difference of oxygen and chlorine; the gradient preparation process not only improves the binding force among the active layers, but also effectively reduces the anode cost. The coating anode has good electrocatalysis performance and service life, has large difference of oxygen and chlorine potentials, high chlorine evolution efficiency and high efficiency of removing chloride ions and calcium ions in the circulating water electrolysis process, and is a better choice for anode materials in the field of circulating cooling water treatment.
Drawings
Fig. 1 is a schematic structural diagram of a coated titanium anode for treatment of recirculated cooling water according to an embodiment of the present invention.
In the figure: 1. an intermediate layer; 2, a transition layer; 3. [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C；4、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C；5、RuO2-IrO2-SnO2-CeO2-Co3O4-C。
FIG. 2 is a flow chart of a preparation method of a coating titanium anode for treatment of circulating cooling water provided by the embodiment of the invention.
FIG. 3 is a graph showing the results of a strengthened lifetime test of a coated titanium anode in a 1M sulfuric acid solution according to an embodiment of the present invention.
Fig. 4 is a graph showing the results of the oxygen evolution potential of the coated titanium anode in 0.5M sulfuric acid and the chlorine evolution potential in saturated sodium chloride.
FIG. 5 is a schematic diagram illustrating a simplified apparatus for circulating cooling water treatment according to an embodiment of the present invention;
in the figure: 6. sealing the constant-temperature electrolytic tank; 7. an electrolyte sampling port; 8. a titanium-based coating anode; 9. an electrolyte; 10. a water circulating pump; 11. a flow meter; 12. a titanium-based cathode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a coating titanium anode for circulating cooling water treatment, a preparation method and application thereof, and the invention is described in detail with reference to the accompanying drawings.
As shown in fig. 1, the coated titanium anode for treatment of recirculated cooling water provided by the embodiment of the present invention is sequentially provided with a titanium substrate, an intermediate layer 1, a transition layer 2 and a surface active layer;
the intermediate layer 1 is TiC; the transition layer 2 is TiO2-Co3O4-C; the surface active layer is made of TiO2、RuO2、IrO2、SnO2、CeO2、Co3O4And C, the surface active layer is [ RuO ] from inside to outside2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C，[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C。
As shown in fig. 2, a method for preparing a coated titanium anode for treatment of recirculated cooling water according to an embodiment of the present invention includes:
s101, performing sand blasting treatment on the titanium base material, and preparing the titanium base material containing the TiC intermediate layer on the basis of the titanium base material subjected to sand blasting;
s102, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.4-1.2 g/LZIFs-67 on the titanium substrate containing the TiC interlayer obtained in the step S101, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
s103, repeating the step S102 for 1-3 times to obtain the TiC intermediate layer and TiO2-Co3O4-a titanium substrate of a C transition layer;
s104, the solution will contain 19g/LRuCl3、4.2g/LH2IrCl6、0.3～1.5g/LSnCl4、0.3～1.5g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.4-1.2 g/LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate S103, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
s105, repeating the step S104 for 3-7 times to obtain the alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
s106, the solution will contain 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3Coating a hydrochloric acid-ethanol mixed solution of 150g/L of butyl titanate and 0.4-1.2 g/LZIFs-67 on the titanium substrate obtained in S105, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
s107, repeating the step S106 times to 7-9 times to obtain the alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
s108, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3And 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step S107, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min;
s109, repeating the step S108 for 1-3 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
The titanium substrate for preparing the TiC-containing interlayer provided by the embodiment of the invention comprises the following steps:
(1) after the titanium substrate was sand-blasted, 10 wt% Na was added2CO3Boiling in alkali solution to remove oil, then acid-washing in boiling oxalic acid solution for at least 1h to remove oxide scale, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
(2) mixing hydrochloric acid and ethanol according to a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
(3) coating a hydrochloric acid-ethanol coating solution of 40-120 g/L malic acid on the dried titanium substrate, and drying for 15min at 60 ℃; and introducing nitrogen into the high-temperature furnace at 200-300 ℃ for roasting for 60-120 min, and introducing argon at 1300-2000 ℃ for roasting for 60-120 min to obtain the titanium substrate containing the TiC intermediate layer.
