CN108070877A - It is a kind of for cathode of electrolysis production and preparation method thereof - Google Patents
It is a kind of for cathode of electrolysis production and preparation method thereof Download PDFInfo
- Publication number
- CN108070877A CN108070877A CN201711099000.1A CN201711099000A CN108070877A CN 108070877 A CN108070877 A CN 108070877A CN 201711099000 A CN201711099000 A CN 201711099000A CN 108070877 A CN108070877 A CN 108070877A
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- Prior art keywords
- oxide
- praseodymium
- rhodium
- coating
- cathode
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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 kind of cathodes for electrolysis production.Coating of the cathode by electrode matrix and coated on electrode matrix surface forms, wherein, the coating is made of ru oxide, praseodymium oxide and rhodium oxide, and the load capacity of the ru oxide is calculated as 5~20g/m with Ru2, the load capacity of the praseodymium oxide is calculated as 0.1~5g/m with Pr2, the load capacity of the rhodium oxide is calculated as 0.1~5g/m with Rh2.Compared with existing cathode, cathode of the invention can reach zero weight-loss ratio, so as to extend electrode life.
Description
Technical field
The present invention relates to a kind of for cathode of electrolysis production and preparation method thereof, particularly for chlor-alkali production.
Background technology
Cathode used in traditional chlor-alkali production electrolytic cell is Ru-Ce coated electrodes, i.e., in nickel or nickel-base alloy electrode surface
Coat one layer of Ru：Ce=20-50%：The ruthenium cerium mixed oxide coatings of 80-50%, the coated electrode exist in use
The caducous problem of coating.
CN101029405A discloses a kind of activated cathode, which is in metal mesh sheet matrix surface coating thickness
Up to 10~30 μm of coating, the material of coating include containing cobalt in group VIII metal in the periodic table of elements, nickel, zinc, ruthenium, cadmium, iridium,
One in one of platinum or the metal salt and the periodic table of elements of several in lanthanide series metal lanthanum, cerium, praseodymium or several metal salts and
Inorganic acid or organic acid acidic materials, which has stronger anti-reflective to current capacity, but the combination of coating and matrix is inadequate
Well, electrolytic weight loss rate is higher.
CN102352517A discloses a kind of high-activity cathode, first passes through the transition zone being made of rhodium nitrate and concentrated nitric acid
Coating liquid forms the transition zone of one layer of nickel oxide and rhodium oxide on Ni substrate surface, then forms titanium dioxide on the transition zone
The active layer of ruthenium, cerium oxide and platinum grain, so as to improve the combination of coating and matrix.Its deficiency is, makes in preparation process
With substantial amounts of citric acid, substantial amounts of carbon residue unavoidably is generated in coating so as to influence coating performance, and the oxygen in transition zone
It is that the corrosion of Ni substrate is generated by nickel nitrate to change nickel, and transition zone quality is difficult to control.
The content of the invention
For the above problem present in existing chlor-alkali production cathode, a kind of zero weight-loss ratio of present invention offer is used for electricity
Solve the cathode of production.
To achieve the above object, the present invention provides following technical solution：
A kind of cathode for electrolysis production is made of electrode matrix and the coating coated on electrode matrix surface, wherein,
The coating is made of ru oxide, praseodymium oxide and rhodium oxide, and the load capacity of the ru oxide is calculated as 5~20g/ with Ru
m2, the load capacity of the praseodymium oxide is calculated as 0.1~5g/m with Pr2, the load capacity of the rhodium oxide is calculated as 0.1~5g/ with Rh
m2。
Preferably, the electrode matrix is nickel or nickel-base alloy.
The preparation method of above-mentioned cathode, includes the following steps：
(1) precursor compound of ruthenium, praseodymium and rhodium is dissolved in water, obtains masking liquid；
(2) masking liquid is dried 5~60 minutes coated on electrode matrix in 100~150 DEG C, then at 400~600 DEG C of burnings
System 5~60 minutes；
(3) operation of step (2) is repeated, until ruthenium, praseodymium and rhodium element reach the requirement of the load capacity.
Preferably, the precursor compound of the ruthenium, praseodymium and rhodium is ruthenium trichloride, praseodymium trichloride, rhodium acetate.
Compared with existing cathode, the coating surface compact of coated electrode of the present invention can be in electrolytic process
Reach zero weight-loss ratio, so as to extend electrode life.
Specific embodiment
The technical solution in present invention will be clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
Embodiment 1
The preparation of Ru-Pr-Rh coated electrodes：
Ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode base
Body, pyrolytic aoxidizes after drying.Ruthenium trichloride, praseodymium trichloride and rhodium acetate is made to change into corresponding oxide.In coating,
RuCl3111.1g/L, PrCl323.7g/L, rhodium acetate 21.3g/L.
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 5 minutes through 150 DEG C after coating, then it is (empty by 600 DEG C
Gas) it fires 5 minutes, it repeats above operation, until making ru oxide in coating (in terms of Ru), praseodymium oxide (in terms of Pr) and rhodium oxygen
The load capacity of compound (in terms of Rh) respectively may be about Ru=20.0g/m2, Pr=5.0g/m2, Rh=5.0g/m2。
Embodiment 2
The preparation of Ru-Pr-Rh coated electrodes：
Ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode base
Body, pyrolytic aoxidizes after drying.Ruthenium trichloride, praseodymium trichloride and rhodium acetate is made to change into corresponding oxide.In coating,
RuCl388.24g/L PrCl35.0g/L, rhodium acetate 0.9g/L.
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 5 minutes through 150 DEG C after coating, then it is (empty by 600 DEG C
Gas) it fires 5 minutes, it repeats above operation, until making ru oxide in coating (in terms of Ru), praseodymium oxide (in terms of Pr) and rhodium oxygen
The load capacity of compound (in terms of Rh) respectively may be about Ru=15g/m2, Pr=1.0g/m2, Rh=0.2g/m2。
Embodiment 3
The preparation of Ru-Pr-Rh coated electrodes：
Ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode base
Body, pyrolytic aoxidizes after drying.Ruthenium trichloride, praseodymium trichloride and rhodium acetate is made to change into corresponding oxide.In coating,
RuCl341.67g/L PrCl30.71g/L, rhodium acetate 0.64g/L.
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 5 minutes through 150 DEG C after coating, then it is (empty by 600 DEG C
Gas) it fires 5 minutes, it repeats above operation, until making ru oxide in coating (in terms of Ru), praseodymium oxide (in terms of Pr) and rhodium oxygen
The load capacity of compound (in terms of Rh) respectively may be about Ru=5g/m2, Pr=0.1g/m2, Rh=0.1g/m2。
Embodiment 4
The preparation of Ru-Pr-Rh coated electrodes：
Ruthenium trichloride, praseodymium trichloride and rhodium acetate are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode base
Body, after drying, pyrolytic aoxidizes in air atmosphere.Ruthenium trichloride, praseodymium trichloride and rhodium acetate resolve into phase at high temperature
The oxide answered.In solution, RuCl362.5g/L PrCl32.67g/L, rhodium acetate 0.47g/L.
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 60 minutes through 100 DEG C after coating, then it is (empty by 400 DEG C
Gas) it fires 60 minutes, it repeats above operation, until making ru oxide in coating (in terms of Ru), praseodymium oxide (in terms of Pr) and rhodium
The load capacity of oxide (in terms of Rh) respectively may be about Ru=10g/m2, Pr=0.5g/m2, Rh=0.1g/m2。
Comparative example 1
Compared with Example 4, coating not rhodium-containing is prepared as follows Ru-Pr coated electrodes：
Ruthenium trichloride and praseodymium trichloride are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode matrix, drying
Afterwards, pyrolytic aoxidizes in air atmosphere.Ruthenium trichloride and praseodymium trichloride resolve into corresponding oxidation in air at high temperature
Object.In solution, RuCl362.5g/L PrCl3 2.67g/L。
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 60 minutes through 100 DEG C after coating, then it is (empty by 400 DEG C
Gas) it fires 60 minutes, it repeats above operation, until making bearing for ru oxide in coating (in terms of Ru) and praseodymium oxide (in terms of Pr)
Carrying capacity respectively may be about Ru=10g/m2, Pr=0.5g/m2。
Comparative example 2
Compared with Example 4, coating is free of praseodymium to Ru-Rh coated electrodes, is prepared as follows：
Ruthenium trichloride and rhodium acetate are dissolved in water, and solution after mixing, is painted on conventional nickel screen electrode matrix, drying
Afterwards, pyrolytic aoxidizes in air atmosphere.Ruthenium trichloride and rhodium acetate resolve into corresponding oxide at high temperature.Solution
In, RuCl362.5g/L, rhodium acetate 0.47g/L.
The coated weight of each masking liquid is about 15~25ml/m2, it is dried 60 minutes through 100 DEG C after coating, then it is (empty by 400 DEG C
Gas) it fires 60 minutes, it repeats above operation, until making bearing for ru oxide in coating (in terms of Ru) and rhodium oxide (in terms of Rh)
Carrying capacity respectively may be about Ru=10g/m2, Rh=0.1g/m2。
It is electrolysed test condition：
1st, 450g/L NaOH solutions；
2nd, current density 8000A/m2；
3rd, 85 DEG C of temperature.
Weight-loss ratio is the loss amount of coating after electrolysis 26h and the ratio of electrolysis Front-coating mirror amount.
| Weight-loss ratio (%) | Initial hydrogen-evolution overpotential (V) | |
| Embodiment 1 | 0 | 1.212 |
| Embodiment 4 | 0 | 1.210 |
| Comparative example 1 (Ru-Pr coatings) | 10 | 1.220 |
| Comparative example 2 (Ru-Rh coatings) | 16 | 1.218 |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of cathode for electrolysis production is made of electrode matrix and the coating coated on electrode matrix surface, wherein, institute
It states coating to be made of ru oxide, praseodymium oxide and rhodium oxide, the load capacity of the ru oxide is calculated as 5~20g/ with Ru
m2, the load capacity of the praseodymium oxide is calculated as 0.1~5g/m with Pr2, the load capacity of the rhodium oxide is calculated as 0.1~5g/ with Rh
m2。
2. cathode according to claim 1, it is characterised in that：The electrode matrix is nickel or nickel-base alloy.
3. the preparation method of cathode described in claim 1, includes the following steps：
(1) precursor compound of ruthenium, praseodymium and rhodium is dissolved in water, obtains masking liquid；
(2) masking liquid is dried 5~60 minutes coated on electrode matrix in 100~150 DEG C, fire 5 then at 400~600 DEG C~
60 minutes；
(3) operation of step (2) is repeated, until ruthenium, praseodymium and rhodium element reach the requirement of the load capacity.
4. preparation method according to claim 3, it is characterised in that：The precursor compound of the ruthenium, praseodymium and rhodium is trichlorine
Change ruthenium, praseodymium trichloride, rhodium acetate.
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| CN108070877B CN108070877B (en) | 2020-07-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113755873A (en) * | 2021-09-14 | 2021-12-07 | 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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| 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 |
| CN113755873A (en) * | 2021-09-14 | 2021-12-07 | 沈阳中科惠友科技发展有限责任公司 | Cathode for seawater electrolysis 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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