CN110129822B - Chlorine gas precipitation electrode and preparation method thereof - Google Patents
Chlorine gas precipitation electrode and preparation method thereof Download PDFInfo
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- CN110129822B CN110129822B CN201910549040.4A CN201910549040A CN110129822B CN 110129822 B CN110129822 B CN 110129822B CN 201910549040 A CN201910549040 A CN 201910549040A CN 110129822 B CN110129822 B CN 110129822B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
A chlorine gas precipitation electrode and a preparation method thereof comprise a metal substrate, wherein the surface of the metal substrate is coated with a metal oxide coating with a catalytic effect, the metal oxide coating is composed of a ruthenium metal oxide, an iridium metal oxide, a titanium metal oxide and a tin metal oxide, and the metal oxide coating comprises the following metal components, wherein the molar ratio of ruthenium is 7% -15%, the molar ratio of iridium is 1% -4.8%, the molar ratio of titanium is 1% -15%, and the molar ratio of tin is 75% -90%. The chlorine evolution electrode is suitable for chlorine production electrolytic cell anodes, and the preparation method thereof.
Description
Technical Field
The invention relates to the field of sodium hydroxide preparation, in particular to a chlorine gas precipitation electrode and a preparation method thereof.
Background
The titanium-based noble metal coating adopted by the chlorine evolution electrode in the traditional electrolysis device effectively reduces the overpotential of anodic chlorine evolution and reduces the operation energy consumption. However, expensive noble metals are required to be consumed to manufacture the coating, the electrode cost is greatly influenced by the price of the noble metal raw materials, in recent years, the market demand of the noble metals is continuously expanded, the resource consumption is greatly increased, the price of the noble metals is continuously increased, particularly, the manufacturing cost of the electrode is rapidly increased due to the noble metals Ru and Ir which play a main catalytic role in the chlorine evolution reaction process, and a new coating which can realize the electrode catalytic function and reduce the cost is very needed.
Generally, the coating cost can be controlled by controlling the dosage of the noble metals Ru and Ir in the anode coating preparation, but because the Ru and Ir catalysts are continuously consumed at a certain speed in the anode chlorine evolution reaction process, if the dosage is less, the service life of the anode is influenced, and the use requirement of a user cannot be met.
Researches show that the low-price Sn element can form metal oxide crystals with the same structure as Ru, Ir and Ti, can refine electrode surface coating particles, improve the catalytic activity of the electrode, and can be used for reducing the cost of a chlorine evolution anode and ensuring the service life of the anode. The chlorine evolution overpotential of Ru, Ir and Sn electrodes prepared in the Dinola CN200980144577.7 patent reaches 60mV under lower operating current density, expensive platinum, palladium and the like are required to be added for modification, the cost control of the electrodes is not facilitated, the binding force of Pt and Pd metal oxides and Ru, Ir and Sn metal oxides is poor, and the service life of the anode is difficult to guarantee.
Aiming at the problems of expensive price and short service life of a multi-element coating of the existing chlorine evolution anode, research and manufacture of the chlorine evolution anode which can ensure good service life of the anode, effectively reduce the manufacturing cost of the coating and simplify the electrode manufacturing process are necessary.
Disclosure of Invention
The invention aims to provide a chlorine evolution electrode which has the advantages of small consumption of noble metals ruthenium and iridium, low manufacturing cost of an anode, large bonding force between metal oxides, long service life and high catalytic activity, can effectively reduce the overpotential of chlorine evolution of the anode and reduce the electric energy consumption, and is very suitable for the anode of a chlorine production electrolytic cell and a preparation method thereof.
The chlorine gas precipitation electrode comprises a metal substrate, wherein the surface of the metal substrate is coated with a metal oxide coating with a catalytic effect, the metal oxide coating is composed of ruthenium metal oxide, iridium metal oxide, titanium metal oxide and tin metal oxide, and the metal oxide coating contains 7-15% of ruthenium element, 1-4.8% of iridium element, 1-15% of titanium element and 75-90% of tin element according to metal components.
The tin element in the tin metal oxide is divalent tin.
Preferably, the molar ratio of the ruthenium element is 8% -12%, the molar ratio of the iridium element is 1.2% -4.0%, the molar ratio of the titanium element is 5% -12%, and the molar ratio of the tin element is 78% -88%.
Preferably, the molar ratio of the ruthenium element is 9% -11%, the molar ratio of the iridium element is 1.5% -3.0%, the molar ratio of the titanium element is 8% -10%, and the molar ratio of the tin element is 80% -85%.
