CN1033657A - The modified anode of lead dioxide that electrolytic industry is used - Google Patents
The modified anode of lead dioxide that electrolytic industry is used Download PDFInfo
- Publication number
- CN1033657A CN1033657A CN 87107489 CN87107489A CN1033657A CN 1033657 A CN1033657 A CN 1033657A CN 87107489 CN87107489 CN 87107489 CN 87107489 A CN87107489 A CN 87107489A CN 1033657 A CN1033657 A CN 1033657A
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- China
- Prior art keywords
- oxide
- modified
- lead dioxide
- anode
- metal
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Abstract
The invention provides a kind of modified anode of lead dioxide of forming by plumbic oxide, cobalt spinel, modified metal-oxide and electrode matrix.This electrode be with valve shape metal oxide or other metal oxides that mix be the compound cobalt spinel of modified oxide as composite catalyst, use composite electric plating method again, with compound catalyzer and PbO
2Codeposition is on electrode matrix.
This electrode is in the chlorine discharge process, and it is low to have a chlorine evolution potential, good conductivity, and current potential is low, the advantage that the life-span is long, and on the major technology index, reached titanium anodic electrical property level.Thereby can be widely used in chlorine industry and other electrolytic processes.
Description
The present invention relates to the used anode of a kind of electrolytic industry, particularly can be widely used in the modified anode of lead dioxide of chlorine industry electrolyzer.
As everyone knows, plumbic oxide is widely used as the anode material of electrolytic industry, is because plumbic oxide has excellent conducting performance, simultaneously, also since it can be easily from lead nitrate solution galvanic deposit on electrode matrix.But blemish in an otherwise perfect thing is anode of lead dioxide no matter be that β type or α type all exist the high shortcoming of chlorine evolution potential, and its application in chlorine-evolution electrolysis industry is restricted.In recent years, generally adopt both at home and abroad and in the electrode activity layer, mix a small amount of electrocatalysis material, improve the technology of electrode performance, also begin to refer on the anode of lead dioxide, Manganse Dioxide is mixed in having in the lead dioxide electrode active coating of reporting on the document, catalyzer such as cobalt nickel spinel, palladous oxide, tricobalt tetroxide, titanium dioxide shackles are to reach the purpose of the chlorine evolution potential that reduces plumbic oxide.As " chlorine industry " fourth phase in 1979, " inorganic chemicals industry " third phase in 1985 is mentioned in lead dioxide plating coat the method for cobalt nickel spinel catalyst on the composite plating, reduces chloride potential to 1.2 volt (5A/ decimetre respectively
2, with respect to mercurous chloride electrode) and 1.17 volts of (20 peace/decimetres
2, with respect to mercurous chloride electrode).But this modified anode of lead dioxide exists the shortcoming that electrolytic coating peels off easily in the operational process, has influenced the work-ing life of electrode.
The object of the invention provides a kind of modified anode of lead dioxide, and it promptly has the chlorine evolution potential of reduction, and easy to make, the life-span is long, can be applied to the electrolysis production of chlorine industry.This electrode is made up of plumbic oxide, cobalt spinel, modified oxide and electrode matrix.
Above-mentioned cobalt spinel, its stoichiometric equation be *
+ 2Y
2 + 3O
4Y is a cobalt ion in the formula, and * can be metallic cations such as Fe, En, Mg, CU, Ni, Co, oxonium ion in the cobalt spinel and metallic cation are the solid matter cubic lattice structure, and it has good catalysis characteristics to analysing the chlorine discharge.In view of the above, the contriver adopts can improve the metal oxide of electrode performance with other, just so-called modified oxide, mix in the cobalt spinel catalyzer crystal, under 200-650 ℃ of high temperature oxidation condition, make the composite catalyst of cobalt spinel and modified oxide, with the physical strength of improving the cobalt spinel catalyst themselves and with β-pbO
2Bonding force, make it to become a kind of stable performance, the catalyzer good to chlorine discharge.On preparation technology, the cobalt spinel catalyzer that adds modified oxide can be added in 1-30 grams per liter ratio with the state of solid powder and contain pb
2+In the ionic electroplate liquid, under galvanic effect, catalyzer powder and pbO
2Codeposition makes modified anode of lead dioxide on conducting base together.
