CN106835195B - A method of the low selenium composite additive electrolytic manganese of addition - Google Patents
A method of the low selenium composite additive electrolytic manganese of addition Download PDFInfo
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- CN106835195B CN106835195B CN201710105243.5A CN201710105243A CN106835195B CN 106835195 B CN106835195 B CN 106835195B CN 201710105243 A CN201710105243 A CN 201710105243A CN 106835195 B CN106835195 B CN 106835195B
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- manganese
- spare
- zinc oxide
- electrolytic manganese
- mixed solution
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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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 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
- 238000005498 polishing Methods 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
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 4
- 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
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 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
- 235000019795 sodium metasilicate Nutrition 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 3
- 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
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion 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
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of methods of the low selenium composite additive electrolytic manganese of addition.Cathode uses stainless steel electrode, and by sand paper polishing, polishing, washing, re-dry is put into 0.5% sodium silicate solution and impregnates 10 ~ 20 minutes, and spare cathode is made in re-dry after washing；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 to 7, then stir mixed solution 0.5 ~ 2 hour at 40 DEG C, and it is spare that electrolyte is made；Electrolyte is put into 40 DEG C of thermostat water baths, is inserted into spare cathode, it is 350 ~ 450 A/m that anode, which uses titanium plate, constant-temperature constant-current electrolysis, electrolytic current density,2, decomposition voltage is 5 ~ 7 V, and electrolysis obtains electrolytic manganese after 4 hours.The method of the present invention is easy to operate, and used bath composition is simple, easy to maintain, forms compound additive by adding zinc oxide, 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.
This method is that the compound additive containing selenium dioxide and zinc oxide is added, can obtain in the manganese sulfate electrolyte of liquid containing ammonium sulfate
Reach 97% or more electrolytic manganese to purity.
Background technology
Electrolytic manganese industry both at home and abroad now, mainly uses the additive of selenium dioxide and sulfur dioxide as electrolytic manganese.I
State's electrolytic manganese factory mainly uses additive of the single selenium dioxide as electrolytic manganese, but selenium can deposit in electrolytic process
In the product of electrolytic manganese so that the manganese Metal purity for being electrolysed out reduces, and the quality of manganese metal is affected, so as to cause electrolytic manganese
The application range of metal receives certain limitation.In addition, the toxicity of selenium is more than arsenic, can significantly be accumulated in human body, therefore
Research of the environmental protection without selenium or low selenium additive becomes important research direction.And sulfur dioxide is used to be electrolysed out as additive
What is come is high-purity manganese that purity is greater than or equal to 99.9%.But the content of sulphur is high in manganese Metal, it is easy to be exceeded, sulfur-containing waste water
Processing cost is high, while also bringing huge pollution to environment.With the continuous development of industry, all trades and professions are to the pure of manganese Metal
Degree requires higher and higher.Therefore, more preferably electrolytic manganese compound additive research and development with application holding to electrolytic manganese industry
Supervention exhibition plays a driving role.
Invention content
It is above-mentioned using single selenium dioxide, sulfur dioxide as electrolytic manganese solution additive it is an object of the invention to overcome
Disadvantage provides a kind of method for adding low selenium composite additive electrolytic manganese.
The specific steps are：
(1) cathode uses stainless steel electrode, 30 ~ 90 points dry at 70 ~ 90 DEG C by sand paper polishing, polishing, washing
Clock is put into 0.5% sodium silicate solution and impregnates 10 ~ 20 minutes, 30 ~ 90 minutes dry at 70 ~ 90 DEG C after washing, is made
Spare cathode.
(2) 1 L mixed solutions are prepared, which 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 a concentration of 5 mg/L of selenium dioxide, a concentration of the 0.5 ~ 1 of zinc oxide
The pH value of mixed solution is adjusted to 7 by mg/L, then stirs mixed solution 0.5 ~ 2 hour at 40 DEG C, and it is standby that electrolyte is made
With.
(3) electrolyte made from step (2) is put into 40 DEG C of thermostat water baths, insertion handles spare through step (1)
Cathode, anode use titanium plate, then start constant-temperature constant-current electrolysis, and electrolytic current density is 350 ~ 450 A/m2, decomposition voltage 5
~ 7 V, electrolysis obtain electrolytic manganese after 4 hours.
The sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are the chemical pure and above purity.
The method of the present invention is easy to operate, and the bath composition of used electrolytic manganese is simple, easy to maintain, selenium in additive
Content is relatively low, forms compound additive by adding suitable zinc oxide, can obtain high-purity electrolysis manganese product, electrolytic manganese
Purity has preferable current efficiency 97% or more, can reduce energy consumption and be good for the environment.
Specific implementation mode
Embodiment：
(1) cathode uses stainless steel electrode, 40 minutes dry at 80 DEG C by sand paper polishing, polishing, washing, is put into
It is impregnated 10 minutes in 0.5% sodium silicate solution, it is 40 minutes dry at 80 DEG C after washing, spare cathode is made.
(2) 1 L mixed solutions, the mixed solution manganese sulfate containing 18g/L and 110 g/L ammonium sulfate are prepared, dioxy is added
The compound additive for changing selenium and zinc oxide, makes a concentration of 5 mg/L of selenium dioxide, a concentration of 0.6mg/L of zinc oxide that will mix
The pH value for closing solution is adjusted to 7, then stirs mixed solution 1 hour at 40 DEG C, and it is spare that electrolyte is made.
(3) electrolyte made from step (2) is put into 40 DEG C of thermostat water baths, insertion handles spare through step (1)
Cathode, anode use titanium plate, then start constant-temperature constant-current electrolysis, and electrolytic current density is 400 A/m2, decomposition voltage 5.5
V, electrolysis obtain electrolytic manganese after 4 hours.
The sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are that chemistry is pure.
Electrolytic manganese depositing homogeneous obtained, smooth, careful, current efficiency 56.8% in the present embodiment.Manganese particle it is smaller and
Size is uniform, and the purity for the electrolytic manganese that electrolysis obtains 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 the specific steps are：
(1) cathode uses stainless steel electrode, 30 ~ 90 minutes dry at 70 ~ 90 DEG C by sand paper polishing, polishing, washing, puts
Enter in 0.5% sodium silicate solution and impregnates 10 ~ 20 minutes, it is 30 ~ 90 minutes dry at 70 ~ 90 DEG C after washing, it is made spare
Cathode；
(2) 1 L mixed solutions are prepared, which contains 15 ~ 25 g/L manganese sulfates and 100 ~ 130 g/L ammonium sulfate, add
The compound additive of selenium dioxide and zinc oxide makes a concentration of 5 mg/L of selenium dioxide, a concentration of 0.5 ~ 1 mg/ of zinc oxide
The pH value of mixed solution is adjusted to 7 by L, then stirs mixed solution 0.5 ~ 2 hour at 40 DEG C, and it is spare that electrolyte is made；
(3) electrolyte made from step (2) is put into 40 DEG C of thermostat water baths, is inserted into the spare the moon handled through step (1)
Pole, anode use titanium plate, then start constant-temperature constant-current electrolysis, and electrolytic current density is 350 ~ 450 A/m2, decomposition voltage is 5 ~ 7
V, electrolysis obtain electrolytic manganese after 4 hours；
The sodium metasilicate, manganese sulfate, ammonium sulfate, selenium dioxide and zinc oxide are the 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 |
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| Publication Number | Publication Date |
|---|---|
| CN106835195A CN106835195A (en) | 2017-06-13 |
| CN106835195B true CN106835195B (en) | 2018-11-06 |
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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 (1)
| Title |
|---|
| 电解锰无硒、无铬清洁制备技术的研究及应用;杨萍;《中南大学硕士学位论文》;20140615;第B023-128页 * |
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| CN106835195A (en) | 2017-06-13 |
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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 |