CN108360018A - Electrolytic manganese composite anode and preparation method thereof - Google Patents
Electrolytic manganese composite anode and preparation method thereof Download PDFInfo
- Publication number
- CN108360018A CN108360018A CN201810231135.7A CN201810231135A CN108360018A CN 108360018 A CN108360018 A CN 108360018A CN 201810231135 A CN201810231135 A CN 201810231135A CN 108360018 A CN108360018 A CN 108360018A
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- China
- Prior art keywords
- composite anode
- cobalt
- tin
- slab
- electrolytic manganese
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/12—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of lead or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
Abstract
The invention discloses a kind of electrolytic manganese composite anodes and preparation method thereof, the tin cobalt master alloy of certain proportion content is added in the lead liquid of melting, it is fully reacted in molten bath, bottom melt is preferentially flowed out and is trapped by gravity, remainder melt injects mold, the hot rolled processing of slab that cast obtains is obtained into composite anode, the cobalt that composite anode includes the tin that mass percent is 10~30% and mass percent is 0.1~5%, surplus is lead.Preparation process serialization degree proposed by the present invention is high, it is at low cost, and the composite anode prepared can low current density, be on active service for a long time under conditions of few output, it is big to solve earth of positive pole quantum of output or even the not output earth of positive pole, it is recycled difficult problem, the consumption of manganese ion and selenium dioxide is reduced, reduces the electrolytic cell slotting period, and composite anode is compared with conventional anode, the addition of non precious metal silver, reduces the cost of production.
Description
Technical field
The present invention relates to technical field of wet metallurgy more particularly to a kind of electrolytic manganese composite anode and preparation method thereof.
Background technology
Up to now, China has become maximum electrolytic manganese producing country and demand state in the world.But power consumption occupies
It is high not under, the resource consumption that has brought huge；The waste residue of electrolytic process discharge cannot be effectively treated, and dirt is brought for environment
Dye, this 2 points are the main bottlenecks for restricting electrolytic manganese development.Existing statistical data shows：1 ton of manganese is often produced, the output earth of positive pole is about
For 150kg.
Lead silver alloy anode because it is easily formed, stablizes in sulfuric acid electrolyte, cheap the advantages that due in electrolytic manganese
It is widely used in industry.But MnO2It is easy to grow to generate loose porous anode on lead silver alloy anode surface
Mud, a large amount of MnO2Generation not only cause the waste of resource, and bring larger pressure for subsequent filtering, roasting.
In order to reduce the generation of the earth of positive pole, usual way is to reduce the effective area of anode plate to increase the electric current of anode
Density.But the area for reducing anode plate influences whether the uniformity of electric force lines distribution, accelerates the edge effect of cathodic discharge process,
To reduce cathode efficiency.Meanwhile the increase of anodic current density, it can also increase anode polarization, accelerating anode accordingly
The corrosion of plate, the PbO of alloy surface2It can enter in the earth of positive pole, there is no the lead in the cost-effective technique removal earth of positive pole at present,
The a large amount of earth of positive pole is mainly outdoor stockpiling.In addition, SeO2It is main additive, MnO in manganese electrolytic process2It can carry secretly certain
The selenium compound of content enters in the earth of positive pole, SeO2Consumption increase with the increase of the earth of positive pole.The selenides of severe toxicity is being stored up
Underground water can be dissolved and penetrated into the process, endanger the safety of ecological environment and water resource.
Invention content
The main purpose of the present invention is to provide a kind of electrolytic manganese composite anodes and preparation method thereof, it is intended to solve electrolysis
The lead silver alloy anode that manganese uses is easy induction MnO2It generates, the technical issues of to generate a large amount of earth of positive pole.
To achieve the above object, it is 10~30% that electrolytic manganese composite anode provided by the invention, which includes mass percent,
The cobalt that tin and mass percent are 0.1~5%, surplus is lead.
