CN114643187A - Nickel cathode active coating of ion-exchange membrane electrolytic cell and nickel cathode surface treatment method - Google Patents
Nickel cathode active coating of ion-exchange membrane electrolytic cell and nickel cathode surface treatment method Download PDFInfo
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- CN114643187A CN114643187A CN202210244087.1A CN202210244087A CN114643187A CN 114643187 A CN114643187 A CN 114643187A CN 202210244087 A CN202210244087 A CN 202210244087A CN 114643187 A CN114643187 A CN 114643187A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
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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
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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
- C25B15/00—Operating or servicing cells
Abstract
The invention belongs to the technical field of chemical industry, and discloses a nickel cathode active coating of an ionic membrane electrolytic cell and a nickel cathode surface treatment method, wherein the nickel cathode surface is cleaned, and corresponding raw materials are weighed according to mass percentage; mixing the raw materials, ball-milling the mixture on a ball mill to form a powdery mixture, and controlling the granularity of the mixture within a certain range; adding varnish and banana oil, and treating to obtain a coating; and brushing the coating on the surface of the nickel cathode, and naturally drying to finish the treatment of the nickel cathode. The invention uses nickel oxide to form a protective layer to protect the nickel surface and prevent the nickel cathode from absorbing hydrogen; meanwhile, the combination of silicon dioxide, ruthenium dioxide, aluminum oxide and radium oxide can form a stabilizer to protect NiO, so that NiO can be effectively prevented from being reduced by hydrogen, and the problem that hydrogen overvoltage gradually rises is solved.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a nickel cathode active coating of an ion-exchange membrane electrolyzer and a nickel cathode surface treatment method.
Background
The electrolytic bath is used as a core production device in the downstream customer production link and is a place for generating electrolytic chemical reaction. The electrolytic cell is a device for converting electric energy into chemical energy, and electrolysis refers to a process in which current passes through an electrolyte solution to generate electrochemical reaction at an electrode terminal. In recent years, the production process of the Chinese caustic soda market is obviously changed, and the proportion of the ionic membrane caustic soda is continuously increased. In 2019, the yield of the ionic membrane caustic soda in China is 4, 245 ten thousand tons, the proportion of the ionic membrane caustic soda is 55%, and the proportion of the membrane caustic soda is reduced to 25%. As far as 2020, China still has 13.5 million tons of diaphragm soda, except for delayed elimination of partial self-service application, the diaphragm soda has high energy consumption and inferior product quality to that of ionic membrane soda, and gradually quits the caustic soda market according to the market law. With the popularization and application of the ion membrane electrolytic cell, the update iteration market of the ion membrane electrolytic cell is gradually expanded, and the requirement of periodic replacement of corresponding equipment and parts also presents an increasing trend year by year. At present, compared with the traditional alkali-making process diaphragm method and mercury method, the ionic membrane electrolytic cell technology has the advantages of energy conservation, high product quality and no mercury and asbestos pollution, so the ionic membrane electrolytic cell technology is considered to be the most advanced and economically reasonable sodium hydroxide production method in the world. The foreign ionic membrane electrolytic cell technology is relatively mature, and mainly comprises the following steps: asahi chemical, Asahi glass, chlorine engineering, Western American systems, England ICI, Germany Wood company, Japan. The technology is strictly kept secret abroad, and only one enterprise Beijing chemical machinery plant which cooperates with the Asahi Kasei corporation in Japan has production capacity at present at home. One of the difficulties in producing ion membrane electrolyzers is the titanium anode and nickel cathode coating technology; the other is ionic membrane technology. At present, the titanium anode coating technology is transparent; the ionic membrane can be solved by an import solution due to long service life; the nickel cathode coating technology is difficult to overcome, the import is expensive, the service life is short, and the technology in China needs to be improved urgently. The technical difficulty of the ion membrane electrolytic cell alkali making is mainly as follows: the nickel cathode has a tendency of absorbing and releasing hydrogen during electrolysis, so that hydrogen overvoltage is increased to cause damage of an ion membrane, and the problem is generally solved by using a coating technology abroad. The coating technology is difficult to overcome in China, the cost of the imported nickel cathode is too high, and the service life is short, so that the ion membrane electrolytic cell cannot be produced in batches.