The technical solution of the present invention is further described with reference to the following specific embodiments.
The invention provides a coating titanium anode for circulating cooling water treatment, as shown in figure 1, the coating on the surface of a titanium substrate is TiC and TiO respectively from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C；
The preparation method of the coating titanium anode for treating the circulating cooling water, provided by the invention, comprises the following steps;
step 1, sand blasting the titanium base material, and then adding 10 wt% of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating a hydrochloric acid-ethanol coating solution of 40-120 g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 200-300 ℃ for 60-120 min, and introducing argon into the high-temperature furnace, roasting at 1300-2000 ℃ for 60-120 min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.4-1.2 g/LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, roasting at 450 ℃ for 15min, repeating the coating, drying and roasting for 1-3 times to obtain a TiC intermediate layer and TiO, wherein the TiC intermediate layer and the TiO are sequentially contained from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、0.3～1.5g/LSnCl4、0.3～1.5g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.4-1.2 g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 3-7 times to obtain the titanium carbide alloy sequentially containing TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.4-1.2 g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 7-9 times to obtain the titanium carbide alloy sequentially containing TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、0.6～3g/LSnCl4、0.6～3g/LCe(NO3)3And 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min; repeating the coating, drying and roasting for 1-3 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
The obtained coating titanium anode is used in the field of treating circulating cooling water by an electrochemical method.
As shown in FIG. 3, curve a in FIG. 3 represents the coated titanium anode prepared by the present invention; curve b in FIG. 3 represents a conventional Ti/RuO2+IrO2+TiO2The anode, from fig. 3, shows that the strengthening life of the coating anode prepared by the invention is effectively improved;
as shown in FIG. 4, curve a in FIG. 4 shows the oxygen evolution potential of the coated titanium anode prepared by the present invention; curve b in fig. 4 represents the chlorine evolution potential of the coated titanium anode prepared according to the invention, and from fig. 4 it is shown that the difference in the oxychlorination potential is greater than 200mV.
Example 1
The preparation method of the coating titanium anode for treating the circulating cooling water, provided by the invention, comprises the following steps;
step 1, sand blasting the titanium substrate, and then adding 10 wt% of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol according to the volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, metal precursors and ZIFs-67;
step 3, coating the hydrochloric acid-ethanol coating solution of 40g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 200 ℃ for 120min, and introducing argon into the high-temperature furnace, roasting at 1300 ℃ for 120min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating the hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.4g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, roasting at 450 ℃ for 15min, repeating the coating, drying and roasting for 3 times to obtain the titanium substrate containing the TiC intermediate layer and the TiO in sequence from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、0.3g/LSnCl4、1.5g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.4g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 7 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、0.6g/LSnCl4、3g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.4g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 7 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、0.6g/LSnCl4、3g/LCe(NO3)3And 0.4g/LZIFs-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, the titanium substrate is dried for 10min at the temperature of 120 ℃, and then is roasted for 15min at the temperature of 450 ℃, so that TiC and TiO are obtained from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Example 2
The invention provides a preparation method of a coating titanium anode for treating circulating cooling water, which comprises the following steps;