The preparation method of the chlorine evolution electrode comprises the following steps:
A. preparing a soluble inorganic salt of ruthenium, a soluble inorganic salt of iridium, a soluble inorganic salt of titanium and a soluble divalent salt of tin, and dissolving the soluble inorganic salt of ruthenium, the soluble inorganic salt of iridium, the soluble inorganic salt of titanium and the soluble divalent salt of tin in water to obtain an aqueous solution of the soluble inorganic salt of ruthenium, an aqueous solution of the soluble inorganic salt of iridium, an aqueous solution of the soluble inorganic salt of titanium and an aqueous solution of the soluble divalent salt of tin;
B. according to the proportion that the molar ratio of ruthenium is 7-15%, the molar ratio of iridium is 1-4.8%, the molar ratio of titanium is 1-15% and the molar ratio of tin is 75-90%, firstly uniformly mixing an aqueous solution of soluble inorganic salt of ruthenium, an aqueous solution of soluble inorganic salt of titanium and an aqueous solution of soluble divalent salt of tin, then adding an aqueous solution of soluble inorganic salt of iridium and uniformly mixing to obtain an inorganic coating solution;
C. cleaning the metal matrix to remove dirt on the surface of the metal matrix and roughen the surface of the metal matrix;
D. coating the inorganic coating solution obtained in the step B on the metal substrate treated in the step C, then carrying out heat treatment on the conductive substrate coated with the coating solution in an oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, forming a metal oxide coating on the outer surface of the metal substrate, then coating a layer of the inorganic coating solution on the newly formed metal oxide coating, then carrying out heat treatment on the conductive substrate coated with the coating solution in the oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, regenerating a new metal oxide coating on the outer surface of the previously formed metal oxide coating, and repeating the steps until the thickness of the metal oxide coating on the surface of the conductive substrate reaches the product requirement, wherein the time of the last heat treatment is 60-300 minutes, thus obtaining the chlorine gas precipitation electrode.
Preferably, in the step B, according to the proportion that the molar ratio of the ruthenium element is 8-12%, the molar ratio of the iridium element is 1.2-4.0%, the molar ratio of the titanium element is 5-12%, and the molar ratio of the tin element is 78-88%, an aqueous solution of a soluble inorganic salt of the ruthenium element, an aqueous solution of a soluble inorganic salt of the titanium element and an aqueous solution of a soluble divalent salt of the tin element are uniformly mixed, and then an aqueous solution of a soluble inorganic salt of the iridium element is added and uniformly mixed to obtain an inorganic coating solution;
the heat treatment temperature for the heat treatment of the conductive substrate coated with the coating solution in the step D is 460-520 ℃, and the heat treatment time is 35-80 minutes; the time of the last heat treatment is 80 minutes to 280 minutes.
Preferably, in the step B, according to the proportion that the molar ratio of the ruthenium element is 9-11%, the molar ratio of the iridium element is 1.5-3.0%, the molar ratio of the titanium element is 8-10%, and the molar ratio of the tin element is 80-85%, an aqueous solution of a soluble inorganic salt of the ruthenium element, an aqueous solution of a soluble inorganic salt of the titanium element and an aqueous solution of a soluble divalent salt of the tin element are uniformly mixed, and then an aqueous solution of a soluble inorganic salt of the iridium element is added and uniformly mixed to obtain an inorganic coating solution;
the heat treatment temperature for the heat treatment of the conductive substrate coated with the coating solution in the step D is 470-500 ℃, and the heat treatment time is 40-60 minutes; the time of the last heat treatment is 90 minutes to 200 minutes.
Preferably, the number of times of applying the inorganic coating solution to the outer surface of the metal substrate and performing the heat treatment in the step D is 7 to 12, and the coating amount of the metal oxide coating layer is 2g/m2—4g/m2。
Preferably, the number of times of applying the inorganic coating solution to the outer surface of the metal substrate and performing the heat treatment in the step D is 8 to 10, and the coating amount of the metal oxide coating layer is 2.5g/m2—3.5g/m2。
Preferably, the soluble inorganic salt of ruthenium element is RuCl3Or RuN4O10The soluble inorganic salt of iridium element is IrCl4Or Ir (NO)3)4The soluble inorganic salt of titanium element is TiCl4Or Ti (NO)3)4The soluble divalent salt of tin element is SnCl2·2H2O or Sn (NO)3)2·20H2O。
The preparation process of the invention adopts inorganic compounds, does not adopt any organic solvent, and has simple coating preparation process, thereby reducing the preparation difficulty and cost of the electrode and avoiding various adverse effects of the organic solvent on operators.