Through the above analysis, the problems and defects of the prior art are as follows: in the prior art, a nickel cathode has a tendency of adsorbing and releasing hydrogen during electrolysis, so that hydrogen overvoltage is increased, and an ionic membrane is easily damaged.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nickel cathode active coating of an ionic membrane electrolytic cell and a nickel cathode surface treatment method.
The invention is realized in such a way, and the nickel cathode active coating and the nickel cathode surface treatment method of the ionic membrane electrolytic cell comprise the following steps:
cleaning the surface of a nickel cathode, and weighing corresponding raw materials according to mass percentage;
mixing the raw materials, performing ball milling on the mixture on a ball mill to form a powdery mixture, and controlling the granularity of the mixture within a certain range;
adding varnish and banana oil, and treating to obtain a coating; and brushing the coating on the surface of the nickel cathode, and naturally drying to finish the treatment of the nickel cathode.
Further, the corresponding raw materials are weighed according to the mass percentage respectively as follows: NiO, SiO2、RuO2、Al2O3、RaO。
Further, the NiO and SiO2、RuO2、Al2O3The RaO comprises the following components in percentage by mass: NiO 43-64%, SiO211％-20％，RuO26％-11％，Al2O34％-10％，RaO 1％-6％。
Further, the NiO and SiO2、RuO2、Al2O3The RaO comprises the following components in percentage by mass: NiO 59% -62%, SiO2 15％-20％，RuO2 8％-11％，Al2O3 5％-10％，RaO 3％-6％。
Further, in the second step, the particle size of the mixture is 250-350 meshes.
Further, in the third step, the coating paint is brushed on the surface of the nickel cathode to a thickness of 0.3 mm.
Further, in the third step, the adding of the varnish and the banana oil for treatment specifically comprises: stirring to a suitable viscosity.
The invention also aims to provide the application of the active coating of the nickel cathode of the ionic membrane electrolytic cell and the surface treatment method of the nickel cathode in the production of sodium hydroxide.
The invention also aims to provide the application of the nickel cathode active coating and the nickel cathode surface treatment method in protecting the nickel surface and preventing the nickel cathode from adsorbing hydrogen.
The invention also aims to provide the application of the active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode in protecting NiO and preventing NiO from being reduced by hydrogen.
In combination with the technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with the technical scheme to be protected and the results and data in the research and development process, and some creative technical effects brought after the problems are solved are analyzed in detail and deeply. The specific description is as follows:
the invention uses nickel oxide to form a protective layer to protect the nickel surface and prevent the nickel cathode from absorbing hydrogen; meanwhile, the combination of silicon dioxide, ruthenium dioxide, aluminum oxide and radium oxide can form a stabilizer to protect NiO, so that NiO can be effectively prevented from being reduced by hydrogen, and the problem that hydrogen overvoltage gradually rises is solved. The nickel oxide NiO in the coating forms a complete adhesion system, and the hydrogen released during the electrolysis of the nickel cathode is mainly prevented from being adsorbed. Experiments have shown that this material is the most dominant material for preventing hydrogen from forming high potentials.
Secondly, considering the technical scheme as a whole or from the perspective of products, the technical effect and advantages of the technical scheme to be protected by the invention are specifically described as follows: the active coating of nickel cathode of ion-exchange membrane electrolyzer and the surface treatment method of nickel cathode are the key protective measures for ion-exchange membrane. The service life of the nickel cathode without the coating is only 1 year, and can reach 6 years after being used.
Third, as an inventive supplementary proof of the claims of the present invention, there are also presented several important aspects:
(1) the expected income and commercial value after the technical scheme of the invention is converted are as follows:
the active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode are key protective measures for the use of the ion-exchange membrane, and can effectively ensure the service life of the nickel cathode. After the patent is implemented, the expected annual output reaches 1 ton, the annual sales amount reaches 100 ten thousand yuan, the product can quickly enter the market, and the blank of the domestic market is compensated.
(2) The technical scheme of the invention fills the technical blank in the industry at home and abroad: nickel cathode coating technology.
(3) The technical scheme of the invention solves the technical problems which are always desired to be solved but are not successfully achieved: the service life of the nickel cathode without the coating is only 1 year, and can reach 6 years after being used.
