CN101892494A - Crystallization inhibitor of electrolytic manganese qualifying liquid - Google Patents
Crystallization inhibitor of electrolytic manganese qualifying liquid Download PDFInfo
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- CN101892494A CN101892494A CN 201010229445 CN201010229445A CN101892494A CN 101892494 A CN101892494 A CN 101892494A CN 201010229445 CN201010229445 CN 201010229445 CN 201010229445 A CN201010229445 A CN 201010229445A CN 101892494 A CN101892494 A CN 101892494A
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- electrolytic manganese
- crystallization inhibitor
- inhibitor
- qualifying liquid
- manganese qualifying
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Abstract
The invention relates to a crystallization inhibitor of electrolytic manganese qualifying liquid. The crystallization inhibitor is a combination solution of a main inhibitor glycine and an auxiliary inhibitor hydroxylamine matter or polycarboxylic acid matter in the mass proportion of 1: (1.5-4). When in use, the mass ratio of the crystallization inhibitor to the electrolytic manganese qualifying liquid is 0.008-0.012. The combination solution of the glycine and the hydroxylamine matter or the polycarboxylic acid matter is used as the crystallization inhibitor of the electrolytic manganese qualifying liquid for the first time, and the inhibitor can effectively inhibit the growth and aggregation of two complex salt crystals of ammonium manganese sulfate and ammonium magnesium sulfate which are main components in the electrolytic manganese qualifying liquid; and by adding the crystallization inhibitor, the yield of crystals can be reduced to original 18.1 percent at most.
Description
Technical field
The present invention relates to electrolytic manganese production technology, be specifically related to the additive in electrolytic manganese qualifying liquid.
Background technology
In the electrolytic manganese process, traditional technology at first wants leaching manganese ore liquid through removal of impurities, and is refining, adds electrolysis additive then, to make electrolytic manganese qualifying liquid, again it carried out electrolysis.Because manganous sulfate, ammonium sulfate and sal epsom in the electrolytic manganese qualifying liquid are easy to depositing crystalline, so, usually cause the obstruction (particularly evident in the winter time) of equipment, pipeline, had a strong impact on ordinary production.For overcoming this defective, comprise following a few class measure in the prior art: (1) reforming equipment, for example increase the outlet bore of anolyte, blocked avoiding; (2) carry out intermittence with artificial or fluid power and stir, concentrate on each pipeline opening to prevent crystallisate; (2) use the hot water injection, with dissolving crystallized thing; (3) manually remove crystallisate---be mostly manually to remove crystallisate with instruments such as chisels with after the pipeline dismounting.Preceding two classes are measures of avoiding blocked, and back two classes are the measures of removing crystallisate.As can be seen, they all are to reduce the remedial afterwards physical method that crystallisate produces, and also promptly all must pay bigger additional cost from these existing measures or method.
Summary of the invention
The objective of the invention is, a kind of crystallization inhibitor that can reduce the electrolytic manganese qualifying liquid of its crystallisate generation is provided.
For realizing described goal of the invention, a kind of like this crystallization inhibitor of electrolytic manganese qualifying liquid is provided, this crystallization inhibitor is by glycine, the combination solution of forming according to 1: 1.5～4 mass ratio with azanol class material or polycarboxylic acid class material.
When use is of the present invention, only be before electrolysis, this crystallization inhibitor and electrolytic manganese qualifying liquid thorough mixing are got final product, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid is 0.008～0.012.
Glycine in the component of the present invention is the simplest compound of structure in the amino acids, only contains an amino and a carboxyl, and it can be used as a kind of ligand and metallic cation forms the glycine chelate thing, is the class in the amino-acid chelate.It is in the component of the present invention to be main inhibitor, the structures shape of its inner complex molecule inner complex have metastable character, the amino of glycine and carboxyl and mn ion and magnesium ion chelating are to belong to oxygen and nitrogen is made ligating atom.Concerning oxygen, electronegative oxygen is oxo stronger with joint efforts than neutral, and when forming inner complex, multidentate ligand has satisfied central ionic ligancy and valency simultaneously, just can obtain " chelating ion " of zero charge, i.e. inner complex salt.The formation of chela ring cause chelating ion than non-chelate ion in the aqueous solution, be difficult to resolve from, thereby have advantages of higher stability.Azanol class material or polycarboxylic acid class material are the inhibitor that helps in the component of the present invention, azanol class material exists with stable azanol ionic species in solution, can form the one dimension title complex with inorganic metal ion, have very strong stability and solubility, polycarboxylic acid class material all contains two or more carboxyls, feasible can be better and mn ion and magnesium ion chelating, form stable solubility ring-type inner complex, and in the aqueous solution, be difficult to resolve from, thereby effectively suppressed main component ammonium manganous sulfate in the electrolytic manganese qualifying liquid, the growth and the gathering of two kinds of complex salt crystals of ammonium magnesium sulfate.
As can be seen, the present invention has the obvious suppression effect to the crystallization of electrolytic manganese qualifying liquid in electrolytic process from scheme and above-mentioned analysis.Also promptly can reduce the generation of crystallisate, and then reduce to stop up, for removing the additional cost that crystallisate is paid for avoiding.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
The crystallization inhibitor of electrolytic manganese qualifying liquid, it is by glycine, the combination solution of forming according to 1: 1.5～4 mass ratio with azanol class material or polycarboxylic acid class material.
Specifically, the azanol class material in the crystallization inhibitor of the present invention comprises diethyl hydroxylamine, phenylbenzene azanol or di-isopropyl azanol.
Polycarboxylic acid class material in the crystallization inhibitor of the present invention comprises citric acid, tartrate or oxysuccinic acid.
Before electrolysis, this crystallization inhibitor and electrolytic manganese qualifying liquid thorough mixing, when this crystallization inhibitor was mixed with electrolytic manganese qualifying liquid, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid was 0.008～0.012.
The present invention had carried out the contrast verification of pilot scale.The prescription and the proportioning of different components, the composition of used electrolytic manganese qualifying liquid is all the same with other processing condition in each time test.Understand and contrast for ease of those skilled in the art, in following checking example table, the crystallization content of the electrolytic manganese qualifying liquid that does not add crystallization inhibitor of the present invention of contrast usefulness is set at 1 (promptly 100%), each verifies that routine crystallization content (%) sees the following form:
1. helping inhibitor is diethyl hydroxylamine
2. helping inhibitor is the phenylbenzene azanol
3. helping inhibitor is the di-isopropyl azanol
4. helping inhibitor is citric acid
5. helping inhibitor is tartrate
6. helping inhibitor is oxysuccinic acid
Those skilled in the art from summary of the invention part about in the Analysis on Mechanism of " helping inhibitor " as can be seen, azanol class material among the present invention or polycarboxylic acid class material are not limited in each three kinds in the checking example.For example: morpholine azanol, 2,2,6,6-tetramethyl--4-hydroxy piperidine azanol, phenylhydroxylamine, succsinic acid, 2-fluoroacetic acid propylmalonic acid all are available.
From each the checking example as can be seen, crystallization inhibitor consumption within the scope of the invention, to reduce crystallization content to influence difference little, and in the crystallization inhibitor main inhibitor with help the proportioning of inhibitor, influence to the minimizing crystallization content is bigger, crystallization content reduces along with the increase that helps the inhibitor proportion, wherein, is that 1: 4 effect is best with the mass ratio of glycine and diethyl hydroxylamine.
Claims (4)
1. the crystallization inhibitor of electrolytic manganese qualifying liquid is characterized in that, this crystallization inhibitor is by glycine, the combination solution of forming according to 1: 1.5～4 mass ratio with azanol class material or polycarboxylic acid class material.
2. according to the crystallization inhibitor of the described electrolytic manganese qualifying liquid of claim 1, it is characterized in that described azanol class material comprises diethyl hydroxylamine, phenylbenzene azanol or di-isopropyl azanol.
3. according to the crystallization inhibitor of the described electrolytic manganese qualifying liquid of claim 1, it is characterized in that described polycarboxylic acid class material comprises citric acid, tartrate or oxysuccinic acid.
4. according to the crystallization inhibitor of claim 1,2 or 3 described electrolytic manganese qualifying liquids, it is characterized in that when described crystallization inhibitor was mixed with electrolytic manganese qualifying liquid, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid was 0.008～0.012.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102294459A CN101892494B (en) | 2010-07-19 | 2010-07-19 | Crystallization inhibitor of electrolytic manganese qualifying liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102294459A CN101892494B (en) | 2010-07-19 | 2010-07-19 | Crystallization inhibitor of electrolytic manganese qualifying liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101892494A true CN101892494A (en) | 2010-11-24 |
| CN101892494B CN101892494B (en) | 2012-02-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010102294459A Expired - Fee Related CN101892494B (en) | 2010-07-19 | 2010-07-19 | Crystallization inhibitor of electrolytic manganese qualifying liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154556A (en) * | 2011-03-02 | 2011-08-17 | 重庆市科学技术研究院 | Method for recovering manganese and magnesium from complex salt crystals generated in manganese electrolysis process |
| CN103540952A (en) * | 2012-07-17 | 2014-01-29 | 吉首大学 | Cyclic organic additive containing nitrogen for efficiently producing electrolytic manganese metal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2317153A (en) * | 1938-07-14 | 1943-04-20 | Chicago Dev Co | Process for the electrodeposition of manganese |
-
2010
- 2010-07-19 CN CN2010102294459A patent/CN101892494B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2317153A (en) * | 1938-07-14 | 1943-04-20 | Chicago Dev Co | Process for the electrodeposition of manganese |
Non-Patent Citations (3)
| Title |
|---|
| 《中国稀土学报》 20080801 孙大贵等 电解制锰添加剂的研究进展 934-937 1-4 第26卷, 2 * |
| 《中国锰业》 19900302 黄志军 美国电解锰生产工艺中添加剂使用概况 41-45 1-4 , 第1期 2 * |
| 《中国锰业》 20090828 蔡大为 我国电解金属锰技术现状及其研究方向 12-16 1-4 第27卷, 第3期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154556A (en) * | 2011-03-02 | 2011-08-17 | 重庆市科学技术研究院 | Method for recovering manganese and magnesium from complex salt crystals generated in manganese electrolysis process |
| CN103540952A (en) * | 2012-07-17 | 2014-01-29 | 吉首大学 | Cyclic organic additive containing nitrogen for efficiently producing electrolytic manganese metal |
| CN103540952B (en) * | 2012-07-17 | 2016-01-06 | 吉首大学 | One type electrolytic gold belongs to the nitrogenous cyclic organic materials additive of manganese High-efficient Production |
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| Publication number | Publication date |
|---|---|
| CN101892494B (en) | 2012-02-29 |
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Granted publication date: 20120229 Termination date: 20120719 |