According to the chlorine evolution electrode, the weight reduction of the metal oxide coating is tested by soaking the chlorine evolution electrode in 32 w% NaOH solution at the temperature of 95 ℃ for 8 hours, and the result shows that the weight reduction (mg) of the service life of the metal oxide coating is 2.9-3.3 mg, while the weight reduction (mg) of the service life of the conventional metal oxide coating is usually 4.0-6.0 mg, which shows that the weight reduction of the service life of the chlorine evolution electrode is optimized, and meanwhile, the dosage of noble metals Ru and Ir in the chlorine evolution electrode coating is obviously reduced, and the manufacturing cost of the electrode is also obviously reduced.
The preparation method of the chlorine evolution electrode uses the divalent tin with a proper proportion in the preparation of the coating solution, thereby realizing the purpose of refining the surface coating particles of the electrode without adding expensive elements such as platinum, palladium and the like, simultaneously improving the catalytic activity of the electrode, and further realizing the reduction of the energy consumption of chlor-alkali electrolysis and the control of the cost of the electrode.
Unlike tetravalent tin, which is more than 70% and can be stably controlled, the coating solution of divalent tin produces an electrode coating in which Sn is deposited in an amount of more than 70%, whereas tetravalent tin has high volatility upon oxidation at high temperature, resulting in less than 30% tin being deposited in the coating and uncontrollable composition. Meanwhile, since the divalent tin is easy to generate oxidation-reduction reaction with other elements in the coating solution and form a complex, the oxide obtained during thermal oxidation is more uniformly distributed and more tightly combined, the particle size of the metal oxide is obviously thinned, the service life of the chlorine evolution electrode is prolonged, and the chlorine evolution potential of the electrode is reduced. Meanwhile, the inorganic salt of the divalent tin is easy to obtain in the market, has low price and can be directly used for preparing the coating liquid, thereby simplifying the coating preparation process and reducing the raw material cost.
Due to the unique technical characteristics of the invention, the chlorine evolution electrode and the preparation method thereof have the characteristics of small consumption of noble metals ruthenium and iridium, low manufacturing cost of the anode, large bonding force between metal oxides, long service life, high catalytic activity, capability of effectively reducing the overpotential of chlorine evolution of the anode and reducing the electric energy consumption, environmental protection, high efficiency and almost no discharge of pollutants, and are very suitable for the anode of a chlorine production electrolytic cell.
Further details and characteristics of the chlorine evolving electrode according to the invention and of the method for its preparation will become clear from a reading of the examples detailed below.
Detailed Description
The chlorine gas precipitation electrode comprises a metal substrate, wherein the surface of the metal substrate is coated with a metal oxide coating with a catalytic effect, the metal oxide coating is composed of ruthenium metal oxide, iridium metal oxide, titanium metal oxide and tin metal oxide, and the metal oxide coating contains 7-15% of ruthenium element, 1-4.8% of iridium element, 1-15% of titanium element and 75-90% of tin element according to metal components.
As a further improvement of the invention, the molar ratio of the ruthenium element is 8-12%, the molar ratio of the iridium element is 1.2-4.0%, the molar ratio of the titanium element is 5-12%, and the molar ratio of the tin element is 78-88%.
As a further improvement of the invention, the molar ratio of the ruthenium element is 9-11%, the molar ratio of the iridium element is 1.5-3.0%, the molar ratio of the titanium element is 8-10%, and the molar ratio of the tin element is 80-85%.
The mass percentages of the ruthenium element, the iridium element, the titanium element and the tin element in the metal oxide coating in terms of metal components in the metal oxide coating can be detected by an X-ray fluorescence tester.
The chlorine precipitation electrode is soaked in a 32 w% NaOH solution at 95 ℃ for 8 hours for strengthening electrolytic corrosion, the weight loss of a metal oxide coating is tested, and the service life of the coating is evaluated, and the result shows that the weight loss (mg) of the service life of the metal oxide coating is 2.9-3.3 mg, while the weight loss (mg) of the service life of the conventional metal oxide coating is usually 4.0-6.0 mg, which shows that the weight loss of the service life of the electrode is optimized, the contents of noble metals Ru and Ir in the prepared chlorine precipitation electrode coating are obviously reduced, and the manufacturing cost of the electrode is also obviously reduced.