(4) The technical scheme of the invention overcomes the technical prejudice that: the use of the coating in an ion membrane electrolysis cell.
Drawings
FIG. 1 is a flow chart of the active coating of nickel cathode and the surface treatment method of nickel cathode in the ion membrane electrolyzer provided by the embodiment of the invention.
FIG. 2 is a graphical representation of the results of a nickel cathode coating test provided by an embodiment of the present invention.
FIG. 3 is a schematic diagram of a nickel cathode of a comparative example provided in the examples of the present invention.
FIG. 4 is a schematic diagram of a nickel cathode according to an embodiment of the present invention.
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.
First, an embodiment is explained. This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
As shown in fig. 1, the method for processing the nickel cathode active coating and the nickel cathode surface of the ionic membrane electrolyzer provided by the embodiment of the invention comprises:
s101: cleaning the surface of the nickel cathode, weighing NiO and SiO according to the mass percentage2、RuO2、Al2O3、RaO；
S102: mixing the raw materials, ball-milling the mixture on a ball mill to form a powdery mixture, and controlling the granularity of the mixture within a certain range;
s103: adding varnish and banana oil, and stirring to a proper viscosity to obtain a coating; and brushing the coating on the surface of the nickel cathode, and naturally drying to finish the treatment of the nickel cathode.
In S101 provided by the embodiment of the invention, NiO and SiO2、RuO2、Al2O3The RaO comprises the following components in percentage by mass: NiO 43-64%, SiO211％-20％，RuO26％-11％，Al2O34％-10％，RaO 1％-6％。
In S101 provided by the embodiment of the invention, NiO and SiO2、RuO2、Al2O3The RaO comprises the following components in percentage by mass: NiO 59% -62%, SiO215％-20％，RuO28％-11％，Al2O35％-10％，RaO 3％-6％。
In the S102 provided in the embodiment of the present invention, the particle size of the mixture is 250-350 mesh.
In S103 provided by the embodiment of the invention, the coating paint is brushed on the surface of the nickel cathode to have a thickness of 0.3 mm.
Example 1
Cleaning the surface of the nickel cathode; weighing NiO according to the mass percentage62％，SiO215％，RuO210％，Al2O38 percent, RaO 5 percent; then mixing the raw materials, and carrying out ball milling on the mixture on a ball mill to form a powdery mixture, wherein the granularity is 250-350 meshes; and adding varnish and banana oil, stirring to a proper viscosity to prepare a coating, brushing the coating on the surface of the nickel cathode to a thickness of about 0.3mm, and naturally drying to finish the treatment of the nickel cathode.
Example 2
Cleaning the surface of the nickel cathode; weighing NiO 60% and SiO according to the mass percentage218％，RuO210％，Al2O38 percent, RaO 4 percent; then mixing the raw materials, and carrying out ball milling on the mixture on a ball mill to form a powdery mixture, wherein the granularity is 250-350 meshes; and adding varnish and banana oil, stirring to a proper viscosity to prepare a coating, brushing the coating on the surface of the nickel cathode to a thickness of about 0.3mm, and naturally drying to finish the treatment of the nickel cathode.
Example 3
Cleaning the surface of the nickel cathode; weighing NiO 59 percent and SiO according to the mass percentage220％，RuO211％，Al2O37 percent of RaO 3 percent; then mixing the raw materials, and carrying out ball milling on the mixture on a ball mill to form a powdery mixture, wherein the granularity is 250-350 meshes; and adding varnish and banana oil, stirring to a proper viscosity to prepare a coating, brushing the coating on the surface of the nickel cathode to a thickness of about 0.3mm, and naturally drying to finish the treatment of the nickel cathode.
Second, evidence of the relevant effects of the examples. The embodiment of the invention achieves some positive effects in the process of research and development or use, and has great advantages compared with the prior art, and the following contents are described by combining data, diagrams and the like in the test process.