step 1, sand blasting the titanium substrate, and then adding 10 wt% of Na2CO3Boiling in the solution, washing with alkali to remove oil, washing with acid in the boiling oxalic acid solution for at least 1h to remove oxide scale, finally washing with tap water, deionized water and alcohol in sequence, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating the hydrochloric acid-ethanol coating solution of 80g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 250 ℃ for 60min, and introducing argon into the high-temperature furnace, roasting at 1700 ℃ for 90min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating the hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.8g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, roasting at 450 ℃ for 15min, repeating the coating, drying and roasting for 2 times to obtain the titanium substrate sequentially containing the TiC intermediate layer and the TiO from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、1.5g/LSnCl4、0.3g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.8g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 5 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、3g/LSnCl4、0.6g/LCe(NO3)3150g/L butyl titanate and 0.8g/L LZIFS-67 of hydrochloric acid-ethanol mixture was coated on the titanium substrate obtained in step 5 at 120 deg.CDrying for 10min, and roasting at 450 deg.C for 15 min; repeating the coating, drying and roasting for 8 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、3g/LSnCl4、0.6g/LCe(NO3)3And 0.8g/LZIFS-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min; repeating the coating, drying and roasting for 2 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Example 3
The preparation method of the coating titanium anode for treating the circulating cooling water, provided by the invention, comprises the following steps;
step 1, sand blasting the titanium substrate, and then adding 10 wt% of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating the hydrochloric acid-ethanol coating solution of 120g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 300 ℃ for 90min, and introducing hydrogen into the high-temperature furnace, roasting at 2000 ℃ for 60min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 1.2g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15min to obtain a TiC intermediate layer and TiO containing the TiC intermediate layer and the TiO in sequence from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、0.9g/LSnCl4、0.9g/LCe(NO3)3Coating 150g/L of butyl titanate and 1.2g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 3 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、1.8g/LSnCl4、1.8g/LCe(NO3)3Coating 150g/L of butyl titanate and 1.2g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 9 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、1.8g/LSnCl4、1.8g/LCe(NO3)3And 1.2g/LZIFS-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min; is repeated onCoating, drying and roasting for 3 times to obtain TiC and TiO2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Example 4
The preparation method of the coating titanium anode for treating the circulating cooling water, provided by the invention, comprises the following steps;
step 1, sand blasting the titanium substrate, and then adding 10 wt% of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating a hydrochloric acid-ethanol coating solution of 60g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 220 ℃ for 100min, and introducing hydrogen into the high-temperature furnace, roasting at 1500 ℃ for 100min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.6g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 3 times to obtain a TiC intermediate layer and TiO2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、1.0g/LSnCl4、0.8g/LCe(NO3)3150g/L of butyl titanate and 0.6g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution are coated on the titanium base material obtained in the step 4, dried at 120 ℃ for 10min,then roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 6 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、2.0g/LSnCl4、1.6g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.6g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 7 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、2.0g/LSnCl4、1.6g/LCe(NO3)3And 0.6g/LZIFS-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min; repeating the coating, drying and roasting for 2 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Example 5
The preparation method of the coating titanium anode for treating the circulating cooling water, provided by the invention, comprises the following steps;
step 1, titanium baseAfter sand blasting, the material is added with 10wt percent of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating a hydrochloric acid-ethanol coating solution of 100g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 270 ℃ for 90min, and introducing hydrogen into the high-temperature furnace, roasting at 1800 ℃ for 80min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 0.9g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 2 times to obtain a TiC intermediate layer and TiO2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、0.6g/LSnCl4、1.2g/LCe(NO3)3Coating 150g/L of butyl titanate and 0.9g/L of LZIFs-67 of hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 5 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、1.2g/LSnCl4、2.4g/LCe(NO3)3Coating 150g/L of butyl titanate and 1.2g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 8 times to obtain the product containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、1.2g/LSnCl4、2.4g/LCe(NO3)3And 0.9g/LZIFs-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15 min; repeating the coating, drying and roasting for 2 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Example 6