Above-mentioned mentioned modified oxide can be the oxide compound such as the TiO of valve shape metal
2, WO
3, MoO
3, ZrO
2, Nb
2O
5, Ta
2O
5, V
2O
5Or other metal oxides, as SnO
2, MnO
2, PbO
2, CrO
2Deng.The modified oxide that mixes in the cobalt spinel should contain a kind of these metal oxides at least, and simultaneously, the total amount of the modified oxide of adding should be greater than 5% mol of cobalt spinel catalyst levels, and less than 100% mol.
Run into the oxide compound of poorly conductive in the above-mentioned alleged modified oxide, can be by doping Sb
2O
5, Fe
2O
3, NiO
2, SbO
2, Cr
2O
3, B
2O
3, CaO, Na
2O, Al
2O
3, pt family metal oxide or their mixture solves.These oxide compounds that are doped in the modified oxide should be able to improve the electroconductibility of oxide compound and the new electrocatalytic surface of the increase of utilizing is arranged, also should be able to improve the performance of composite catalyst, adulterated oxide compound consumption should be less than 50% mol of the modified oxide consumption that is doped simultaneously.
Being used for conducting base of the present invention can be the titanium matrix, and graphite matrix is coated with α-pbO
2Or β-pbO
2Graphite matrix, ceramic matrix, plastic substrate.
Modified anode of lead dioxide according to the present invention's preparation.In analysing the chlorine discharge process, have good conductivity, stability is high, solved the known simple plating exfoliation problem that exists during for catalyzer with the cobalt spinel.The lead dioxide electrode of this modification simultaneously contains sufficient electrocatalysis material in coating.It can the discharge of catalysis chlorine.After the discharge of long-time big electric current was used, overpotential was still very low.Therefore, kind electrode of the present invention can be widely used in sodium, the muriate of potassium, the electrolysis of iodide, bromide: can be used for the electrolysis that time chlorine is made salt, oxymuriate; Also can be used for organic oxidation; Galvanic protection and other electrolytic processes.In chlorine industry, can be used as the electrolytic anode of diaphram tank, ion-exchange membrane tank.Be particularly conducive to the improvement of graphite anode cell, can on the graphite anode matrix, plate coating of the present invention.Reach and reduce the chlorine discharge potential, make the dimensional stabilizing of graphite anode, prevent the negative and positive interpolar, reduce bath voltage, increased the work-ing life of graphite anode apart from increase.
Following embodiment is in order to further specify concrete formation of the present invention.
Embodiment 1,
With 0.291 mol Co(NO
3)
26H
2O and 0.146 mol Mg(NO
3)
2Solution in add 14 gram NaOH, when producing precipitation and being washed with water to PH=7, will be 125 ℃ of oven dry down behind the sedimentation and filtration, 410 ℃ of following sintering 40 minutes, make MgCO then
2O
4Spinel.
Composite catalyst is pressed MgCO
2O
43.0 gram (weight), Sbcl
30.137 gram (weight), Sncl
4, 5H
2After putting into porcelain cup after O 0.647 gram (weight), 2.25 milliliters of propyl carbinols, 36%HCL0.3～0.5 milliliter prepare and stirring, 125 ℃ of oven dry down, put into 500-520 ℃ muffle furnace sintering 30 minutes again, coming out of the stove grinds to form fine powder after naturally cooling to room temperature, makes MgCo
2O
4-SnO
2-SbO * composite catalyst.
