CN106835195A - A kind of method for adding low selenium composite additive electrolytic manganese - Google Patents
A kind of method for adding low selenium composite additive electrolytic manganese Download PDFInfo
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- CN106835195A CN106835195A CN201710105243.5A CN201710105243A CN106835195A CN 106835195 A CN106835195 A CN 106835195A CN 201710105243 A CN201710105243 A CN 201710105243A CN 106835195 A CN106835195 A CN 106835195A
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- CN
- China
- Prior art keywords
- manganese
- standby
- mixed solution
- electrolytic manganese
- negative electrode
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 26
- 239000011572 manganese Substances 0.000 title claims abstract description 26
- 239000000654 additive Substances 0.000 title claims abstract description 20
- 230000000996 additive effect Effects 0.000 title claims abstract description 20
- 239000011669 selenium Substances 0.000 title claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims abstract description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 238000005498 polishing Methods 0.000 claims abstract description 4
- 239000004576 sand Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 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 description 2
- 239000000126 substance Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind of method for adding low selenium composite additive electrolytic manganese.Negative electrode uses stainless steel electrode, and by sand papering, polishing, washing, re-dry is put into 0.5% sodium silicate solution and soaks 10 ~ 20 minutes, and re-dry after washing is obtained standby negative electrode；1 L mixed solutions are prepared, the mixed solution sulfur acid manganese and ammonium sulfate add the compound additive of selenium dioxide and zinc oxide, and the pH value of mixed solution is adjusted into 7, mixed solution is then obtained electrolyte standby in being stirred 0.5 ~ 2 hour at 40 DEG C；Electrolyte is put into 40 DEG C of thermostat water baths, standby negative electrode is inserted, anode uses titanium plate, and constant-temperature constant-current electrolysis, electrolytic current density is 350 ~ 450 A/m2, decomposition voltage is 5 ~ 7 V, and electrolysis obtains electrolytic manganese after 4 hours.The inventive method is simple to operate, and the bath composition for being used is simple, it is easy to safeguard, compound additive is formed by adding zinc oxide, and Se content is relatively low, can obtain ultrafine high-purity powder product.
Description
Technical field
The invention belongs to electrolytic manganese technical field, more particularly to a kind of method for adding low selenium composite additive electrolytic manganese.
The method is in the manganese sulfate electrolyte of liquid containing ammonium sulfate, to add the compound additive containing selenium dioxide and zinc oxide, can be obtained
More than 97% electrolytic manganese is reached to purity.
Background technology
Electrolytic manganese industry both at home and abroad now, the main additive for using selenium dioxide and sulfur dioxide as electrolytic manganese.I
State's electrolytic manganese factory mainly uses single selenium dioxide as the additive of electrolytic manganese, but selenium can be deposited in electrolytic process
In the product of electrolytic manganese so that electrolysis manganese Metal purity reduction out, the quality of manganese metal is have impact on, so as to cause electrolytic manganese
The range of application of metal receives certain limitation.In addition, the toxicity of selenium is more than arsenic, significantly can be accumulated in human body, therefore
Research of the environmental protection without selenium or low selenium additive turns into important research direction.And use sulfur dioxide as additive, it is electrolysed out
What is come is high-purity manganese of the purity more than or equal to 99.9%.It is easily exceeded but the content of sulphur is high in manganese Metal, sulfur-containing waste water
Processing cost is high, while also bringing huge pollution to environment.With continuing to develop for industry, all trades and professions are to the pure of manganese Metal
Degree requires more and more higher.Therefore, more preferably electrolytic manganese compound additive research and development with application holding to electrolytic manganese industry
Supervention exhibition plays a driving role.
The content of the invention
It is above-mentioned using single selenium dioxide, sulfur dioxide as electrolytic manganese solution additive it is an object of the invention to overcome
A kind of shortcoming, there is provided method of the low selenium composite additive electrolytic manganese of addition.
Concretely comprise the following steps：
(1) negative electrode uses stainless steel electrode, by sand papering, polishing, washing, in being dried 30 ~ 90 minutes at 70 ~ 90 DEG C, puts
Enter in 0.5% sodium silicate solution and soak 10 ~ 20 minutes, dried 30 ~ 90 minutes at 70 ~ 90 DEG C after washing, be obtained standby
Negative electrode.
(2) 1 L mixed solutions are prepared, the mixed solution contains 15 ~ 25 g/L manganese sulfates and 100 ~ 130 g/L ammonium sulfate, then
The compound additive of selenium dioxide and zinc oxide is added, makes the concentration of selenium dioxide for 5 mg/L, oxidation zinc concentration is 0.5 ~ 1
Mg/L, 7 are adjusted to by the pH value of mixed solution, and in being stirred 0.5 ~ 2 hour at 40 DEG C mixed solution then is obtained into electrolyte standby
With.
(3) electrolyte obtained in step (2) is put into 40 DEG C of thermostat water baths, insertion is standby through step (1) treatment
Negative electrode, anode uses titanium plate, then starts constant-temperature constant-current electrolysis, and electrolytic current density is 350 ~ 450 A/m2, decomposition voltage is 5
~ 7 V, electrolysis obtains electrolytic manganese after 4 hours.
The sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are chemical pure and above purity.
The inventive method is simple to operate, and the bath composition of the electrolytic manganese for being used is simple, it is easy to safeguard, selenium in additive
Content is relatively low, and compound additive is formed by adding appropriate zinc oxide, can obtain high-purity electrolysis manganese product, electrolytic manganese
Purity and with preferable current efficiency, reducing energy consumption and can be conducive to environmental protection more than 97%.