The invention provides a preparation method of a coating titanium anode for treating circulating cooling water, which comprises the following steps;
step 1, sand blasting the titanium substrate, and then adding 10 wt% of Na2CO3Boiling in an alkali washing solution to remove oil, then carrying out acid washing in a boiling oxalic acid solution for at least 1h to remove oxide skins, finally sequentially washing with tap water, deionized water and alcohol, and drying for later use;
step 2, mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and ZIFs-67;
step 3, coating the hydrochloric acid-ethanol coating solution of 110g/L malic acid on the dried titanium substrate, drying at 60 ℃ for 15min, introducing nitrogen into a high-temperature furnace, roasting at 280 ℃ for 100min, and introducing hydrogen into the high-temperature furnace, roasting at 1800 ℃ for 90min to obtain the titanium substrate containing the TiC intermediate layer;
step 4, coating a hydrochloric acid-ethanol mixed solution containing 150g/L of butyl titanate and 1.0g/L of LZIFs-67 on the titanium substrate obtained in the step 3, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15min to obtain a TiC intermediate layer and TiO sequentially from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
step 5, mixing the solution containing 19g/LRuCl3、4.2g/LH2IrCl6、1.2g/LSnCl4、0.6g/LCe(NO3)3Coating 150g/L of butyl titanate and 1.0g/L of LZIFS-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 4, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 5 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
step 6, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、2.4g/LSnCl4、1.2g/LCe(NO3)3Coating 150g/L of butyl titanate and 1.0g/L of LZIFs-67 hydrochloric acid-ethanol mixed solution on the titanium substrate obtained in the step 5, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min; repeating the coating, drying and roasting for 9 times to obtain the titanium carbide alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C and [ RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step 7, mixing the solution containing 38g/LRuCl3、8.4g/LH2IrCl6、2.4g/LSnCl4、1.2g/LCe(NO3)3And 1.2g/LZIFs-67 of hydrochloric acid-ethanol mixed solution is coated on the titanium substrate obtained in the step 6, dried at 120 ℃ for 10min and then roasted at 450 ℃ for 15min to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C-coated titanium anodes.
Performance testing
The electrochemical treatment performance test of the coating titanium anode prepared in the embodiments 1, 2, 3, 4, 5 and 6 of the invention is carried out, and the method comprises the following steps: respectively cutting four coating anode samples made of 1cm x 1cm, inserting a first part, a titanium sheet cathode and a saturated calomel electrode into an electrolytic cell containing 0.5M sulfuric acid solution, inserting a second part, the titanium sheet cathode and the saturated calomel electrode into an electrolytic cell containing saturated sodium chloride solution, respectively testing oxygen evolution potential and chlorine evolution potential (calculating oxygen-chlorine potential difference) by adopting an electrochemical workstation, wherein the temperature of the electrolyte is 25 ℃, and the current density of the anode is 200A/M2(ii) a Inserting the third part and titanium sheet cathode into an electrolytic cell containing 1M sulfuric acid solution, and performing an enhanced life test experiment by using a direct current power supply (the electrode is regarded as invalid when the cell pressure rises 5V compared with the initial stage), wherein the electrolyte temperature is 40 ℃, and the anode current density is 20000A/M2(ii) a Inserting the fourth part and titanium sheet cathode into an electrolytic cell containing 3.5% sodium chloride solution, and performing constant current electrolysis with DC power supply, wherein the temperature of the electrolyte is 25 deg.C, and the current density of the anode is 1500A/m2And after electrolysis for 1h, measuring the effective chlorine content in the electrolyte by adopting a chemical analysis method (calculating the chlorine analysis efficiency). The above results are shown in Table 1.
TABLE 1 coating titanium Anode electrochemical Performance test results
Figure BDA0003234964060000181
As can be seen from Table 1, the difference between the oxygen-chlorine potentials of the six coating titanium anodes prepared by the method is more than 200mV, the strengthening service life is more than 120h, and the chlorine evolution potential is more than 85%. The three important parameters are all compared with the traditional Ti/RuO2+IrO2+TiO2The good anode shows that the coating titanium anode prepared by the invention is in circulationThe application of the annular water treatment system has advantages.
