CN108070877B - Cathode for electrolytic production and preparation method thereof - Google Patents

Cathode for electrolytic production and preparation method thereof Download PDF

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Publication number
CN108070877B
CN108070877B CN201711099000.1A CN201711099000A CN108070877B CN 108070877 B CN108070877 B CN 108070877B CN 201711099000 A CN201711099000 A CN 201711099000A CN 108070877 B CN108070877 B CN 108070877B
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coating
oxide
praseodymium
ruthenium
rhodium
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CN108070877A (en
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胡媛媛
陈晓丽
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Jiangsu Ancan Technology Co ltd
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Jiangsu Ancan Technology Co ltd
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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
    • 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

Abstract

The invention discloses a cathode for electrolytic production. The cathode consists of an electrode substrate and a coating coated on the surface of the electrode substrate, wherein the coating consists of ruthenium oxide, praseodymium oxide and rhodium oxide, and the loading amount of the ruthenium oxide is 5-20 g/m in terms of Ru2The loading amount of the praseodymium oxide is 0.1-5 g/m in terms of Pr2The loading amount of the rhodium oxide is 0.1-5 g/m calculated as Rh2. Compared with the existing cathode coating, the cathode coating of the invention can reach zero weight loss rate, thereby prolonging the service life of the electrode.

Description

Cathode for electrolytic production and preparation method thereof
Technical Field
The invention relates to a cathode for electrolytic production and a preparation method thereof, in particular to a cathode for chlor-alkali production.
Background
The cathode used in the traditional chlor-alkali production electrolytic cell is a Ru-Ce coated electrode, namely a layer of Ru is coated on the surface of a nickel or nickel-based alloy electrode: 20-50% of Ce: 80-50% of ruthenium-cerium mixed oxide coating, and the coating electrode has the problem that the coating is easy to fall off in the using process.
CN101029405A discloses an active cathode, which is a coating with a thickness of 10-30 μm coated on the surface of a metal mesh substrate, wherein the coating is made of metal salt containing one or more of cobalt, nickel, zinc, ruthenium, cadmium, iridium and platinum in VIII group metals in the periodic table, one or more of lanthanum, cerium and praseodymium in lanthanide series metals in the periodic table, and inorganic acid or organic acid acidic substances.
CN102352517A discloses a high activity cathode, which is prepared by forming a transition layer of nickel oxide and rhodium oxide on the surface of a nickel substrate through a transition layer coating solution composed of rhodium nitrate and concentrated nitric acid, and then forming an active layer of ruthenium dioxide, cerium oxide and platinum particles on the transition layer, thereby improving the bonding of the coating and the substrate. The method has the defects that a large amount of citric acid is used in the preparation process, so that the influence on the coating performance caused by a large amount of carbon residue generated on the coating cannot be avoided, nickel oxide in the transition layer is generated by the corrosion of nickel nitrate on a nickel substrate, and the quality of the transition layer is not easy to control.
Disclosure of Invention
Aiming at the problems of the cathode for producing the chlor-alkali, the invention provides the cathode for electrolytic production with zero weight loss rate.
In order to achieve the purpose, the invention provides the following technical scheme:
the cathode for electrolytic production consists of an electrode substrate and a coating coated on the surface of the electrode substrate, wherein the coating consists of ruthenium oxide, praseodymium oxide and rhodium oxide, and the loading amount of the ruthenium oxide is 5-20 g/m in terms of Ru2The loading amount of the praseodymium oxide is 0.1-5 g/m in terms of Pr2The loading amount of the rhodium oxide is 0.1-5 g/m calculated as Rh2。
Preferably, the electrode substrate is nickel or a nickel-based alloy.
The preparation method of the cathode comprises the following steps:
(1) dissolving precursor compounds of ruthenium, praseodymium and rhodium in water to obtain a coating liquid;
(2) coating the coating liquid on an electrode substrate, drying for 5-60 minutes at 100-150 ℃, and firing for 5-60 minutes at 400-600 ℃;
(3) and (3) repeating the operation of the step (2) until the ruthenium, praseodymium and rhodium elements meet the requirement of the loading amount.
Preferably, the precursor compounds of ruthenium, praseodymium and rhodium are ruthenium trichloride, praseodymium trichloride and rhodium acetate.
Compared with the existing cathode coating, the coating surface of the coating electrode is compact and compact, and the zero weight loss rate can be achieved in the electrolytic process, so that the service life of the electrode is prolonged.
Detailed Description
The technical solutions in the present disclosure will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a Ru-Pr-Rh coating electrode:
ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, the solution is coated on a conventional nickel screen electrode substrate after being uniformly mixed, and the nickel screen electrode substrate is dried and then decomposed and oxidized at high temperature. So that the ruthenium trichloride, the praseodymium trichloride and the rhodium acetate are converted into corresponding oxides. In the coating, RuCl3111.1g/L，PrCl323.7g/L and 21.3g/L of rhodium acetate.
The coating amount of each coating liquid is about 15-25 ml/m2Drying at 150 ℃ for 5 minutes after coating, baking at 600 ℃ (air) for 5 minutes, and repeating the above operations until the loading amounts of ruthenium oxide (calculated as Ru), praseodymium oxide (calculated as Pr) and rhodium oxide (calculated as Rh) in the coating are respectively about 20.0g/m2、Pr＝5.0g/m2、Rh＝5.0g/m2。
Example 2
Preparing a Ru-Pr-Rh coating electrode:
ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, the solution is coated on a conventional nickel screen electrode substrate after being uniformly mixed, and the nickel screen electrode substrate is dried and then decomposed and oxidized at high temperature. So that the ruthenium trichloride, the praseodymium trichloride and the rhodium acetate are converted into corresponding oxides. In the coating, RuCl388.24g/L，PrCl35.0g/L and rhodium acetate 0.9 g/L.
The coating amount of each coating liquid is about 15-25 ml/m2Drying at 150 ℃ for 5 minutes after coating, baking at 600 ℃ (air) for 5 minutes, and repeating the above operations until the loading amounts of ruthenium oxide (calculated as Ru), praseodymium oxide (calculated as Pr) and rhodium oxide (calculated as Rh) in the coating are respectively about 15g/m Ru2、Pr＝1.0g/m2、Rh＝0.2g/m2。
Example 3
Preparing a Ru-Pr-Rh coating electrode:
ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, the solution is coated on a conventional nickel screen electrode substrate after being uniformly mixed, and the nickel screen electrode substrate is dried and then decomposed and oxidized at high temperature. So that the ruthenium trichloride, the praseodymium trichloride and the rhodium acetate are converted into corresponding oxides. In the coating, RuCl341.67g/L，PrCl30.71g/L and 0.64g/L of rhodium acetate.
The coating amount of each coating liquid is about 15-25 ml/m2Drying at 150 ℃ for 5 minutes after coating, baking at 600 ℃ (air) for 5 minutes, and repeating the above operations until the loading amounts of ruthenium oxide (calculated as Ru), praseodymium oxide (calculated as Pr) and rhodium oxide (calculated as Rh) in the coating are respectively about 5g/m Ru2、Pr＝0.1g/m2、Rh＝0.1g/m2。
Example 4
Preparing a Ru-Pr-Rh coating electrode:
ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, the solution is coated on a conventional nickel screen electrode substrate after being uniformly mixed, and the nickel screen electrode substrate is dried and then is subjected to pyrolysis and oxidation in the air atmosphere. Ruthenium trichloride, praseodymium trichloride and rhodium acetate are decomposed into corresponding oxides at high temperature. In solution, RuCl362.5g/L，PrCl32.67g/L and rhodium acetate 0.47 g/L.
The coating amount of each coating liquid is about 15-25 ml/m2Drying the coating at 100 ℃ for 60 minutes after coating, then firing the coating at 400 ℃ (air) for 60 minutes, and repeating the operation till the loading amounts of ruthenium oxide (calculated as Ru), praseodymium oxide (calculated as Pr) and rhodium oxide (calculated as Rh) in the coating are respectively about 10g/m (Ru) ° 10g/m2、Pr＝0.5g/m2、Rh＝0.1g/m2。
Comparative example 1
Compared with the Ru-Pr coating electrode in example 4, the Ru-Pr coating electrode has no rhodium, and is prepared specifically as follows:
ruthenium trichloride and praseodymium trichloride are dissolved in water, the solution is coated on a conventional nickel screen electrode substrate after being uniformly mixed, and the nickel screen electrode substrate is dried and then is subjected to pyrolysis and oxidation in the air atmosphere. Ruthenium trichloride and praseodymium trichloride decompose to the corresponding oxides at high temperatures in air. In solution, RuCl362.5g/L，PrCl32.67g/L。
The coating amount of each coating liquid is about 15-25 ml/m2Drying at 100 ℃ for 60 minutes after coating, baking at 400 ℃ (air) for 60 minutes, and repeating the above operations until the loading amounts of ruthenium oxide (calculated as Ru) and praseodymium oxide (calculated as Pr) in the coating are respectively about 10g/m2、Pr＝0.5g/m2。
Comparative example 2
Compared with the Ru-Rh coated electrode in example 4, the coating does not contain praseodymium, and is specifically prepared as follows:
dissolving ruthenium trichloride and rhodium acetate in water, uniformly mixing the solution, coating the solution on a conventional nickel screen electrode substrate, drying, and carrying out pyrolysis and oxidation in an air atmosphere. Ruthenium trichloride and rhodium acetate decompose at high temperatures to the corresponding oxides. In solution, RuCl362.5g/L and 0.47g/L of rhodium acetate.
The coating amount of each coating liquid is about 15-25 ml/m2After coating, drying at 100 ℃ for 60 minutes, then firing at 400 ℃ (air) for 60 minutes, and repeating the above operations until the loading of ruthenium oxide (calculated as Ru) and rhodium oxide (calculated as Rh) in the coating is about Ru to 10g/m2、Rh＝0.1g/m2。
Electrolytic test conditions:
1. 450g/L NaOH solution;
2. current density 8000A/m2；
3. The temperature was 85 ℃.
The weight loss ratio is the ratio of the loss amount of the coating after electrolysis for 26h to the amount of the coating before electrolysis.
Weight loss ratio (%) Initial hydrogen evolution potential (V)
Example 1 0 1.212
Example 4 0 1.210
COMPARATIVE EXAMPLE 1 (Ru-Pr coating) 10 1.220
COMPARATIVE EXAMPLE 2 (Ru-Rh coating) 16 1.218
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (3)

1. The cathode for electrolytic production consists of an electrode substrate and a coating coated on the surface of the electrode substrate, wherein the coating consists of ruthenium oxide, praseodymium oxide and rhodium oxide, and the loading amount of the ruthenium oxide is 10g/m in terms of Ru2The load amount of the praseodymium oxide is 0.5g/m in terms of Pr2The supported amount of the rhodium oxide is 0.1g/m in terms of Rh2；
The electrode substrate is nickel or nickel-based alloy.
2. The method of preparing the cathode of claim 1, comprising the steps of:
(1) dissolving precursor compounds of ruthenium, praseodymium and rhodium in water to obtain a coating liquid;
(2) coating the coating liquid on an electrode substrate, drying for 5-60 minutes at 100-150 ℃, and firing for 5-60 minutes at 400-600 ℃;
(3) and (3) repeating the operation of the step (2) until the ruthenium, praseodymium and rhodium elements meet the requirement of the loading amount.
3. The method of claim 2, wherein: the precursor compounds of ruthenium, praseodymium and rhodium are ruthenium trichloride, praseodymium trichloride and rhodium acetate.
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CN108998807A (en) * 2018-06-28 2018-12-14 江苏安凯特科技股份有限公司 A kind of improved Ru-Ce coated electrode
CN112941550A (en) * 2019-11-25 2021-06-11 蓝星(北京)化工机械有限公司 Cathode bottom net for zero polar distance electrolytic bath cathode and preparation method thereof
CN115725997A (en) * 2021-08-25 2023-03-03 蓝星(北京)化工机械有限公司 High current density electrolytic active cathode and preparation method thereof
CN113755873B (en) * 2021-09-14 2024-02-09 沈阳中科惠友科技发展有限责任公司 Cathode for seawater electrolysis and preparation method thereof

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