The nickel cathode treated in the example 1-the nickel cathode untreated in the example 3 and the sample cell were put into an ion membrane electrolysis cell, after the installation, the secondary refined salt solution was introduced into the anode, the NaOH dilute solution was introduced into the cathode, and after 1 hour of operation, the electrode potentials were as shown in Table 1:
TABLE 1 test results of prototype
The electrode potential is general data for detecting the hydrogen potential on the surface of the nickel cathode, and the qualified standard of the electrode potential is generally less than or equal to 1.25. As is evident from table 1, the electrode potential through the nickel cathode active coating meets the quality requirements; the coating can lead the service life of the nickel cathode to reach 10 years after test.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (10)
1. The nickel cathode active coating and the nickel cathode surface treatment method for the ionic membrane electrolytic cell are characterized by comprising the following steps:
cleaning the surface of a nickel cathode, and weighing corresponding raw materials according to mass percentage;
mixing the raw materials, performing ball milling on the mixture on a ball mill to form a powdery mixture, and controlling the granularity of the mixture within a certain range;
adding varnish and banana oil, and treating to obtain a coating; and brushing the coating on the surface of the nickel cathode, and naturally drying to finish the treatment of the nickel cathode.
2. The active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode of claim 1, wherein the corresponding raw materials are weighed according to the mass percentage respectively as follows: NiO, SiO2、RuO2、Al2O3、RaO。
3. Such as rightThe active coating for nickel cathode of ion-exchange membrane electrolyzer and the method for treating the surface of nickel cathode of claim 2, wherein said NiO and SiO are2、RuO2、Al2O3The RaO comprises the following components in percentage by mass:
NiO 43％-64％，SiO2 11％-20％，RuO2 6％-11％，Al2O3 4％-10％，RaO 1％-6％。
4. the active coating for nickel cathode of ion-exchange membrane electrolyzer of claim 2 and the method for surface treatment of nickel cathode of the electrolyzer of claim 2, wherein said NiO, SiO2、RuO2、Al2O3The RaO comprises the following components in percentage by mass:
NiO 59％-62％，SiO2 15％-20％，RuO2 8％-11％，Al2O3 5％-10％，RaO 3％-6％。
5. the active coating for nickel cathode of ion-exchange membrane electrolyzer and the method for treating the surface of nickel cathode as claimed in claim 1, wherein in the second step, the particle size of the mixture is 250-350 mesh.
6. The active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode of claim 1, wherein in the third step, the coating paint is brushed on the surface of the nickel cathode to a thickness of 0.3 mm.
7. The active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode of claim 1, wherein in the third step, the addition of the varnish and the banana oil for treatment specifically comprises: stirring to a suitable viscosity.
8. The use of the active coating of a nickel cathode for an ion-exchange membrane cell according to any one of claims 1 to 7 and of a method for the surface treatment of a nickel cathode in the production of sodium hydroxide.
9. The use of the active coating of nickel cathode of an ion-exchange membrane electrolyzer according to any one of claims 1 to 7 and of the method for treating the surface of a nickel cathode for protecting the surface of nickel and preventing the nickel cathode from adsorbing hydrogen.
10. The application of the active coating of the nickel cathode of the ion-exchange membrane electrolyzer and the surface treatment method of the nickel cathode in protecting NiO and preventing NiO from being reduced by hydrogen.
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| CN202210244087.1A CN114643187A (en) | 2022-03-10 | 2022-03-10 | Nickel cathode active coating of ion-exchange membrane electrolytic cell and nickel cathode surface treatment method |
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| CN202210244087.1A CN114643187A (en) | 2022-03-10 | 2022-03-10 | Nickel cathode active coating of ion-exchange membrane electrolytic cell and nickel cathode surface treatment method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0129088A1 (en) * | 1983-06-21 | 1984-12-27 | SIGRI GmbH | Cathode for aqueous electrolysis |
| CN103014751A (en) * | 2012-12-28 | 2013-04-03 | 北京化工大学 | Active cathode and preparation method thereof |
| CN114008249A (en) * | 2020-01-09 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
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2022
- 2022-03-10 CN CN202210244087.1A patent/CN114643187A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0129088A1 (en) * | 1983-06-21 | 1984-12-27 | SIGRI GmbH | Cathode for aqueous electrolysis |
| CN103014751A (en) * | 2012-12-28 | 2013-04-03 | 北京化工大学 | Active cathode and preparation method thereof |
| CN114008249A (en) * | 2020-01-09 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
Non-Patent Citations (1)
| Title |
|---|
| 程殿彬主编: "《科学史上的动人时刻 伟大的走钢丝者》", vol. 3, 天津科学技术出版社, pages: 174 * |
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