CN1015480B - Titanium alloy anode for electrolysis and manufacturing method thereof - Google Patents
Titanium alloy anode for electrolysis and manufacturing method thereofInfo
- Publication number
- CN1015480B CN1015480B CN87101005A CN87101005A CN1015480B CN 1015480 B CN1015480 B CN 1015480B CN 87101005 A CN87101005 A CN 87101005A CN 87101005 A CN87101005 A CN 87101005A CN 1015480 B CN1015480 B CN 1015480B
- Authority
- CN
- China
- Prior art keywords
- anode
- alloy
- electrolysis
- titanium
- alloy anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 2
- 238000005242 forging Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 7
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electrolytic Production Of Metals (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a titanium alloy anode for producing manganese dioxide by electrolysis and a production method thereof. The structure of the titanium alloy anode of the invention mainly comprises an anode bar (1) and a channel steel frame (2) made of an easily conductive metal, wherein the upper end (3) of the anode bar (1) is connected with the channel steel frame (2) by using a fusible metal (4), the alloy of the anode adopts titanium as a base, and elements such as iron, chromium, manganese, nickel and the like are added, so that the alloy is easy to melt, has good plasticity and is 50-200A/m2No passivation is generated in the range of electrolysis current density. The electrode is not only suitable for producing manganese dioxide by electrolysis, but also can be used for storage batteries and other electrolysis industries.
Description
The present invention relates to the anode that electrolysis is used, relate in particular to Ti-alloy anode that electrolysis uses and preparation method thereof.Be applicable to production of manganese dioxide by electrolysis.Also can be used as store battery and other electrolytic industries.
Electrolytic manganese dioxide is high-quality battery and the indispensable raw material of dyestuffs industries strong oxidizer.Reaction formula during production of manganese dioxide by electrolysis is: Mn
2++ 2H
2O-2e → MnO
2+ 4H
+Temperature of reaction is 90-100 ℃, and reacted Manganse Dioxide is deposited on the inert anode.This is one and relates to the manganese hydrolysis after the absorption and the complex reaction of disproportionation.Because of limited by chemical technology.Speed of response is slow.Current density is low, is about 7-12mAcm
-2Bath voltage is between-2.2 to-3.0V.
Production of manganese dioxide by electrolysis.General at present graphite and the lead anode of adopting.This class anode causes product easily and is infected with.Make the quality product variation.And work-ing life is short.Anode material is time-consuming takes a lot of work and change.Metal niobium, tantalum and titanium all can be used as anode material.But by contrast, the price of titanium is cheaper.The anode material of doing preferably.Make anode with pure titanium.Intrinsic corrosion resistant advantage.But it in use easily forms a kind of high-resistance oxide film that has in the surface, may thicken the degree that can not conduct electricity to actual under certain condition, that is produce passivation phenomenon, and bath voltage is significantly risen, and power consumption increases.In addition, in the electrolytic manganese dioxide process, be deposited on the situation that Manganse Dioxide on the pure titanium anode easily produces the be full of cracks peeling, electrolytic process is worsened.
Therefore, in order effectively to solve the difficult problem of the easy passivation of pure titanium anode, this has been carried out broad research both at home and abroad.Soviet Union's certificate of invention 484893 has proposed a kind of titanium manganese alloy anode.The composition of this anode alloy contains manganese 6-16%, and surplus is a titanium.Evidence, this titanium manganese alloy anode are difficult for passivation when using.But the titanium manganese alloy that this invention proposed, melting be difficulty, the easy embrittlement of alloy, and electrolytic bath voltage is higher.
The purpose of this invention is to provide semipermanent Ti-alloy anode of a kind of production of manganese dioxide by electrolysis use and preparation method thereof.Ti-alloy anode of the present invention also is applicable to other electrolytic industries.Feature of the present invention is compared with known titanium manganese alloy anode, and melting is easier, has good plasticity under reasonable process conditions; Bath voltage is stable at allowed band, and does not produce passivation at sizable electrolytic current density scope inner anode.Another characteristics of the present invention are to adopt commaterial to make anode bodies, and anode bodies is solid bar-shaped, ovalize, rhombus or section.
For achieving the above object, in known metal titanium, add metallic elements such as iron, chromium, manganese, content is respectively 6～8% manganese, 4～6% chromium, 1～3 iron, surplus is a titanium.