Then, the coating titanium anodes prepared in embodiments 1, 2, 3, 4, 5, and 6 of the present invention were tested for performance of circulating water treatment, and the method was: placing the prepared coating titanium anode and a titanium sheet cathode with similar area into a simulated circulating cooling water solution (2.5g/L calcium chloride water solution), and performing an electrolysis experiment by using a direct-current power supply, wherein the temperature of the electrolyte is 25 ℃, and the current density of the anode is 300A/m2The volume of the electrolytic bath is 60L, and the electrode area is 50cm2Respectively monitoring the cell pressure and Cl after 2h of electrolysis-Concentration value of (1), Ca2+The concentration values and the cathode fouling quality of (B) are shown in Table 2.
TABLE 2 coating titanium anode electrolysis circulating water performance test results
Figure BDA0003234964060000182
As can be seen from Table 2, the six kinds of coated titanium anodes prepared by the method of the present invention have low tank pressure, small variation and Cl in the process of electrolytic treatment of circulating water-The removal rate of (1) is 6.9-7.7%, and Ca is2+The removal rate of (a) is 7.4 to 8.7%, and the mass of the cathode structure is 0.24 to 0.27 g. The four important parameters are all compared with the traditional Ti/RuO2+IrO2+TiO2The anode is good, which shows that the coating titanium anode prepared by the invention has good electrochemical performance in the circulating water treatment process.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A coating titanium anode for treatment of circulating cooling water is characterized in that the coating titanium anode for treatment of circulating cooling water is sequentially provided with a titanium substrate, an intermediate layer, a transition layer and a surface active layer;
the intermediate layer is TiC;
the transition layer is TiO2-Co3O4-C；
The surface active layer is made of TiO2、RuO2、IrO2、SnO2、CeO2、Co3O4And C, the surface active layer is [ RuO ] from inside to outside2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C，[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C。
2. The preparation method of the coating titanium anode for the treatment of the circulating cooling water as claimed in claim 1, wherein the preparation method of the coating titanium anode for the treatment of the circulating cooling water comprises the following steps:
step one, carrying out sand blasting treatment on a titanium substrate, and preparing the titanium substrate containing a TiC intermediate layer based on the titanium substrate subjected to sand blasting;
coating the mixed coating agent A on the titanium substrate containing the TiC interlayer obtained in the step one, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step three, repeating the step two for 1-3 times to obtain the alloy sequentially containing a TiC intermediate layer and TiO from inside to outside2-Co3O4-a titanium substrate of a C transition layer;
coating the mixed coating agent B on the titanium base material obtained in the step three, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step five, repeating the step four for 3-7 times to obtain the alloy containing TiC and TiO in sequence from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-a C-coated titanium substrate;
coating the mixed coating agent C on the titanium base material obtained in the fifth step, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step seven, repeating the step six 7-9 times to obtain the alloy sequentially containing TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-a C-coated titanium substrate;
step eight, coating the mixed coating agent D on the titanium base material obtained in the step seven, drying at 120 ℃ for 10min, and roasting at 450 ℃ for 15 min;
step nine, repeating the step eight 1-3 times to obtain TiC and TiO from inside to outside2-Co3O4-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](1)-C、[RuO2-IrO2-SnO2-CeO2-Co3O4-TiO2](2)-C and RuO2-IrO2-SnO2-CeO2-Co3O4-C coated titanium anodes.
3. The method for preparing the coating titanium anode for the treatment of the circulating cooling water according to claim 2, wherein in the first step, the preparation of the titanium substrate with the TiC interlayer comprises the following steps:
(1) after the titanium substrate was sand-blasted, 10 wt% Na was added2CO3Boiling in alkali solution to remove oil, then acid-washing in boiling oxalic acid solution for at least 1h to remove oxide scale, washing with tap water, deionized water and alcohol in sequence, and drying for later use;
(2) mixing hydrochloric acid and ethanol in a volume ratio of 1:40 to prepare a hydrochloric acid-ethanol mixed solvent, and preparing coating liquid by dissolving malic acid, a metal precursor and a zeolite imidazole framework compound ZIFs-67;
(3) coating a hydrochloric acid-ethanol coating solution of 40-120 g/L malic acid on the dried titanium substrate, and drying at 60 ℃ for 15 min; and introducing nitrogen into the high-temperature furnace at 200-300 ℃ for roasting for 60-120 min, and introducing argon at 1300-2000 ℃ for roasting for 60-120 min to obtain the titanium substrate containing the TiC intermediate layer.