The chlorine precipitation electrode provided by the invention tests 4KA/m under the electrolytic condition of 3.5mol/L NaCl solution at 90 DEG C2The electrode chlorine evolution overpotential under the current density is 33.7 mV-40.4 mV, compared with 4KA/m in the prior art2The overpotential for electrode chlorine evolution under current density is usually more than 60mV, which shows that the chlorine evolution electrode of the invention has excellent operation performance under high current density, effectively reduces the overpotential for electrode chlorine evolution, and has obvious energy-saving effect.
The preparation process of the invention adopts inorganic compounds, does not adopt any organic solvent, and has simple coating preparation process, thereby reducing the preparation difficulty and cost of the electrode and avoiding various adverse effects of the organic solvent on operators.
The preparation method of the chlorine evolution electrode uses the divalent tin with a proper proportion in the preparation of the coating solution, thereby realizing the purpose of refining the surface coating particles of the electrode without adding expensive elements such as platinum, palladium and the like, simultaneously improving the catalytic activity of the electrode, and further realizing the reduction of the energy consumption of chlor-alkali electrolysis and the control of the cost of the electrode.
Unlike tetravalent tin, which is more than 70% and can be stably controlled, the coating solution of divalent tin produces an electrode coating in which Sn is deposited in an amount of more than 70%, whereas tetravalent tin has high volatility upon oxidation at high temperature, resulting in less than 30% tin being deposited in the coating and uncontrollable composition. Meanwhile, since the divalent tin is easy to generate oxidation-reduction reaction with other elements in the coating solution and form a complex, the oxide obtained during thermal oxidation is more uniformly distributed and more tightly combined, the particle size of the metal oxide is obviously thinned, the service life of the chlorine evolution electrode is prolonged, and the chlorine evolution potential of the electrode is reduced. Meanwhile, the inorganic salt of the divalent tin is easy to obtain in the market, has low price and can be directly used for preparing the coating liquid, thereby simplifying the coating preparation process and reducing the raw material cost.
Example 1
The preparation method of the chlorine evolution electrode comprises the following steps:
A. preparing a soluble inorganic salt of ruthenium, a soluble inorganic salt of iridium, a soluble inorganic salt of titanium and a soluble divalent salt of tin, and dissolving the soluble inorganic salt of ruthenium, the soluble inorganic salt of iridium, the soluble inorganic salt of titanium and the soluble divalent salt of tin in water to obtain an aqueous solution of the soluble inorganic salt of ruthenium, an aqueous solution of the soluble inorganic salt of iridium, an aqueous solution of the soluble inorganic salt of titanium and an aqueous solution of the soluble divalent salt of tin;
the soluble inorganic salt of ruthenium is RuCl3Or RuN4O10The soluble inorganic salt of iridium element is IrCl4Or Ir (NO)3)4The soluble inorganic salt of titanium element is TiCl4Or Ti (NO)3)4The soluble divalent salt of tin element is SnCl2·2H2O or Sn (NO)3)2·20H2O。
B. According to the proportion that the molar ratio of ruthenium is 7-15%, the molar ratio of iridium is 1-4.8%, the molar ratio of titanium is 1-15% and the molar ratio of tin is 75-90%, firstly uniformly mixing an aqueous solution of soluble inorganic salt of ruthenium, an aqueous solution of soluble inorganic salt of titanium and an aqueous solution of soluble divalent salt of tin, then adding an aqueous solution of soluble inorganic salt of iridium and uniformly mixing to obtain an inorganic coating solution;
C. cleaning the metal matrix to remove dirt on the surface of the metal matrix and roughen the surface of the metal matrix;
D. coating the inorganic coating solution obtained in the step B on the metal substrate treated in the step C, then carrying out heat treatment on the conductive substrate coated with the coating solution in an oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, forming a metal oxide coating on the outer surface of the metal substrate, then coating a layer of the inorganic coating solution on the newly formed metal oxide coating, then carrying out heat treatment on the conductive substrate coated with the coating solution in the oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, regenerating a new metal oxide coating on the outer surface of the previously formed metal oxide coating, and repeating the steps until the thickness of the metal oxide coating on the surface of the conductive substrate reaches the product requirement, wherein the time of the last heat treatment is 60-300 minutes, thus obtaining the chlorine gas precipitation electrode.