Specific embodiment
Embodiment：
(1) negative electrode uses stainless steel electrode, by sand papering, polishing, washing, in being dried 40 minutes at 80 DEG C, is put into 0.5%
Sodium silicate solution in soak 10 minutes, after washing at 80 DEG C dry 40 minutes, be obtained standby negative electrode.
(2) 1 L mixed solutions, the mixed solution manganese sulfate containing 18g/L and 110 g/L ammonium sulfate are prepared, dioxy is added
Change the compound additive of selenium and zinc oxide, make the concentration of selenium dioxide for 5 mg/L, oxidation zinc concentration is 0.6mg/L, will be mixed
The pH value for closing solution is adjusted to 7, and in being stirred 1 hour at 40 DEG C mixed solution then is obtained into electrolyte standby.
(3) electrolyte obtained in step (2) is put into 40 DEG C of thermostat water baths, insertion is standby through step (1) treatment
Negative electrode, anode uses titanium plate, then starts constant-temperature constant-current electrolysis, and electrolytic current density is 400 A/m2, decomposition voltage is 5.5
V, electrolysis obtains electrolytic manganese after 4 hours.
It is pure that the sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are chemistry.
Obtained electrolytic manganese depositing homogeneous in the present embodiment, smooth, careful, current efficiency is 56.8%.Manganese particle it is smaller and
Size is homogeneous, and the purity of the electrolytic manganese that electrolysis is obtained after 4 hours reaches 97.6%.
Claims (1)
1. a kind of method for adding low selenium composite additive electrolytic manganese, it is characterised in that concretely comprise the following steps：
(1) negative electrode uses stainless steel electrode, by sand papering, polishing, washing, in being dried 30 ~ 90 minutes at 70 ~ 90 DEG C, puts
Enter in 0.5% sodium silicate solution and soak 10 ~ 20 minutes, dried 30 ~ 90 minutes at 70 ~ 90 DEG C after washing, be obtained standby
Negative electrode；
(2) 1 L mixed solutions are prepared, the mixed solution contains 15 ~ 25 g/L manganese sulfates and 100 ~ 130 g/L ammonium sulfate, adds
The compound additive of selenium dioxide and zinc oxide, makes the concentration of selenium dioxide for 5 mg/L, and oxidation zinc concentration is 0.5 ~ 1 mg/
L, 7 are adjusted to by the pH value of mixed solution, and in being stirred 0.5 ~ 2 hour at 40 DEG C mixed solution then is obtained into electrolyte standby；
(3) electrolyte obtained in step (2) is put into 40 DEG C of thermostat water baths, standby the moon that insertion is processed through step (1)
Pole, anode uses titanium plate, then starts constant-temperature constant-current electrolysis, and electrolytic current density is 350 ~ 450 A/m2, decomposition voltage is 5 ~ 7
V, electrolysis obtains electrolytic manganese after 4 hours；
The sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are chemical pure and above purity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710105243.5A CN106835195B (en) | 2017-02-26 | 2017-02-26 | A method of the low selenium composite additive electrolytic manganese of addition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710105243.5A CN106835195B (en) | 2017-02-26 | 2017-02-26 | A method of the low selenium composite additive electrolytic manganese of addition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106835195A true CN106835195A (en) | 2017-06-13 |
| CN106835195B CN106835195B (en) | 2018-11-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710105243.5A Active CN106835195B (en) | 2017-02-26 | 2017-02-26 | A method of the low selenium composite additive electrolytic manganese of addition |
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Citations (4)
| 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 |
| CN102691072A (en) * | 2012-06-01 | 2012-09-26 | 湘西自治州三泰精细化工有限责任公司 | Special additive for electrolytic manganese metal and preparation method thereof |
| CN104789755A (en) * | 2015-04-23 | 2015-07-22 | 中南大学 | Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal |
| CN106119891A (en) * | 2016-08-30 | 2016-11-16 | 中信大锰矿业有限责任公司 | A kind of energy saving technique in electrolytic manganese electrowinning process |
-
2017
- 2017-02-26 CN CN201710105243.5A patent/CN106835195B/en active Active
Patent Citations (4)
| 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 |
| CN102691072A (en) * | 2012-06-01 | 2012-09-26 | 湘西自治州三泰精细化工有限责任公司 | Special additive for electrolytic manganese metal and preparation method thereof |
| CN104789755A (en) * | 2015-04-23 | 2015-07-22 | 中南大学 | Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal |
| CN106119891A (en) * | 2016-08-30 | 2016-11-16 | 中信大锰矿业有限责任公司 | A kind of energy saving technique in electrolytic manganese electrowinning process |
Non-Patent Citations (2)
| Title |
|---|
| 云正宽: "《冶金工程设计》", 30 June 2006 * |
| 杨萍: "电解锰无硒、无铬清洁制备技术的研究及应用", 《中南大学硕士学位论文》 * |
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| CN106835195B (en) | 2018-11-06 |
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| PB01 | Publication | ||
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| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170613 Assignee: Guilin Xinglong Metal Products Processing Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044396 Denomination of invention: A Method for Adding Low Selenium Composite Additives to Electrolytic Manganese Granted publication date: 20181106 License type: Common License Record date: 20231027 |
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| EE01 | Entry into force of recordation of patent licensing contract |