To achieve the above object, the preparation method of electrolytic manganese composite anode provided by the invention, includes the following steps：
1) tin-cobalt master alloy is prepared
After glass putty and cobalt powder are stirred at room temperature uniformly, it is placed in melting in vaccum sensitive stove, tin-cobalt master alloy is made；
2) slab is prepared
After lead liquid is added in molten bath and is heated to 250~350 DEG C, tin-cobalt master alloy is added in lead liquid,
It is kept stirring 5~60min after tin-cobalt master alloy melting, and 3/2nds to four/3rds are discharged from molten bath bottom
The melt of volume, remaining melt inject mold, and demoulding obtains slab；
3) steel slab surface is heat-treated
Composite anode is obtained using hot-rolled process processing slab.
Preferably, the cobalt that the tin and mass percent that tin-cobalt master alloy is 80~95% by mass percent are 5~20%
It constitutes.
Preferably, glass putty and cobalt powder 30~60min of melting at 1100~1300 DEG C in step 1) is made tin-cobalt mother and closes
Gold.
Preferably, it is added in molten bath and reuses as lead liquid from the melt that molten bath bottom is discharged in step 2).
Preferably, step 3) be specially first by heating of plate blank to 250~300 DEG C and keep the temperature 30~60min, then to slab into
Row rolling, is made composite anode.
Preferably, when being rolled to slab, the deflection of calendering is the 10~60% of original slab thickness, controls slab
Final thickness is 6~7mm.
In technical solution proposed by the present invention, the tin cobalt master alloy of certain proportion content is added in the lead liquid of melting,
It is fully reacted in molten bath, bottom melt is preferentially flowed out and trapped by gravity, and remainder melt injects mold, will pour into a mould
To the hot rolled processing of slab obtain composite anode, composite anode includes the tin and quality percentage that mass percent is 10~30%
Than the cobalt for 0.1~5%, surplus is lead.MnO can be effectively inhibited using the composite anode2In the growth of polar board surface,
Output or even not the output earth of positive pole less, effectively improve the utilization of manganese resource and rare element selenium in electrolytic manganese production process
Rate, while reducing the power consumption of manganese electrolytic process.
Compared with prior art, the present invention has the advantages that：
1) earth of positive pole quantity that manganese electrolytic process is discharged dramatically is reduced, the slotting period is shortened, alleviates
It is electrolysed the pressure of follow-up workshop section's processing earth of positive pole；
2) anode potential is significantly reduced, it is energy-saving to achieve the purpose that；
3) power line is more uniformly spread, and the edge effect of cathode is curbed；
4) additive SeO2Consumption reduce, bring larger economic benefit；
5) corrosion rate of anode reduces, and extends the service life of anode；
6) cost of manufacture of Anode for electrolytic manganese is reduced.
Specific implementation mode
Embodiment 1
The electrolytic manganese composite anode of the present invention, the percent mass proportioning of ingredient are as follows：Sn：28.3%, cobalt：3.8%,
Remaining is lead.
The composite anode is prepared especially by following steps：
1) tin-cobalt master alloy is prepared
It is added high-purity glass putty and high-purity cobalt powder in graphite crucible, the mass percent of glass putty and cobalt powder is as follows：Tin 80%,
Cobalt 20%.Mixed-powder is stirred at room temperature to uniform, graphite crucible is placed in melting 40min in vaccum sensitive stove, vacuum sense
It is 1200 DEG C to answer the temperature of stove.
2) slab is prepared
Lead liquid is added in molten bath and is heated to 300 DEG C, the lead liquid that tin-cobalt master alloy addition is melted waits for that tin-cobalt mother closes
It is kept stirring 5 minutes in after gold fusing, the melt of 3/4ths volumes is discharged from molten bath bottom and collects for use, remaining melt
Inject mold.
It should be noted that since the tin of lead liquor ratio melting, cobalt are all heavy, molten bath bottom is the molten lead for having minute quantity tin and cobalt
Liquid, this part melt cannot reach the required metal proportioning of composite anode, therefore it need to be discharged from bottom, leave upper layer
Melt.The metal ratio of the melt on upper layer reaches the required proportioning of composite anode, can be utilized to prepare slab, be arranged by bottom
The melt gone out can be used as the lead liquid for preparing slab step next time.
In addition, since cobalt is immiscible with lead, and tin forms the alloy of arbitrary proportion with lead, tin and cobalt are easy to form alloy,
Cobalt is enable to incorporate lead on a small quantity under the action of tin so that active element cobalt and tin can be smoothly introduced in lead liquid, to effectively
Inhibit MnO in electrolytic process2In the growth of anode surface.The generation that the earth of positive pole is controlled from the source of electrolytic process, not only helps
In the efficient utilization for the clean manufacturing and manganese resource for realizing electrolytic manganese, and there is extremely important meaning to preserving the ecological environment
Justice.
3) steel slab surface is heat-treated
Slab is heated in Muffle furnace 60 minutes, control fire box temperature is 250 DEG C.It is immediately rolled with calender after taking out slab
Composite anode is made in system, wherein rolling pass is 4 times, obtains the composite anode that final thickness is 6 millimeters.
Specifically, when being rolled to slab, the deflection of calendering is the 10~60% of original slab thickness, controls slab
Final thickness be 6~7mm, the corrosion rate of composite anode can be reduced.
Using above-mentioned composite anode and stainless steel cathode, like poles spacing is 6 centimetres, is electrolysed using industrial electrolytic manganese
Liquid, with 700A/m at 35 DEG C2Anodic current density, 400A/m2Cathode-current density carry out electrolysis 6 hours, the same terms
The more traditional lead silver alloy anode of lower tank voltage lowers about 80mV, and anodic attack rate reduces by 50%, SeO in electrolyte2Loss
Rate reduces by 50%, and cathode efficiency is without significant change.Electrolyte keeps limpid transparent, nothing in electrolytic cell after electrolysis 6 hours
The earth of positive pole generates, without suspended particulate in anolyte.
Embodiment 2
The electrolytic manganese composite anode of the present invention, the percent mass proportioning of ingredient are as follows：Sn：22.3%, cobalt：2.1%,
Remaining is lead.
The composite anode is prepared especially by following steps：
1) tin-cobalt master alloy is prepared
It is added high-purity glass putty and high-purity cobalt powder in graphite crucible, the mass percent of glass putty and cobalt powder is as follows：Tin 85%,
Cobalt 15%.Mixed-powder is stirred at room temperature to uniform, graphite crucible is placed in melting 50min in vaccum sensitive stove, vacuum sense
It is 1150 DEG C to answer the temperature of stove.
2) slab is prepared
Lead liquid is added in molten bath and is heated to 320 DEG C, the lead liquid that tin-cobalt master alloy addition is melted waits for that master alloy is molten
It is kept stirring in after change 20 minutes, the melt of 70% volume is discharged from molten bath bottom and collects for use, remaining melt injection mould
Tool.
3) steel slab surface is heat-treated
Slab is heated in Muffle furnace 40 minutes, control fire box temperature is 280 DEG C.It is immediately rolled with calender after taking out slab
Composite anode is made in system, wherein rolling pass is 3 times, obtains the composite anode that final thickness is 6.5 millimeters.
Using above-mentioned composite anode and stainless steel cathode, like poles spacing is 6 centimetres, is electrolysed using industrial electrolytic manganese
Liquid, with 700A/m at 35 DEG C2Anodic current density, 400A/m2Cathode-current density carry out electrolysis 6 hours, the same terms
The more traditional lead silver alloy anode of lower tank voltage lowers about 75mV, and anodic attack rate reduces by 50%, SeO in electrolyte2Loss
Rate reduces by 50%, and cathode efficiency is without significant change.Electrolyte keeps limpid transparent, nothing in electrolytic cell after electrolysis 6 hours
The earth of positive pole generates, without suspended particulate in anolyte.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention, every at this
Under the design of invention, using equivalent structure transformation made by present specification, or directly/it is used in other correlations indirectly
Technical field be included in the present invention scope of patent protection in.
Claims (7)
1. a kind of electrolytic manganese composite anode, which is characterized in that the composite anode includes that mass percent is 10~30%
The cobalt that tin and mass percent are 0.1~5%, surplus is lead.
2. the preparation method of electrolytic manganese composite anode as described in claim 1, which is characterized in that include the following steps：
1) tin-cobalt master alloy is prepared
After glass putty and cobalt powder are stirred at room temperature uniformly, it is placed in melting in vaccum sensitive stove, tin-cobalt master alloy is made；
2) slab is prepared
After lead liquid is added in molten bath and is heated to 250~350 DEG C, tin-cobalt master alloy is added in lead liquid,
It is kept stirring 5~60min after tin-cobalt master alloy melting, and 3/2nds to four/3rds volumes are discharged from molten bath bottom
Melt, remaining melt injects mold, and demoulding obtains slab；
3) steel slab surface is heat-treated
Composite anode is obtained using hot-rolled process processing slab.
3. the preparation method of electrolytic manganese composite anode according to claim 2, which is characterized in that tin-cobalt master alloy by
The cobalt that the tin and mass percent that mass percent is 80~95% are 5~20% is constituted.
4. the preparation method of electrolytic manganese composite anode according to claim 2, which is characterized in that in step 1) glass putty and
Tin-cobalt master alloy is made in cobalt powder 30~60min of melting at 1100~1300 DEG C.
5. the preparation method of electrolytic manganese composite anode according to claim 2, which is characterized in that from molten bath in step 2)
The melt of bottom discharge, which is added as lead liquid in molten bath, to be reused.
6. the preparation method of electrolytic manganese composite anode according to claim 2, which is characterized in that step 3) is specially first
Heating of plate blank to 250~300 DEG C and is kept the temperature into 30~60min, then slab is rolled, composite anode is made.
7. the preparation method of electrolytic manganese composite anode according to claim 6, which is characterized in that rolled to slab
When, the deflection of calendering is the 10~60% of original slab thickness, and the final thickness for controlling slab is 6~7mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810231135.7A CN108360018A (en) | 2018-03-20 | 2018-03-20 | Electrolytic manganese composite anode and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810231135.7A CN108360018A (en) | 2018-03-20 | 2018-03-20 | Electrolytic manganese composite anode and preparation method thereof |
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| CN108360018A true CN108360018A (en) | 2018-08-03 |
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| CN201810231135.7A Pending CN108360018A (en) | 2018-03-20 | 2018-03-20 | Electrolytic manganese composite anode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113686836A (en) * | 2021-07-27 | 2021-11-23 | 超威电源集团有限公司 | Method for detecting impurity content in lead of lead-acid storage battery raw material |
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|---|---|---|---|---|
| GB952551A (en) * | 1962-02-13 | 1964-03-18 | Monte Amiata Societa Mineraria | Process for the production of metallic manganese by electrolytic separation |
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| CN101235521A (en) * | 2007-01-29 | 2008-08-06 | 中南大学 | Energy-saving anode for non-ferrous metal electrodeposition |
| CN103898354A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Lead alloy anode material for zinc electrodeposition and rolling method thereof |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN103668342B (en) * | 2013-11-29 | 2016-03-09 | 中南大学 | A kind of manganese electrolysis titanium based composite anode and preparation method |
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-
2018
- 2018-03-20 CN CN201810231135.7A patent/CN108360018A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB952551A (en) * | 1962-02-13 | 1964-03-18 | Monte Amiata Societa Mineraria | Process for the production of metallic manganese by electrolytic separation |
| CN1209469A (en) * | 1997-08-26 | 1999-03-03 | 苏勇 | Electrolytic anode plate |
| CN101235521A (en) * | 2007-01-29 | 2008-08-06 | 中南大学 | Energy-saving anode for non-ferrous metal electrodeposition |
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| CN103668342B (en) * | 2013-11-29 | 2016-03-09 | 中南大学 | A kind of manganese electrolysis titanium based composite anode and preparation method |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN106191930A (en) * | 2016-07-04 | 2016-12-07 | 北京有色金属研究总院 | A kind of electrification is metallurgical with alloy lead anode plate and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| COI,IN G. FINK ET AL.: "ANODES FOR THE ELECTROWINNING OF MANGANESE", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113686836A (en) * | 2021-07-27 | 2021-11-23 | 超威电源集团有限公司 | Method for detecting impurity content in lead of lead-acid storage battery raw material |
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Application publication date: 20180803 |