In the step B, according to the proportion that the molar ratio of the ruthenium element is 8-12%, the molar ratio of the iridium element is 1.2-4.0%, the molar ratio of the titanium element is 5-12% and the molar ratio of the tin element is 78-88%, uniformly mixing an aqueous solution of a soluble inorganic salt of the ruthenium element, an aqueous solution of a soluble inorganic salt of the titanium element and an aqueous solution of a soluble divalent salt of the tin element, then adding an aqueous solution of a soluble inorganic salt of the iridium element and uniformly mixing to obtain an inorganic coating solution;
the heat treatment temperature for the heat treatment of the conductive substrate coated with the coating solution in the step D is 460-520 ℃, and the heat treatment time is 35-80 minutes;
and E, when the conductive substrate is subjected to heat treatment in the step E, the heat treatment temperature is 460-520 ℃, and the heat treatment time is 80-280 minutes.
In the step B, according to the proportion that the molar ratio of the ruthenium element is 9-11%, the molar ratio of the iridium element is 1.5-3.0%, the molar ratio of the titanium element is 8-10% and the molar ratio of the tin element is 80-85%, the aqueous solution of the soluble inorganic salt of the ruthenium element, the aqueous solution of the soluble inorganic salt of the titanium element and the aqueous solution of the soluble divalent salt of the tin element are uniformly mixed, and then the aqueous solution of the soluble inorganic salt of the iridium element is added and uniformly mixed to obtain an inorganic coating solution;
the heat treatment temperature for the heat treatment of the conductive substrate coated with the coating solution in the step D is 470-500 ℃, and the heat treatment time is 40-60 minutes;
and E, when the conductive substrate is subjected to heat treatment in the step E, the heat treatment temperature is 460-520 ℃, and the heat treatment time is 90-200 minutes.
As a further improvement of the invention, the number of times of applying the inorganic coating solution to the outer surface of the metal substrate and performing the heat treatment in the above step D is 7 to 12, and the single-layer coating amount of the metal oxide coating is 2g/m2—4g/m2。
As a further improvement of the invention, the number of times of applying the inorganic coating solution to the outer surface of the metal substrate and performing the heat treatment in the above step D is 8 to 10 times, and the single-layer coating amount of the metal oxide coating is 2.5g/m2—3.5g/m2。
Example 2
The preparation method of the chlorine evolution electrode comprises the following steps:
(1) roughening and cleaning the metal matrix: the metal matrix is made of a TA1 mesh titanium plate, a titanium mesh with the mesh size of 6mm x 3mm x 1mm is adopted, after the mesh titanium plate is leveled, the mesh titanium plate is heated to boiling by using sulfuric acid with the weight percentage concentration of 20-25% for pickling for 1-4h to remove surface dirt, meanwhile, the surface of the metal matrix is rough, after pickling is finished, the metal matrix is washed clean by pure water and dried for later use.
(2) Preparing a coating solution: preparing inorganic coating solution according to element mole ratio of Ru 7%, Ir 1%, Ti 2% and Sn 90%, and preparing 0.1ml TiCl under the condition of cold bath below-20 DEG C4Adding a solution containing 1.8ml of RuCl3Placing the hydrochloric acid aqueous solution in a container, standing to normal temperature, adding 8ml of dilute hydrochloric acid aqueous solution into the container, adding 6.222g of SnCl into the container2·2H2O inorganic salt, stirring to SnCl2·2H2The O inorganic salt was completely dissolved, and then 0.5ml of IrCl was added to the vessel4And (3) uniformly stirring the hydrochloric acid aqueous solution, finally adding 18ml of dilute hydrochloric acid aqueous solution into the container, fixing the volume to 30ml, shaking up, standing for 30 minutes, and observing that the coating liquid is free of precipitate for use.
(3) Preparing an electrode coating: coating the coating solution prepared in the step (2) on the metal substrate treated in the step (1), and carrying out heat treatment at 450 ℃ for 30 min; then repeating the coating solution for 10 times, each time coating the coating solution, heat-treating at 450 deg.C for 30min, and finally coating the coating solution layer, and heat-treating at 500 deg.C for 120 min.
Example 3
The preparation method of the chlorine evolution electrode comprises the following steps:
(1) roughening and cleaning the metal matrix: the metal matrix is made of a TA1 mesh titanium plate, a titanium mesh with the mesh size of 6mm x 3mm x 1mm is adopted, after the mesh titanium plate is leveled, the mesh titanium plate is heated to boiling by using sulfuric acid with the weight percentage concentration of 20-25% for pickling the mesh titanium plate for 2-3h, surface dirt is removed, meanwhile, the surface of the metal matrix is rough, after pickling is finished, the metal matrix is washed clean by using pure water, and the metal matrix is dried for later use.
(2) Preparing a coating solution: preparing inorganic coating solution according to element molar ratio of Ru 15%, Ir 1%, Ti 2% and Sn 82%, and adding 0.1ml TiCl under the condition of cold bath at the temperature of below-20 DEG C43.9ml of RuCl were added3Placing in a container containing hydrochloric acid aqueous solution, standing to normal temperature, adding 8ml dilute hydrochloric acid aqueous solution, adding 5.864g SnCl2·2H2O inorganic salt, stirring to SnCl2·2H2The O inorganic salt was completely dissolved, and then 0.5ml of IrCl was added to the vessel4And (3) uniformly stirring the hydrochloric acid aqueous solution, finally adding 16ml of dilute hydrochloric acid aqueous solution into the container, fixing the volume to 30ml, shaking up, standing for 30 minutes, and observing that the coating liquid is free of precipitate.
(3) Preparing an electrode coating: coating the coating solution prepared in the step (2) on the metal substrate treated in the step (1), performing heat treatment at 450 ℃ for 30min, repeating coating solution and heat treatment for 8 times, starting from the coating solution coated at the 2 nd time, performing heat treatment at 500 ℃ for 60min each time, and performing heat treatment at 530 ℃ for 300min after the coating solution is coated on the final layer.
Example 4
The preparation method of the chlorine evolution electrode comprises the following steps:
(1) roughening and cleaning the metal matrix: the metal matrix is made of a TA1 mesh titanium plate, a titanium mesh with the mesh size of 6mm x 3mm x 1mm is adopted, after the mesh titanium plate is leveled, sulfuric acid with the weight percentage concentration of 20-25% is used for heating to boiling and then pickling the mesh titanium plate for 3-4 hours, surface dirt is removed, meanwhile, the surface of the metal matrix is rough, after pickling is finished, the metal matrix is washed clean by pure water and dried for later use.
(2) Preparing a coating solution: preparing an inorganic coating solution according to the element molar ratio of Ru 10%, Ir 3%, Ti 2% and Sn 85%, adding 0.1ml of TiCl4 into a container containing 2.6ml of RuCl3 hydrochloric acid aqueous solution under a cold bath condition at the temperature of lower than-20 ℃, standing to normal temperature, adding 8ml of dilute hydrochloric acid aqueous solution into the container, adding 6.079g of SnCl 2.2H2O inorganic salt into the container, stirring to completely dissolve the SnCl 2.2H2O inorganic salt, then adding 1.5ml of IrCl4 hydrochloric acid aqueous solution into the container, uniformly stirring, finally adding 16ml of dilute hydrochloric acid aqueous solution into the container, fixing the volume to 30ml, shaking uniformly, standing for 30 minutes, and observing that the coating solution can be used without precipitation.
(3) Preparing an electrode coating: coating the coating solution prepared in the step (2) on the metal substrate treated in the step (1), performing heat treatment at 450 ℃ for 30min, repeating the coating solution and the heat treatment for 9 times, starting from the coating solution for the 2 nd time, performing heat treatment at 485 ℃ for 30min each time, and performing heat treatment at 530 ℃ for 180min after the final layer of the coating solution is coated.
Example 5
The preparation method of the chlorine evolution electrode comprises the following steps:
(1) roughening and cleaning the metal matrix: the metal matrix is made of a TA1 mesh titanium plate, a titanium mesh with the mesh size of 6mm x 3mm x 1mm is adopted, after the mesh titanium plate is leveled, sulfuric acid with the weight percentage concentration of 20-25% is used for heating to boiling and then pickling the mesh titanium plate for 3-4 hours, surface dirt is removed, meanwhile, the surface of the metal matrix is rough, after pickling is finished, the metal matrix is washed clean by pure water and dried for later use.
(2) Preparing a coating solution: preparing inorganic coating solution according to element molar ratio of Ru 10%, Ir 3%, Ti 2% and Sn 85%, and cooling bath at temperature lower than-20 deg.C to obtain 0.182g Ti (NO)3)4Adding into a container containing 3.1ml of RuN4O10 acidic aqueous solution, adding small amount of dilute nitric acid aqueous solution into the container, stirring to completely dissolve Ti (NO3)4, standing to room temperature, adding 15.722gSn (NO3) 2.20H 2O inorganic salt into the container, stirring to dissolve Sn (NO3)3)2·20H2And completely dissolving the inorganic salt O, adding 1.8ml of Ir (NO3)4 acidic aqueous solution, uniformly stirring, finally adding 13ml of dilute nitric acid aqueous solution into the container, fixing the volume to 30ml, shaking uniformly, standing for 30 minutes, and observing that the coating liquid can be used without precipitation.
(3) Preparing an electrode coating: coating the coating solution prepared in the step (2) on the metal substrate treated in the step (1), performing heat treatment at 450 ℃ for 30min, repeating coating of the coating solution and the heat treatment for 9 times, performing heat treatment at 485 ℃ for 30min from the 2 nd time, and performing heat treatment at 530 ℃ for 180min after coating the coating solution on the final layer.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (9)
1. The chlorine precipitation electrode is characterized by comprising a metal substrate, wherein the surface of the metal substrate is coated with a metal oxide coating with a catalytic effect, the metal oxide coating is composed of a ruthenium metal oxide, an iridium metal oxide, a titanium metal oxide and a tin metal oxide, and the metal oxide coating contains 7-15% of ruthenium element, 1-4.8% of iridium element, 1-15% of titanium element and 75-90% of tin element according to metal components;
the chlorine precipitation electrode is prepared by the following steps:
A. preparing a soluble inorganic salt of ruthenium, a soluble inorganic salt of iridium, a soluble inorganic salt of titanium and a soluble divalent salt of tin, and dissolving the soluble inorganic salt of ruthenium, the soluble inorganic salt of iridium, the soluble inorganic salt of titanium and the soluble divalent salt of tin in water to obtain an aqueous solution of the soluble inorganic salt of ruthenium, an aqueous solution of the soluble inorganic salt of iridium, an aqueous solution of the soluble inorganic salt of titanium and an aqueous solution of the soluble divalent salt of tin;
B. according to the proportion that the molar ratio of ruthenium is 7-15%, the molar ratio of iridium is 1-4.8%, the molar ratio of titanium is 1-15% and the molar ratio of tin is 75-90%, firstly uniformly mixing an aqueous solution of soluble inorganic salt of ruthenium, an aqueous solution of soluble inorganic salt of titanium and an aqueous solution of soluble divalent salt of tin, then adding an aqueous solution of soluble inorganic salt of iridium and uniformly mixing to obtain an inorganic coating solution;
C. cleaning the metal matrix to remove dirt on the surface of the metal matrix and roughen the surface of the metal matrix;
D. coating the inorganic coating solution obtained in the step B on the metal substrate treated in the step C, then carrying out heat treatment on the conductive substrate coated with the coating solution in an oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, forming a metal oxide coating on the outer surface of the metal substrate, then coating a layer of the inorganic coating solution on the newly formed metal oxide coating, then carrying out heat treatment on the conductive substrate coated with the coating solution in the oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, regenerating a new metal oxide coating on the outer surface of the previously formed metal oxide coating, and repeating the steps until the thickness of the metal oxide coating on the surface of the conductive substrate reaches the product requirement, wherein the time of the last heat treatment is 60-300 minutes, thus obtaining the chlorine gas precipitation electrode.
2. The chlorine evolving electrode according to claim 1, characterized in that said molar ratio of the ruthenium element is between 8% and 12%, the molar ratio of the iridium element is between 1.2% and 4.0%, the molar ratio of the titanium element is between 5% and 12% and the molar ratio of the tin element is between 78% and 88%.
3. The chlorine evolving electrode according to claim 2, characterized in that said molar ratio of ruthenium is between 9% and 11%, of iridium is between 1.5% and 3.0%, of titanium is between 8% and 10% and of tin is between 80% and 85%.
4. The preparation method of the chlorine evolution electrode is characterized by comprising the following steps:
A. preparing a soluble inorganic salt of ruthenium, a soluble inorganic salt of iridium, a soluble inorganic salt of titanium and a soluble divalent salt of tin, and dissolving the soluble inorganic salt of ruthenium, the soluble inorganic salt of iridium, the soluble inorganic salt of titanium and the soluble divalent salt of tin in water to obtain an aqueous solution of the soluble inorganic salt of ruthenium, an aqueous solution of the soluble inorganic salt of iridium, an aqueous solution of the soluble inorganic salt of titanium and an aqueous solution of the soluble divalent salt of tin;
B. according to the proportion that the molar ratio of ruthenium is 7-15%, the molar ratio of iridium is 1-4.8%, the molar ratio of titanium is 1-15% and the molar ratio of tin is 75-90%, firstly uniformly mixing an aqueous solution of soluble inorganic salt of ruthenium, an aqueous solution of soluble inorganic salt of titanium and an aqueous solution of soluble divalent salt of tin, then adding an aqueous solution of soluble inorganic salt of iridium and uniformly mixing to obtain an inorganic coating solution;
C. cleaning the metal matrix to remove dirt on the surface of the metal matrix and roughen the surface of the metal matrix;
D. coating the inorganic coating solution obtained in the step B on the metal substrate treated in the step C, then carrying out heat treatment on the conductive substrate coated with the coating solution in an oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, forming a metal oxide coating on the outer surface of the metal substrate, then coating a layer of the inorganic coating solution on the newly formed metal oxide coating, then carrying out heat treatment on the conductive substrate coated with the coating solution in the oxygen-containing atmosphere at the heat treatment temperature of 450-550 ℃ for 30-100 minutes, regenerating a new metal oxide coating on the outer surface of the previously formed metal oxide coating, and repeating the steps until the thickness of the metal oxide coating on the surface of the conductive substrate reaches the product requirement, wherein the time of the last heat treatment is 60-300 minutes, thus obtaining the chlorine gas precipitation electrode.
5. The process for producing an electrode for precipitating chlorine as claimed in claim 4, wherein in the step B, an aqueous solution of a soluble inorganic salt of ruthenium, an aqueous solution of a soluble inorganic salt of titanium and an aqueous solution of a soluble divalent salt of tin are first mixed in a proportion of from 8 to 12% by mole of ruthenium, from 1.2 to 4.0% by mole of iridium, from 5 to 12% by mole of titanium and from 78 to 88% by mole of tin, and then an aqueous solution of a soluble inorganic salt of iridium is added and mixed to obtain an inorganic coating solution;
and D, performing heat treatment on the conductive substrate coated with the coating solution at the heat treatment temperature of 460-520 ℃, wherein the heat treatment time is 35-80 minutes, and the last heat treatment time is 80-280 minutes.
6. The process for producing an electrode for precipitating chlorine as claimed in claim 5, wherein in the step B, an aqueous solution of a soluble inorganic salt of ruthenium, an aqueous solution of a soluble inorganic salt of titanium and an aqueous solution of a soluble divalent salt of tin are first mixed in a proportion of 9 to 11% by mole of ruthenium, 1.5 to 3.0% by mole of iridium, 8 to 10% by mole of titanium and 80 to 85% by mole of tin, and then an aqueous solution of a soluble inorganic salt of iridium is added and mixed to obtain an inorganic coating solution;
the heat treatment temperature for the heat treatment of the conductive substrate coated with the coating solution in the step D is 470-500 ℃, and the heat treatment time is 40-60 minutes; the time of the last heat treatment is 90 minutes to 200 minutes.
7. The method of claim 4, 5 or 6, wherein the step D of applying the inorganic coating solution to the outer surface of the metal substrate and heat-treating the metal substrate is carried out 7 to 12 times, and the amount of the metal oxide coating layer is 2g/m2—4g/m2。
8. The method according to claim 7, wherein the step D comprises applying the inorganic coating solution to the outer surface of the metal substrate and heat-treating the metal substrate 8 to 10 times, and the coating amount of the metal oxide coating layer is 2.5g/m2—3.5g/m2。
9. Process for the preparation of an electrode for the evolution of chlorine according to claim 8, characterized in that said soluble inorganic salt of ruthenium is RuCl3Or RuN4O10The soluble inorganic salt of iridium element is IrCl4Or Ir (NO)3)4The soluble inorganic salt of titanium element is TiCl4Or Ti (NO)3)4Solubility of tin element twoThe salt is SnCl2·2H2O or Sn (NO)3)2·20H2O。
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| CN1275638A (en) * | 1993-08-13 | 2000-12-06 | 帝国化学工业公司 | Application of electrolytic cell in preparation of oxygen |
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| CN101880891A (en) * | 2010-04-13 | 2010-11-10 | 大连理工大学 | High-stability DSA anode for preparing chlorine by electrolysis and preparation method thereof |
| CN103210122A (en) * | 2010-11-26 | 2013-07-17 | 德诺拉工业有限公司 | Anode for electrolytic evolution of chlorine |
| CN107002257A (en) * | 2014-11-24 | 2017-08-01 | 德诺拉工业有限公司 | The anode that electrolysis for chlorine is separated out |
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| CN1275638A (en) * | 1993-08-13 | 2000-12-06 | 帝国化学工业公司 | Application of electrolytic cell in preparation of oxygen |
| CN101532147A (en) * | 2009-02-26 | 2009-09-16 | 中国船舶重工集团公司第七二五研究所 | Nanocrystal metal oxide composite electrode and method for preparing same |
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