CN102703926B - Selenium-free additive for high-efficiency production of electrolytic manganese - Google Patents
Selenium-free additive for high-efficiency production of electrolytic manganese Download PDFInfo
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- CN102703926B CN102703926B CN201210168997.2A CN201210168997A CN102703926B CN 102703926 B CN102703926 B CN 102703926B CN 201210168997 A CN201210168997 A CN 201210168997A CN 102703926 B CN102703926 B CN 102703926B
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- China
- Prior art keywords
- additive
- selenium
- electrolytic
- manganese
- electrolytic manganese
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Abstract
The invention relates to a selenium-free additive for high-efficiency production of electrolytic manganese, wherein the additive is composed of one or combination of thiosulfate (MxS2O3, x is equal to 1, 2), polythionate (MxSnO6, x is equal to 1, 2, n is equal to 2,3,4,5,6,7), and metabisulfite (MxS2O5, x is equal to 1, 2); the additive does not contain selenium dioxide, and can be used for producing electrolytic manganese instead of existing selenium dioxide; use of the additive can increase electrolytic efficiency, at the same time, the additive is environmental friendly, and does not pollute the environment.
Description
Technical field
The present invention relates to electrolytic metal Mn production field, particularly a kind of without selenium electrolytic metal Mn High-efficient Production additive.
Background technology
As far back as manganese metal in 1774, by Sweden chemist society, strangled from pyrolusite and find, to A.J.AllMand and the method for ceramic diaphragm electrolysis for A.N.Cambell of nineteen twenty-three Britain, electrolysis goes out manganese metal.But to middle forties, just find the additive that is applicable to electrolytic manganese, electrolytic manganese just really steps into industrial production like this.From electrolytic manganese industrial development progress, additive plays a part particularly important in whole electrolytic manganese industry.Main additive for electrolytic manganese production is SeO now
2and SO
2, in actual production practice, use tin anhydride as additive, from current efficiency, stability aspect, be better than sulfurous gas, therefore domestic present electrolytic manganese industry substantially all uses tin anhydride as additive.But tin anhydride belongs to highly toxic substance, human body is had to very large injury, also pollute the environment simultaneously, and SeO
2market value is very high, and in production, additive cost is also just very high.Due in producing, use tin anhydride in addition, cause selenium content in product can reach 0.04-0.08%, greatly reduce like this quality product, affected the Application Areas of manganese.
Part producer is used SO both at home and abroad
2as additive, but SO
2under electrolysis temperature, (40 ℃ of >) is easy to volatilization, causes SO in production line environment
2concentration is high, workman's production operation inclement condition, and current efficiency is only 55～60%.
Aspect electrolytic manganese production, Chinese scholars has been done large quantity research to additive, such as people such as Yao Yuexiang, proposes supplementary additive and SeO
2mixed, reach the object that reduces selenium consumption; Charles etc. are with 0.15-0.50mg/L Zn
2+with 0.10g/L SO
2make additive, gained manganese metal is used purity to reach 99.9%.Other use is at present without selenium electrolysis tech, although can reduce pollution to a certain extent, its current efficiency is than using SeO
2generally reduce.
Summary of the invention
The object of the present invention is to provide and plant electrolytic metal Mn High-efficient Production additive nontoxic, environmentally safe.
Of the present invention without selenium electrolytic metal Mn High-efficient Production additive, it is characterized in that its polythionate (M
xs
no
6, x=1,2, n=2-7) and lay particular stress on sulphite (M
xs
2o
5, x=1,2) in a kind of or their combination form, the additive forming for 2 kinds and two or more above-mentioned substance, wherein various components are to mix in any proportion, the consumption of described additive in electrolytic solution is 40-200mg/L.
Above-mentioned polythionate (M used
xs
no
6, x=1,2, n=2-7) be dithionate (M
xs
2o
6x=1,2), trithionate (M
xs
3o
6, x=1,2), tetrathionate (M
xs
4o
6, x=1,2), pentathionate (M
xs
5o
6, x=1,2), hexapolythionate (M
xs
6o
6, x=1,2) and connect seven vitriol (M
xs
7o
6, x=1,2) general designation.
Polythionate and lay particular stress on each material in sulphite and can use as additive separately, also can be mixed according to arbitrary proportion by thiosulphate, polythionate and any 2 kinds or two or more material of laying particular stress in sulphite.