4. The method for preparing the coating titanium anode for the treatment of the circulating cooling water as claimed in claim 2, wherein in the second step, the mixed coating agent A comprises the following components: 150g/L of butyl titanate and 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixture.
5. The method for preparing the coating titanium anode for the treatment of the circulating cooling water as claimed in claim 2, wherein in the fourth step, the mixed coating agent B comprises: 19g/L RuCl3、4.2g/L H2IrCl6、0.3～1.5g/L SnCl4、0.3～1.5g/L Ce(NO3)3150g/L of butyl titanate and 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixed solution.
6. The method for preparing the coating titanium anode for the treatment of the circulating cooling water as claimed in claim 2, wherein in the sixth step, the mixed coating agent C comprises: 38g/L RuCl3、8.4g/L H2IrCl6、0.6～3g/L SnCl4、0.6～3g/L Ce(NO3)3150g/L of butyl titanate and 0.4-1.2 g/L of ZIFs-67 hydrochloric acid-ethanol mixed solution.
7. The method for preparing the coating titanium anode for the treatment of the circulating cooling water as claimed in claim 2, wherein in the eighth step, the mixed coating agent D comprises the following components: 38g/L RuCl3、8.4g/L H2IrCl6、0.6～3g/L SnCl4、0.6～3g/L Ce(NO3)3And 0.4-1.2 g/LZIFS-67 of hydrochloric acid-ethanol mixture.
8. Use of a coated titanium anode as claimed in claim 1 in the treatment of recirculating cooling water.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900368A (en) * 2006-06-30 2007-01-24 福州大学 Titanium anode containing ruthenium coating of high cerium content and its preparing method
CN101469434A (en) * 2007-12-27 2009-07-01 中国蓝星（集团）股份有限公司 Active anode for hydrochloric acid electrolysis and preparation thereof
CN105621537A (en) * 2015-05-27 2016-06-01 财团法人未来素材研究团 Producing method of DLC/TI electrode for water treatment having multi-layer interface structure
CN106381507A (en) * 2016-09-09 2017-02-08 武汉大学 Inert anode used for melting triple carbonate electrolysis system
CN109518221A (en) * 2019-01-08 2019-03-26 福州大学 A kind of surface is rich in the gradient distribution Ni―Ti anode and preparation method thereof of iridium dioxide
CN112795908A (en) * 2020-12-18 2021-05-14 西安泰金工业电化学技术有限公司 Preparation method of titanium anode with titanium-based coating

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6589405B2 (en) * 2000-05-15 2003-07-08 Oleh Weres Multilayer oxide coated valve metal electrode for water purification
US10981811B2 (en) * 2012-10-08 2021-04-20 California Institute Of Technology Self-contained, PV-powered domestic toilet and wastewater treatment system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900368A (en) * 2006-06-30 2007-01-24 福州大学 Titanium anode containing ruthenium coating of high cerium content and its preparing method
CN101469434A (en) * 2007-12-27 2009-07-01 中国蓝星（集团）股份有限公司 Active anode for hydrochloric acid electrolysis and preparation thereof
CN105621537A (en) * 2015-05-27 2016-06-01 财团法人未来素材研究团 Producing method of DLC/TI electrode for water treatment having multi-layer interface structure
CN106381507A (en) * 2016-09-09 2017-02-08 武汉大学 Inert anode used for melting triple carbonate electrolysis system
CN109518221A (en) * 2019-01-08 2019-03-26 福州大学 A kind of surface is rich in the gradient distribution Ni―Ti anode and preparation method thereof of iridium dioxide
CN112795908A (en) * 2020-12-18 2021-05-14 西安泰金工业电化学技术有限公司 Preparation method of titanium anode with titanium-based coating

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