Accompanying drawings Ti-alloy anode structure of the present invention.
Fig. 1 is the Ti-alloy anode structure.
Fig. 2 and Fig. 3 are several sections of Ti-alloy anode body.
Titanium alloy electrode structure of the present invention is made up of the alloy bar 1 and the metal channel-section steel frame 2 of easy conductive of section, special surface, and Ti-alloy anode rod 1 upper end 3 usefulness fusible metals 4 are vertically fixed on the channel-section steel frame 2.The spacing of anode bar is 10-20mm.
The section of Ti-alloy anode rod 1 of the present invention can be oval, rhombus, and the size at its a, b two ends is respectively 25-30mm and 5-6mm, also can be abnormity, and its a end is 5-6mm, and the b end is 25-30mm.
Embodiment one
With the 78-80% titanium, 6-80% manganese, 4-6% chromium, the hybrid alloys of 1-3% iron is pressed into square billet, again 50-60 is propped up this class alloy square billet and is welded into consumable electrode, carries out melting then.Vacuum or protective atmosphere are adopted in melting.After treating that the secondary consumable smelting finishes, bar is carried out forge hot in 900-1050 ℃ of temperature range, be rolled into ellipse then after 850-1000 ℃ of insulation, rhombus or different form carry out shrend or air cooling.Made alloy plasticity is good, fine fisssure is only arranged when being bent to 180 °, but use properties is not influenced.Accuse fracture during to 29-45 ° and the titanium manganese alloy is curved.
At H
2SO
440g/l+MnSO
4H
2In the bent type electrolytic solution of O130g/l, the erosion rate of blunt titanium anode and Ti-alloy anode of the present invention sees Table 1.
Pure titanium anode of table 1 and anodic erosion rate of the present invention
Pure titanium anode 0.703g/m
2H
Anode 0.007g/m of the present invention
2H
Embodiment two
Ti-alloy anode of the present invention is at the 80A electric current, and electrolysis 558h peels off and do not do behind the product to continue at 100A/m under the situation that any reverse electrode handles
2Carry out the electrolysis comparison test under the current density.Electrolytic solution is: H
2SO
440g/l+MnSO
4H
2O130g/l, electrolysis time 360h, pure titanium anode, graphite anode and anodic of the present invention use and the results are shown in Table 2.(table 2 is seen the literary composition back)
Ti-alloy anode of the present invention is compared with titanium manganese alloy anode, has overcome smelting composition and homogeneity and has been difficult to problems such as control, has eliminated the fragility of titanium manganese alloy, and impact value can reach 1kgM/cm
2More than, can satisfy the requirement of electrolysis production antianode material mechanical performance.
Titanium alloy electrode of the present invention is at 50-200A/m
2The electrolytic current density scope below the bath voltage 4V, does not produce passivation phenomenon, provides favourable condition to improving electrolytic single groove output.
Under suitable electrolysis process condition, be mainly the γ-MnO of discharge performance the best with electrode gained electrolytic production of the present invention
2Crystal.
With the electrolytic product of Ti-alloy anode of the present invention, its Manganse Dioxide content (in butt) can reach more than 91%.The content of iron is lower than graphite anode in the electrolytic production.
The pure titanium anode of the discharge performance of the electrolytic production of Ti-alloy anode of the present invention and parallel test is suitable with the electrolytic production of graphite anode.
The erosion resistance of Ti-alloy anode of the present invention in electrolytic solution is better than pure titanium anode greatly, so its corrosion-resistant life is length far beyond pure titanium anode, Faradaic current efficient surpasses pure titanium anode and graphite anode.
Test-results shows that Ti-alloy anode of the present invention is compared with pure titanium anode, and bath voltage is stable, and technology controlling and process is convenient, and adaptability is strong.Bath voltage changes also less under temperature, tank liquor change in concentration situation.So Ti-alloy anode of the present invention is the comparatively ideal anode material of electrolytic manganese dioxide; Widely applicable, also can be used for store battery and other electrolytic industries; Working life is long, reaches the semipermanent level.