With graphite (20 * 5 * 85) is that anode, copper are negative electrode.Anodic current density is 3 peace/decimetres
2Plating solution formula is pb(NO
3)
21 mol, Ni(NO
3)
20.1 mol, Cu(NO
3)
20.1 mol, NaF0.1 grams per liter temperature of electroplating solution is 25 ℃, and electroplating time 30 minutes makes β-pbO
2Electrolytic coating adds MgCo then in electroplate liquid
2O
4-SnO
2-SbO * composite catalyst is to 4 grams per liters.With pneumatic blending and induction stirring, anodic current density is 4 peace/decimetres
2, the composite plating time promptly makes the alleged modified anode of lead dioxide of the present invention after being 2 hours.This anode is 10 peace/decimetres in current density in 70 ℃ of saturated NaCl solution
2Under to record anode potential be 1.116 volts (with respect to mercurous chloride electrodes).In 220 grams per liter NaCl+5MNaOH solution, under 90-95 ℃, anodic current density is 200 peace/decimetres
2, the reinforcing life of anodic coating complete loss is 50 hours.
Example 2:
Titanium matrix (20 * 2 * 85) placed 15% HCl solution to boil to take out after 1 hour clean up, the prescription brushing of using following composition then is on the titanium plate.
SbCl
33.2 gram
SnCl
45H
2O 15.1 grams
5 milliliters of HCL (38%)
30 milliliters of propyl carbinols
Under 125 ℃ temperature, dry then, put into 550 ℃ muffle furnace sintering 10 minutes, brush four times, make on the titanium matrix and form SnO
2-SbO
XThe middle layer is beneficial to plate modified anode of lead dioxide on the titanium matrix.
In Co: Mg: Zr=12: 6: the ratio 1(mol ratio) is with 5.654 gram Co(NO
3)
26H
2O, 2.91 milliliters of 3.33Mg(NO
3)
2Solution and 90ml0.018ZrO(NO
3)
2Solution mixes, continuous stirring and drying under 125 ℃ of temperature, and sintering is 30 minutes in the most rearmounted 375 ℃ muffle furnace, makes composite catalyst.
By the plating solution formula of example 1, anodic current density is 8 peace/decimetres
2, add the composite catalyzing agent content to 2 grams per liters, pneumatic blending, composite plating 1.5 hours makes modified anode of lead dioxide.This anode is at 10 peace/decimetres
2Under to record anode potential be 1.181 volts (with respect to mercurous chloride electrodes), the anode reinforcing life is 41 hours.
Example 3, and the titanium matrix of the individual same size heavy brushing SnO that powers on
2-SbO
XZone of oxidation after, one of them titanium matrix powers on and deposits modified oxide Co
3O
4-SnO
2-SbO
XThe modified anode of lead dioxide of catalyzer.Another titanium matrix powers on and deposits simple CO
3O
4The anode of lead dioxide of catalyzer, by respectively adding catalyst content to 1 grams per liter in example 2 electroplate liquid formulations, be 8 peace/decimetres in anodic current density
2, 15-20 ℃ of plating tank temperature under 30 minutes the condition of electroplating time, makes two kinds of electrodes respectively.(one of them is a modified anode of lead dioxide of the present invention) adopts the reinforcing life test in the example 1 to test respectively.The result is as follows: when the anode purifying lost efficacy, the reinforcing life that is mixed with the anode of lead dioxide of the composite catalyst that modified oxide forms of the present invention was 17 hours, and the reinforcing life of the anode of lead dioxide of simple cobalt spinel is 9 hours.
Example 4:
4 gram CO
3O
4The solid powder, adding 30,76ml0.045MZrO(NO
3)
2Solution stirs, dries, and 450 ℃ of following sintering 45 minutes, by the plating solution formula of example 1, makes matrix with graphite, electroplates last 30 minute of β-pbo earlier
2Composite plating 2 hours again behind the layer.This moment, anodic current density was 6 peace/decimetres
2, composite catalyzing agent content 8 grams per liters, the cobalt spinel CO in the composite catalyst
3O
4With " modified oxide " ZrO
2Mol ratio be 12: 1.This anode is at anodic current density 100 peace/decimetres
2, recording electropotential after turning round 950 hours in 55 ℃ the saturated brine is 1.170 volts (with respect to mercurous chloride electrodes).