The salt of described additive is corresponding sodium salt, sylvite, manganese salt, ammonium salt, in actual production, according to easy acquired and various salt costs, chooses applicable salt, and the result of use of different salts in electrolytic manganese production do not have significant difference.
Apply additive of the present invention, directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 at 100-120g/L, pH that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 at 100-120g/L, pH.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
Additive of the present invention does not contain tin anhydride, nontoxic, environmentally safe, and easy and safe to operate, the feature of environmental protection is good, and current efficiency and use SeO
2more close or slightly high (this additive current efficiency>=70%, SeO
2current efficiency 68～70%, SO
2current efficiency 55～60%), improve quality product simultaneously, compare SeO
2and SO
2operational condition as additive is more simple.This additive also can reduce the generation of surface manganese knot for electrolysis, improve product appearance quality.
Embodiment:
In order to understand better the present invention, below in conjunction with embodiment, further set forth content of the present invention, but content of the present invention is not only confined to embodiment.
Get two kinds of tetrathionate and pentathionate as mixed additive, in mixed additive, various materials respectively account for 20～80%, and this additive is 60mg/L at electrolytic solution consumption.
Additive without selenium electrolytic metal Mn High-efficient Production directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 in 100-120g/L, pH value that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 in 100-120g/L, pH value.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
At the electrolytic manganese factory of producing 5000 tons per year, carry out production test.Use SeO
2, SO
2with the additive providing of the present invention and process condition contrast, in Table two:
Table two
Embodiment tri-
Get three kinds of thiosulphate, dithionate and trithionates as mixed additive, in mixed additive, various materials respectively account for 15～70%, and this additive consumption in electrolytic solution is 120mg/L.
Additive without selenium electrolytic metal Mn High-efficient Production directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 in 100-120g/L, pH value that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 in 100-120g/L, pH value.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
At the electrolytic manganese factory of producing 5000 tons per year, carry out production test.Use SeO
2, SO
2with the additive providing of the present invention and process condition contrast, in Table three:
Table three
Embodiment tetra-
Get thiosulphate, dithionate, trithionate and lay particular stress on sulphite as mixed additive, the various materials of mixed additive respectively account for 10～70%, and this additive is 200mg/L at electrolytic solution consumption.
Additive without selenium electrolytic metal Mn High-efficient Production directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 in 100-120g/L, pH value that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 in 100-120g/L, pH value.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
At the electrolytic manganese factory of producing 5000 tons per year, carry out production test.Use SeO
2, SO
2with the additive providing of the present invention and process condition contrast, in Table four:
Table four
Embodiment five
Get trithionate as additive, this additive consumption in electrolytic solution is 90mg/L.
Additive without selenium electrolytic metal Mn High-efficient Production directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 in 100-120g/L, pH value that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 in 100-120g/L, pH value.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
At the electrolytic manganese factory of producing 5000 tons per year, carry out production test.Use SeO
2, SO
2with the additive providing of the present invention and process condition contrast, in Table five:
Table five
Embodiment six
Get hexapolythionate and connect seven vitriol as mixed additive, in mixed additive, various materials respectively account for 10～90%, and this additive consumption in electrolytic solution is 40mg/L.
Additive without selenium electrolytic metal Mn High-efficient Production directly can be at the existing SeO that uses
2on electrolytic producer apparatus as additive, apply, use manufacturing condition of the present invention to be: it is that 30-35g/L, ammonium sulfate content are controlled at 6.5-6.8 in 100-120g/L, pH value that qualifying liquid requires manganese content.In electrolyzer, requiring manganese content is that 14-18g/L, ammonium sulfate content are controlled at 7.4-8.0 in 100-120g/L, pH value.Groove temperature control is at 42-48 ℃; Electrolysing period is 24 hours.
At the electrolytic manganese factory of producing 5000 tons per year, carry out production test.Use SeO
2, SO
2with the additive providing of the present invention and process condition contrast, in Table six:
Table six
Use SeO
2contrast in Table seven with the electrolytic metal Mn sheet foreign matter content of Additive Production provided by the invention:
Table seven
The substance classes that additive provided by the present invention is used in preparation is more, and no matter single kind material is used is still used in combination the current efficiency that can reach higher, will not enumerate.Use additive nontoxic pollution-free of the present invention, current efficiency is high, and can improve the exterior quality of electrolytic manganese, improves workman's operating environment simultaneously, and produce the waste water producing and more easily process, thus the production cost of reduction electrolytic manganese.
Claims (4)
1. without a selenium electrolytic metal Mn High-efficient Production additive, it is characterized in that it is by polythionate (M
xs
no
6, x=1,2, n=2-7) and lay particular stress on sulphite (M
xs
2o
5, x=1,2) in a kind of or their combination form, its consumption in electrolytic solution is 40-200mg/L.
2. according to claim 1 without selenium electrolytic metal Mn High-efficient Production additive, it is characterized in that polythionate (M
xs
no
6, x=1,2, n=2-7) refer to dithionate (M
xs
2o
6x=1,2), trithionate (M
xs
3o
6, x=1,2), tetrathionate (M
xs
4o
6, x=1,2), pentathionate (M
xs
5o
6, x=1,2), hexapolythionate (M
xs
6o
6, x=1,2) and connect seven vitriol (M
xs
7o
6, x=1,2).
3. according to claim 1 and 2 without selenium electrolytic metal Mn High-efficient Production additive, it is characterized in that polythionate and laying particular stress on sulphite is corresponding sodium salt, sylvite, manganese salt, ammonium salt.
4. according to claim 1 without selenium electrolytic metal Mn High-efficient Production additive, it is characterized in that the additive that forms for 2 kinds and two or more above-mentioned substance, wherein various components are to mix in any proportion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168997.2A CN102703926B (en) | 2012-05-19 | 2012-05-19 | Selenium-free additive for high-efficiency production of electrolytic manganese |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210168997.2A CN102703926B (en) | 2012-05-19 | 2012-05-19 | Selenium-free additive for high-efficiency production of electrolytic manganese |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102703926A CN102703926A (en) | 2012-10-03 |
| CN102703926B true CN102703926B (en) | 2014-11-26 |
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| CN201210168997.2A Expired - Fee Related CN102703926B (en) | 2012-05-19 | 2012-05-19 | Selenium-free additive for high-efficiency production of electrolytic manganese |
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| CN105603454B (en) * | 2016-01-25 | 2018-03-27 | 吉首大学 | The production method and electrolysis additive of a kind of electrolytic manganese metal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6244593A (en) * | 1985-08-21 | 1987-02-26 | Nippon Kokan Kk <Nkk> | Manufacture of zinc-manganese alloy electroplated steel sheet |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1004363B (en) * | 1985-06-06 | 1989-05-31 | 福建师范大学 | Concurrent production of electrolytic metallic manganese and fibred electrolytic manganese dioxide |
| CN101260538B (en) * | 2008-05-07 | 2010-09-29 | 泸溪县熙邦科技有限责任公司 | Environmental protection highly effective additive for electrolyzing selenium-free manganese metal and preparation method thereof |
| CN101717957B (en) * | 2009-11-24 | 2011-04-20 | 中国地质大学（武汉） | Organic additive for production of electrolytic manganese and preparation method thereof |
-
2012
- 2012-05-19 CN CN201210168997.2A patent/CN102703926B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6244593A (en) * | 1985-08-21 | 1987-02-26 | Nippon Kokan Kk <Nkk> | Manufacture of zinc-manganese alloy electroplated steel sheet |
Non-Patent Citations (2)
| Title |
|---|
| 电解金属锰含硫量影响因素浅析;陈本忠等;《矿冶工程》;19960331;第16卷(第1期);第43页第1栏第4段 * |
| 陈本忠等.电解金属锰含硫量影响因素浅析.《矿冶工程》.1996,第16卷(第1期),第43页第1栏第4段. * |
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Effective date of registration: 20190905 Address after: 416100 North Industrial Park, Wuxi Town, Luxi County, Tujia and Miao Autonomous Prefecture, Western Hunan Province Patentee after: Hunan Haohong New Materials Technology Co., Ltd. Address before: 416000 People's South Road, Jishou City, Hunan Province, Hunan Xiangxi Economic Development Zone Patentee before: Xiangxi Autonomous Prefecture Minerals and New Material Technological Innovation Service Center |
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