CN101892494B - Crystallization inhibitor of electrolytic manganese qualifying liquid - Google Patents
Crystallization inhibitor of electrolytic manganese qualifying liquid Download PDFInfo
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- CN101892494B CN101892494B CN2010102294459A CN201010229445A CN101892494B CN 101892494 B CN101892494 B CN 101892494B CN 2010102294459 A CN2010102294459 A CN 2010102294459A CN 201010229445 A CN201010229445 A CN 201010229445A CN 101892494 B CN101892494 B CN 101892494B
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- electrolytic manganese
- crystallization inhibitor
- qualifying liquid
- inhibitor
- 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 several types of measures in the prior art: (1) reforming equipment, for example increase the outlet bore of anolyte, blocked avoiding; (2) carry out intermittence with manual work or fluid power and stir, concentrate on each pipeline opening to prevent crystallisate; (2) use the hot water injection, with dissolving crystallized thing; (3) the artificial crystallisate that removes---be mostly to carry out manual work with instruments such as chisels and remove crystallisate with after the pipeline dismounting.Preceding two types is the measure of avoiding blocked, and back two types is the measure of removing crystallisate.Can find out that from these existing measures or method they all are to reduce the remedial afterwards physical method that crystallisate produces, and also promptly all must pay bigger additional cost.
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 said goal of the invention, a kind of like this crystallization inhibitor of electrolytic manganese qualifying liquid is provided, this crystallization inhibitor is by glycocoll, 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, get final product this crystallization inhibitor and electrolytic manganese qualifying liquid thorough mixing, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid is 0.008～0.012.
Glycocoll 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 a type in the amino-acid chelate.It is in the component of the present invention to be main suppressor factor, the structures shape of its inner complex molecule inner complex have metastable character, the amino of glycocoll and carboxyl and mn ion and mg 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 causes chelating ion to be difficult to resolve in the aqueous solution than non-chelate ion leaving, thereby has advantages of higher stability.Azanol class material or polycarboxylic acid class material are the suppressor factor 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 mg ion chelating; Form stable solubility ring-type inner complex, and in the aqueous solution, be difficult to resolve and leave, thereby effectively suppressed the growth and the gathering of staple ammonium manganous sulfate, two kinds of complex salt crystals of ammonium magnesium sulfate in the electrolytic manganese qualifying liquid.
Can find out that from scheme and above-mentioned analysis the present invention has the obvious suppression effect to the crystallization of electrolytic manganese qualifying liquid in electrolytic process.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.
Below in conjunction with embodiment the present invention is further described.
Embodiment
The crystallization inhibitor of electrolytic manganese qualifying liquid, it is by glycocoll, 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 Hydrocerol A, tartrate or oxysuccinic acid.
Before electrolysis, this crystallization inhibitor and electrolytic manganese qualifying liquid thorough mixing, when mixing this crystallization inhibitor with electrolytic manganese qualifying liquid, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid is 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.For ease of it will be apparent to those skilled in the art that and contrast, in following checking example table, be set at 1 to the crystallization content of the electrolytic manganese qualifying liquid that does not add crystallization inhibitor of the present invention of contrast usefulness (promptly 100%), the routine crystallization content (%) of each checking sees the following form:
1. helping suppressor factor is diethyl hydroxylamine
2. helping suppressor factor is the phenylbenzene azanol
3. helping suppressor factor is the di-isopropyl azanol
4. helping suppressor factor is Hydrocerol A
5. helping suppressor factor is tartrate
6. helping suppressor factor is oxysuccinic acid
Those skilled in the art from summary of the invention part about finding out in the Analysis on Mechanism of " helping suppressor factor " that 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 checking example, can find out; Crystallization inhibitor consumption within the scope of the invention, to reduce crystallization content to influence difference little, and main suppressor factor and the proportioning that helps suppressor factor in the crystallization inhibitor; Influence to reducing crystallization content is bigger; Crystallization content reduces along with the increase that helps the suppressor factor proportion, wherein, is that 1: 4 effect is best with the mass ratio of glycocoll and diethyl hydroxylamine.
Claims (2)
1. the crystallization inhibitor of electrolytic manganese qualifying liquid is characterized in that, the combination solution that this crystallization inhibitor is made up of according to 1: 1.5～4 mass ratio glycocoll and azanol class material; Wherein, said azanol class material is diethyl hydroxylamine, phenylbenzene azanol or di-isopropyl azanol.
2. according to the crystallization inhibitor of the said electrolytic manganese qualifying liquid of claim 1, it is characterized in that when mixing this crystallization inhibitor with electrolytic manganese qualifying liquid, the mass ratio of this crystallization inhibitor and electrolytic manganese qualifying liquid is 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 CN101892494A (en) | 2010-11-24 |
| CN101892494B true 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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Families Citing this family (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 |
| 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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| US2317153A (en) * | 1938-07-14 | 1943-04-20 | Chicago Dev Co | Process for the electrodeposition of manganese |
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| CN101892494A (en) | 2010-11-24 |
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Granted publication date: 20120229 Termination date: 20120719 |