Record experimental data from embodiment 1-4, illustrate and adopt the modified anode of lead dioxide that the present invention makes owing in coating, contain sufficient electrocatalysis material, the discharge that it can catalysis chlorine, for a long time, after the discharge of big electric current was used, overpotential was still very low. Therefore the modified anode of lead dioxide of the present invention's proposition is in the chlorine discharge process, has good conductivity, stability is high, the coating that has existed when having solved merely take cobalt spinel as catalyst holds flaky problem, and on main technical indicator, reach the electrical property level of shackles titanium anode. Thereby can be widely used in chlorine industry, and other electrolytic processes.
Claims (6)
1, a kind of modified anode of lead dioxide that is used for electrolytic industry, its composition comprises plumbic oxide, cobalt spinel and electrode matrix are formed, the present invention is characterised in that this modified anode of lead dioxide also includes modified metal-oxide, above-mentioned plumbic oxide, cobalt spinel and modified metal-oxide use the composite electric plating method codeposition on electrode matrix with the pole catalyze layer form.
2, modified anode of lead dioxide according to claim 1 is characterized in that modified metal-oxide is a valve shape metal oxide, as TiO
2, ErO
2, MoO
3, WO
3, Nb
2O
5, V
2O
5, Ta
2O
5With other metal oxide such as MnO
2, PbO
2, CrO
2, Sb
2O
3
3, modified anode of lead dioxide according to claim 1 is characterized in that modified oxide can be a doping agent with following metal oxide, as Sb
2O
5, Fe
2O
3, NiO
2, Co
2O
3, SbO
2, Na
2OCr
2O
3, B
2O
3, CaO, Al
2O
3With the pt family metal oxide, to increase the electroconductibility and the electrocatalysis of modified metal-oxide.
4, according to claim 1,2 described modified anode of lead dioxide, at least to contain a kind of modified metal-oxide in it is characterized in that forming, the modified metal-oxide total amount of Jia Ruing should be greater than 5% mol, less than 100% molar cobalt spinel catalyst consumption simultaneously.
5, modified anode of lead dioxide according to claim 3, the doping agent consumption that it is characterized in that being doped in the modified metal-oxide should be less than 50% mol of the modified metal-oxide consumption that is doped.
6, modified anode of lead dioxide according to claim 1 is characterized in that used electrode matrix is the titanium matrix, and graphite matrix is coated with α-pbo
2Or β-pbo
2Graphite matrix, ceramic matrix, plastic substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87107489 CN1033657A (en) | 1987-10-27 | 1987-10-27 | The modified anode of lead dioxide that electrolytic industry is used |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87107489 CN1033657A (en) | 1987-10-27 | 1987-10-27 | The modified anode of lead dioxide that electrolytic industry is used |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1033657A true CN1033657A (en) | 1989-07-05 |
Family
ID=4816103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87107489 Pending CN1033657A (en) | 1987-10-27 | 1987-10-27 | The modified anode of lead dioxide that electrolytic industry is used |
Country Status (1)
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|---|---|
| CN (1) | CN1033657A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073747C (en) * | 1993-09-04 | 2001-10-24 | 中国科学院青海盐湖研究所 | Active lead dioxide electrode and preparing method and use |
| CN1320171C (en) * | 2004-11-25 | 2007-06-06 | 复旦大学 | Lead dioxide electrode and preparing method thereof |