Three kinds of anode material use propertieies of table 2 relatively
Pure titanium anode graphite anode anode of the present invention
Electrolytic current density 50 50 100
A/m
2
Electrolysis time, h 360 360 360
The anode surface state is scratched skin, peels off local cracking, smooth surface,
The place is mud shape peeling and is chocolate
Bath voltage, V 1.86 1.72 2.86
Mean value
Groove temperature T, ℃ 101-91.5 101-91.5 101-91.5
Claims (4)
1, the Ti-alloy anode used of a kind of production of manganese dioxide by electrolysis is characterized in that the weight of this anode alloy consists of: 6-8% manganese, and 4-6% chromium, 1-3% iron, all the other are titanium.
2, Ti-alloy anode according to claim 2 is characterized in that anode adopts the solid rod.
3,, it is characterized in that shape ovalize, rhombus or the special-shaped section of anode bar according to claim 1 or the described Ti-alloy anode of claim 2.
4, a kind of production method of Ti-alloy anode according to claim 1 is characterized in that hot forging temperature is 900-1050 ℃, and hot-rolled temperature is 850-1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101005A CN1015480B (en) | 1987-03-30 | 1987-03-30 | Titanium alloy anode for electrolysis and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101005A CN1015480B (en) | 1987-03-30 | 1987-03-30 | Titanium alloy anode for electrolysis and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101005A CN87101005A (en) | 1988-10-19 |
| CN1015480B true CN1015480B (en) | 1992-02-12 |
Family
ID=4813102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101005A Expired CN1015480B (en) | 1987-03-30 | 1987-03-30 | Titanium alloy anode for electrolysis and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015480B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100555722C (en) * | 2005-07-28 | 2009-10-28 | 株式会社神户制钢所 | Titanium for electrodes |
| ITMI20061974A1 (en) * | 2006-10-16 | 2008-04-17 | Industrie De Nora Spa | ANODE FOR ELECTROLYSIS |
| CN101694001B (en) * | 2009-10-10 | 2011-05-18 | 中信大锰矿业有限责任公司 | Preparation method of Ti-Mn-diffusion titanium anode plate for electrolytic manganese dioxide |
-
1987
- 1987-03-30 CN CN87101005A patent/CN1015480B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87101005A (en) | 1988-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717969A (en) | Alloy material suitable for inert anode of metal fused-salt electrolysis cell | |
| CN106947874B (en) | A kind of method that two-step method prepares high purity titanium | |
| CN111534714B (en) | Nb and Al-containing titanium bronze alloy strip and preparation method thereof | |
| CN111842855B (en) | Method for preparing TA10 residual material into cast ingot by using duplex process | |
| CN102011144A (en) | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer | |
| US6129822A (en) | Insoluble titanium-lead anode for sulfate electrolytes | |
| CN1410599A (en) | Method of producing aluminium scandium alloy by electrolysis | |
| CN1733953A (en) | A kind of high-strength high-conductivity copper alloy and preparation method thereof | |
| CN1015480B (en) | Titanium alloy anode for electrolysis and manufacturing method thereof | |
| CN112921360B (en) | Method for preparing rare earth metal by molten salt electrolysis | |
| CN102433581B (en) | Method for preparing novel anode material for electro-deposition of nonferrous metals | |
| JPS60221591A (en) | Manufacture of fluorine | |
| CN1974859B (en) | Titanium alloy anode for electrolyzing manganese dioxide and manufacturing method thereof | |
| CN107287470B (en) | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material | |
| CN112981467B (en) | Method for reducing carbon pollution in molten salt electrolysis process | |
| CN112176372B (en) | A kind of method for preparing cobalt-tantalum alloy coating at low temperature by using cobalt dichloride and tantalum pentachloride as raw materials | |
| CN1122848A (en) | Prepn. of cerium-magnesium alloy by electrolytic eutectoid of chloride | |
| CN1020926C (en) | Palladium-silver-based alloy material | |
| CN116265617A (en) | A kind of method that molten salt electrolysis prepares metal hafnium | |
| Mantell | Electrodeposition of powders for powder metallurgy | |
| CN117107302B (en) | A fence-type titanium-based metal oxide gradient composite anode plate for non-ferrous metal electrodeposition and a preparation method thereof | |
| JPH06212470A (en) | Titanium alloy anode electrode for electrolysis of manganese dioxide | |
| CN115319424B (en) | Processing method of thin-wall iridium crucible and thin-wall iridium crucible | |
| CN105063660B (en) | A kind of method that nano-silicon powder is directly prepared in electrorefining processes | |
| CN110699560A (en) | VAR smelting method of high-purity vanadium ingot |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |