CN101469434A - Active anode for hydrochloric acid electrolysis and preparation thereof - Google Patents
Active anode for hydrochloric acid electrolysis and preparation thereof Download PDFInfo
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- CN101469434A CN101469434A CNA2007103047090A CN200710304709A CN101469434A CN 101469434 A CN101469434 A CN 101469434A CN A2007103047090 A CNA2007103047090 A CN A2007103047090A CN 200710304709 A CN200710304709 A CN 200710304709A CN 101469434 A CN101469434 A CN 101469434A
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Abstract
The invention provides an active anode for hydrochloric acid electrolysis. A metallic matrix is coated with an active coating, preferably a metallic matrix of titanium, nickel or titanium palladium alloy; the active coating comprises one or more of VIII family metal salt in periodic table of elements, preferably cobalt, nickel, palladium, ruthenium, iridium or platinum salt, one or more of IV family metal salt in the periodic table of elements, preferably titanium salt or zircon salt, and inorganic acid, preferably hydrochloric acid or sulfuric acid, wherein the metal content of the VIII family metal salt is 100 to 200 grams/liter; the metal content of the IV family metal salt is 30 to 70 grams/liter; and the concentration of the inorganic acid is 50 to 100 grams/liter. The active anode is prepared by coating the active coating on the metallic matrix through thermal dissociation. The active anode for hydrochloric acid electrolysis has stable performance, good electricity-saving effect, longer service life, simple manufacturing process and evenly distributed coating.
Description
Technical field
The present invention relates to a kind of active anode, particularly relate to a kind of active anode that is used for electrolysis of hydrochloric acid, but also relate to the preparation method of this active anode.
Background technology
Having put down in writing many anodes that are used for electrolysis of hydrochloric acid in the prior art document, as a carbon based anode, is to be coated with the material of tool catalytic activity and the anode that makes on carbon back; The B anode is made of corrosion-resistant substrate, and has used a kind of coating of electrochemical activity thereon; The powder that c will have electrochemical activity at conductive base by thermospray is coated onto on the carrier or the like.The experiment of carrying out at conventional anode shows that after having passed through one period short duration of service, the active layer of carrier will peel off.Reason is that the bonding force between carrier and the active layer is poor on the one hand, between active layer and carrier corrosion has taken place on the other hand, and this corrosion makes the bonding state between active layer and the carrier worsen more, thus the destruction that causes anode coating.
It is before applying catalytic active layer a special middle layer to be set on anode to also have a kind of anode in addition, this middle layer is made up of titanium carbide and titanium boride and is coated on the carrier by flame plating or plasma spraying, this electrode has good stability, but manufacturing process is comparatively complicated.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of active anode that is used for electrolysis of hydrochloric acid, this active anode stable performance, and long service life, the bonding force of base material and activated coating is good, and coating is evenly distributed, and the manufacturing process of this active anode is simple.
For solving the problems of the technologies described above, the invention provides a kind of active anode that is used for electrolysis of hydrochloric acid, wherein, on metallic matrix, be coated with activated coating, be preferably titanium, nickel or titanium palldium alloy metallic matrix, this activated coating comprises: in the periodic table of elements in the VIII family metal-salt one or several, be preferably cobalt, nickel, palladium, ruthenium, iridium or platinum salt, and wherein metal content is 100～200 grams per liters; In the periodic table of elements in the IV family metal-salt one or several is preferably titanium or zirconates, and wherein metal content is 30～70 grams per liters; Mineral acid is preferably hydrochloric acid or sulfuric acid, and concentration is 50～100 grams per liters.
The above-mentioned active anode that is used for electrolysis of hydrochloric acid, wherein, the thickness of described activated coating is 10 μ m～30 μ m.
The present invention also provides a kind of preparation method of above-mentioned active anode, comprises the steps:
A) pre-treatment is with the metal base surface oil removing;
B) preparation activated coating;
C) thermal dissociation is coated on activated coating on the metallic matrix, burns in containing the atmosphere of oxygen and applies and burn till.
The preparation method of above-mentioned active anode, wherein, described step a) also comprises anneal, and annealing temperature is 400～750 ℃, and the treatment time is 1～2 hour.
The preparation method of above-mentioned active anode, wherein, described step a) also comprises the chemical erosion processing after anneal, and used acid is the sulfuric acid of 10 grams per liters～60 grams per liter weight, and temperature is 50 ℃ of extremely boilings, and be 1～6 hour duration of contact.
The preparation method of above-mentioned active anode, wherein, the thermal dissociation condition of described step c) is:
Dry: 20～200 ℃ of 5～30 minutes times of temperature;
Burn and apply: 300～600 ℃ of 10～50 minutes times of temperature;
Burn till: 400～700 ℃ of 10～120 minutes times of temperature.
The active anode that is used for electrolysis of hydrochloric acid of the present invention, stable performance have good electricity-saving effect and long work-ing life, and manufacturing process is simple, and coating is evenly distributed.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
With removers the greasy dirt on titanium net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 400 ℃, and the treatment time is 2 hours.After annealing, in 70 ℃, the sulphuric acid soln of 30 grams per liter weight, placed 4 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 80 grams per liters;
Iridic chloride 90 grams per liters;
Titanium tetrachloride 40 grams per liters;
Hydrochloric acid 70 grams per liters.
40 ℃ of dryings after 30 minutes, sample is placed in the stove with 400 ℃ of heating 15 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 10 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 400 ℃ 50 minutes.
Embodiment two
With removers the greasy dirt on titanium net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 600 ℃, and the treatment time is 1.5 hours.After annealing, in 50 ℃, the sulphuric acid soln of 60 grams per liter weight, placed 1 hour, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 100 grams per liters;
Titanium tetrachloride 30 grams per liters;
Hydrochloric acid 50 grams per liters.
100 ℃ of dryings after 15 minutes, sample is placed in the stove with 600 ℃ of heating 40 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 20 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 600 ℃ 10 minutes.
Embodiment three
With removers the greasy dirt on titanium palldium alloy net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 700 ℃, and the treatment time is 1 hour.After annealing, in the vitriolic boiling solution of 40 grams per liter weight, placed 5 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 125 grams per liters;
Iridic chloride 75 grams per liters;
Titanium tetrachloride 70 grams per liters;
Sulfuric acid 80 grams per liters.
20 ℃ of dryings after 30 minutes, sample is placed in the stove with 300 ℃ of heating 50 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 25 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 400 ℃ 120 minutes.
Embodiment four
With removers the greasy dirt on titanium palldium alloy net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 750 ℃, and the treatment time is 1.5 hours.After annealing, in the vitriolic boiling solution of 10 grams per liter weight, placed 6 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 90 grams per liters;
Iridic chloride 50 grams per liters;
Zirconium tetrachloride 60 grams per liters;
Hydrochloric acid 70 grams per liters.
200 ℃ of dryings after 5 minutes, sample is placed in the stove with 500 ℃ of heating 20 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 30 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 500 ℃ 80 minutes.
Metal active anode provided by the invention, through usefulness JSM-840 type scanning electronic microscope, VANTAGE, the D14105 energy dispersive spectrometry is measured the structure of this its coating, show the multi-hole type lamellar structure that this coating is made up of the crystal grain that varies in size, surface-area is big.
Performance to the active anode of the foregoing description detects in the laboratory, and its detected result is as follows:
1. chlorine evolution potential: (judging the important indicator of anode performance quality), its test result sees Table one.
Testing conditions:
Concentration of hydrochloric acid solution 16%
60 ℃ of temperature
Current density 2,3,3.6,4,5KA/m
2
2. several different anodes are 3KA/m at 60 ℃, 16% hydrochloric acid, current density
2Under loss of weight experiment, test result sees Table two.
As can be seen, the current potential of test piece 1 active anode is lower, and has higher work-ing life from table two.
From above embodiment detected result as can be seen, more than the active anode of each embodiment under each current density, current potential all can reach requirement, and the current potential of embodiment four is low than the current potential of embodiment one, two, three, more power saving, intensified electrolysis weightlessness is less.
Table two
Claims (10)
1, a kind of active anode that is used for electrolysis of hydrochloric acid is characterized in that, is coated with activated coating on metallic matrix, and this activated coating comprises:
In the periodic table of elements in the VIII family metal-salt one or several, wherein metal content is 100～200 grams per liters;
In the periodic table of elements in the IV family metal-salt one or several, wherein metal content is 30～70 grams per liters;
Mineral acid, concentration are 50～100 grams per liters.
2, active anode as claimed in claim 1 is characterized in that, described metallic matrix is titanium, nickel or titanium palldium alloy.
3, active anode as claimed in claim 1 or 2 is characterized in that, the thickness of described activated coating is 10 μ m～30 μ m.
4, active anode as claimed in claim 1 or 2 is characterized in that, described VIII family metal-salt is cobalt, nickel, palladium, ruthenium, iridium or platinum salt.
5, active anode as claimed in claim 1 is characterized in that, described IV family metal-salt is titanium or zirconates.
6, active anode as claimed in claim 1 or 2 is characterized in that, described mineral acid is hydrochloric acid or sulfuric acid.
7, the preparation method of the described active anode of a kind of claim 1 is characterized in that, comprises the steps:
A) pre-treatment is with the metal base surface oil removing;
B) preparation activated coating;
C) thermal dissociation is coated on activated coating on the metallic matrix, burns in containing the atmosphere of oxygen and applies and burn till.
8, method as claimed in claim 7 is characterized in that, described step a) also comprises anneal, and annealing temperature is 400～750 ℃, and the treatment time is 1～2 hour.
9, method as claimed in claim 8 is characterized in that, described step a) also comprises the chemical erosion processing after anneal, and used acid is the sulfuric acid of 10 grams per liters～60 grams per liter weight, and temperature is 50 ℃ of extremely boilings, and be 1～6 hour duration of contact.
10, method as claimed in claim 7 is characterized in that, the thermal dissociation condition of described step c) is:
Dry: 20～200 ℃ of 5～30 minutes times of temperature;
Burn and apply: 300～600 ℃ of 10～50 minutes times of temperature;
Burn till: 400～700 ℃ of 10～120 minutes times of temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103047090A CN101469434A (en) | 2007-12-27 | 2007-12-27 | Active anode for hydrochloric acid electrolysis and preparation thereof |
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| CNA2007103047090A CN101469434A (en) | 2007-12-27 | 2007-12-27 | Active anode for hydrochloric acid electrolysis and preparation thereof |
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| CNA2007103047090A Pending CN101469434A (en) | 2007-12-27 | 2007-12-27 | Active anode for hydrochloric acid electrolysis and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972178A (en) * | 2018-04-26 | 2019-07-05 | 北京科技大学 | A kind of preparation method of high activity iridium zirconium composite oxides inert anode |
| CN109972177A (en) * | 2018-04-26 | 2019-07-05 | 北京科技大学 | A kind of preparation method of long-life iridium zirconium composite oxides inert anode |
| CN113800606A (en) * | 2021-08-28 | 2021-12-17 | 西安电子科技大学 | Coating titanium anode for treatment of circulating cooling water, preparation method and application |
-
2007
- 2007-12-27 CN CNA2007103047090A patent/CN101469434A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972178A (en) * | 2018-04-26 | 2019-07-05 | 北京科技大学 | A kind of preparation method of high activity iridium zirconium composite oxides inert anode |
| CN109972177A (en) * | 2018-04-26 | 2019-07-05 | 北京科技大学 | A kind of preparation method of long-life iridium zirconium composite oxides inert anode |
| CN113800606A (en) * | 2021-08-28 | 2021-12-17 | 西安电子科技大学 | Coating titanium anode for treatment of circulating cooling water, preparation method and application |
| CN113800606B (en) * | 2021-08-28 | 2022-06-21 | 西安电子科技大学 | Coating titanium anode for treatment of circulating cooling water, preparation method and application |
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