| CN100580143C (en) * | 2007-02-07 | 2010-01-13 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
| CN102280626A (en) * | 2010-06-13 | 2011-12-14 | 宝山钢铁股份有限公司 | Composite lead dioxide electrode plate and manufacturing method thereof |
| CN108048865A (en) * | 2017-11-17 | 2018-05-18 | 江苏安凯特科技股份有限公司 | A kind of electrode and its preparation method and application |
| CN109110882A (en) * | 2018-09-12 | 2019-01-01 | 浙江海洋大学 | A kind of method of electrochemistry removal paraxylene |
| CN111785536A (en) * | 2020-08-11 | 2020-10-16 | 苏州柯诺思高新材料有限公司 | Preparation method of asymmetric capacitor nano lead dioxide based composite electrode |
| CN112340905A (en) * | 2020-10-28 | 2021-02-09 | 清华苏州环境创新研究院 | Method and device for multi-wavelength ultraviolet-electrochemical sectional treatment of wastewater |
| CN112573626A (en) * | 2020-12-11 | 2021-03-30 | 广东电网有限责任公司电力科学研究院 | Titanium electrode and preparation method and application thereof |
| CN115287697A (en) * | 2022-06-20 | 2022-11-04 | 天津大学 | High-dispersion in-situ reduction multi-valence tungsten-doped nickel-loaded zirconium dioxide anode material, and preparation and application thereof |
-
1987
- 1987-10-27 CN CN 87107489 patent/CN1033657A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073747C (en) * | 1993-09-04 | 2001-10-24 | 中国科学院青海盐湖研究所 | Active lead dioxide electrode and preparing method and use |
| CN1320171C (en) * | 2004-11-25 | 2007-06-06 | 复旦大学 | Lead dioxide electrode and preparing method thereof |
| CN100580143C (en) * | 2007-02-07 | 2010-01-13 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
| CN102280626A (en) * | 2010-06-13 | 2011-12-14 | 宝山钢铁股份有限公司 | Composite lead dioxide electrode plate and manufacturing method thereof |
| CN108048865B (en) * | 2017-11-17 | 2020-04-28 | 江苏安凯特科技股份有限公司 | Electrode and preparation method and application thereof |
| CN108048865A (en) * | 2017-11-17 | 2018-05-18 | 江苏安凯特科技股份有限公司 | A kind of electrode and its preparation method and application |
| CN109110882A (en) * | 2018-09-12 | 2019-01-01 | 浙江海洋大学 | A kind of method of electrochemistry removal paraxylene |
| CN109110882B (en) * | 2018-09-12 | 2021-09-14 | 浙江海洋大学 | Method for electrochemically removing p-xylene |
| CN111785536A (en) * | 2020-08-11 | 2020-10-16 | 苏州柯诺思高新材料有限公司 | Preparation method of asymmetric capacitor nano lead dioxide based composite electrode |
| CN112340905A (en) * | 2020-10-28 | 2021-02-09 | 清华苏州环境创新研究院 | Method and device for multi-wavelength ultraviolet-electrochemical sectional treatment of wastewater |
| CN112340905B (en) * | 2020-10-28 | 2023-08-11 | 苏州清初环境科技有限公司 | Method and device for multi-wavelength ultraviolet-electrochemical sectional treatment of wastewater |
| CN112573626A (en) * | 2020-12-11 | 2021-03-30 | 广东电网有限责任公司电力科学研究院 | Titanium electrode and preparation method and application thereof |
| CN115287697A (en) * | 2022-06-20 | 2022-11-04 | 天津大学 | High-dispersion in-situ reduction multi-valence tungsten-doped nickel-loaded zirconium dioxide anode material, and preparation and application thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CI01 | Correction of invention patent gazette |
Correction item: Abstract Correct: Two lead False: Abstract 1.2 Two alumina Number: 27 Volume: 5 Correction item: Denomination of Invention Correct: Modified two lead oxide anodes for electrolytic industry False: Modified two alumina anode for electrolytic industry Number: 27 Volume: 5 |
|
| ERR | Gazette correction |
Free format text: CORRECT: ABSTRACT NO. 1, 2 ROW; FROM: DIOXO ALUMINUM TO: PLUMBUM DIOXIDE |
|
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |