CN102424490B - Treatment process for recycling chromate waste water in producing electrolytic manganese metal - Google Patents
Treatment process for recycling chromate waste water in producing electrolytic manganese metal Download PDFInfo
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- CN102424490B CN102424490B CN2011103254773A CN201110325477A CN102424490B CN 102424490 B CN102424490 B CN 102424490B CN 2011103254773 A CN2011103254773 A CN 2011103254773A CN 201110325477 A CN201110325477 A CN 201110325477A CN 102424490 B CN102424490 B CN 102424490B
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Abstract
The invention discloses a treatment process for recycling chromate waste water in producing electrolytic manganese metal, comprising the following steps: adding a potassium dichromate solution in chromate waste water from a passivation tank to obtain a mixed solution A after mixing, and reputting the mixed solution A into the passivation tank for recycling; when impurity content in the chromate waste water is high, filtering the chromate waste water through a filter press for removing impurities, then adding an electrolytic catholyte and reducing Cr<6+> to Cr<3+> to obtain a mixed solution B after the reaction, and sending the mixed solution B into a manganese sulfate lixiviating tank through a pump for recycling. The concentration of the chromate waste water from the passivation tank is 5-9 g/L, the concentration of the potassium dichromate solution is 30-35 g/L, and the concentration of chromium in the mixed solution A is 13-17 g/L. According to the invention, the chromate waste water is recycled, the discharge problem of the chromate waste water is solved, the construction fund and processing cost are saved, and the pollution discharge capacity to the environment is reduced.
Description
Technical field
The invention belongs to waste water treatment process technical field in the Chemical Manufacture, especially relate to the treatment process of chromate waste water recycle in a kind of electrolytic metal Mn production.
Background technology
In the production process of electrolytic metal Mn, from manganous sulfate electrolytic solution, the manganese metal of electrolysis production is attached on the negative electrode, be exposed in the air easily oxidized, so earlier the negative electrode that adheres to the manganese metal, soak 3min through deactivation slot, outside surface forms fine and close manganese dioxide membrane, stop further oxidation, described passivation just is converted into MnO with Mn
2Oxidising process.Contain a large amount of sexavalent chrome etc. in the waste water of deactivation slot discharging, this is the most unmanageable part in the waste water from electrolytic metal manganese production.Traditional treatment process has three kinds, method one: be hexavalent chrome reduction trivalent chromium with Sulfothiorine under acidic conditions, the add-on of Sulfothiorine is chromic 4.5 times, neutralizes with sodium hydroxide solution then, make trivalent chromium generate precipitation of hydroxide, filtered and recycled chromium slag.Method two: with the sexavalent chrome in the ferrous sulfate reducing waste water, and with the lime neutralization, form the chromium hydroxide precipitation that is insoluble in water, filtered and recycled chromium slag, this method is adopted by most producers.Method three: activated carbon treatment method.Gac has absorption or reductive action to sexavalent chrome, and these two kinds of effects are shifted with the variation of the pH value of waste water.Be 4～6.5 o'clock at pH, sexavalent chrome is with HCrO
4 -And CrO
4 2-Ionic forms is by charcoal absorption; Cr under strong acidic condition
6+Be reduced to Cr by gac
3+, Cr
3+Hardly by charcoal absorption.Since gac, acid, and alkali consumption is big, the processing costs height.
Summary of the invention
The technical problem to be solved in the present invention provide a kind of electrolytic metal Mn that reduces chromium slag discharging produce in the treatment process of chromate waste water recycle.
The treatment process of chromate waste water recycle added potassium bichromate solution during a kind of electrolytic metal Mn was produced in the chromate waste water from deactivation slot, obtained mixed liquor A after the mixing, mixed liquor A is sent into deactivation slot again recycle; Foreign matter content filters by pressure filter and to remove impurity and obtain filtrate more for a long time in from the chromate waste water of deactivation slot, adds electrolysis cathode liquid in filtrate, with Cr
6+Be reduced to Cr
3+, behind the question response, obtain mixed liquid B, with pump mixed liquid B is sent into the manganous sulfate leaching vat and recycle.
Preferably, be that to add concentration in the chromate waste water of 5～9g/L be the potassium bichromate solution of 30～35g/L at the total chromium concn from deactivation slot, make the total chromium concn that mixes in the solution of back reach 13～17g/L, obtain mixed liquor A, then mixed liquor A is sent into deactivation slot again and recycle; Foreign matter content filters by pressure filter and to obtain filtrate after removing impurity more for a long time in from the chromate waste water of deactivation slot, adds electrolysis cathode liquid in filtrate, makes Cr
6+Be reduced to Cr
3+, behind the question response, obtain mixed liquid B, with pump mixed liquid B is sent into the manganous sulfate leaching vat and recycle.
Described electrolysis cathode liquid refers to manganese sulfate solution.
Described impurity too much refers to solution comparatively muddy the time.
Principle of work of the present invention is: in the future total chromium concn of self-passivation groove is in the chromate waste water of low concentration of 5～9g/L, adds the potassium bichromate K that total chromium concn is the high density of 30～35g/L
2Cr
2O
7Solution just replenishes Cr
6+, after total chromium concn reaches 13～17g/L, send into deactivation slot again and recycle; If behind the life-time service, find that foreign matter content increases in the chromate waste water, then after pressure filter filters, add electrolysis cathode liquid MnSO just
4Solution is with Cr
6+Be reduced to Cr
3+, after the reaction, with pump mixed liquid B is sent into the manganous sulfate leaching vat, the manganous sulfate leaching vat will contain Cr for the preparation of the electrolytic solution manganous sulfate
3+Manganese solution send over, and use it for catholyte and recycle.The filter residue that waste water is crossed behind the pressure filter focuses on.
Advantage of the present invention and effect: will contain the cycling utilization of wastewater of chromium, and not only solve the emission problem of chromate waste water, and save construction fund and processing cost, and reduce the discharge amount of pollution to environment.
Embodiment
In order to understand the present invention, the invention will be further described below by specific embodiment.
Embodiment one
Total chromium concn of self-passivation groove obtains the mixed liquor A that total chromium concn is 15g/L for the 7g/L chromate waste water joins the potassium bichromate solution that total chromium concn is 32g/L after the mixing in the future, with mixed liquor A, sends into deactivation slot again and recycles;
In from the chromate waste water of deactivation slot foreign matter content more for a long time, then chromate waste water need through pressure filter filter remove most of impurity after, add electrolysis cathode liquid, with Cr
6+Be reduced to Cr
3+, after reacting completely, obtain mixed liquid B, with pump mixed liquid B is sent into the manganous sulfate leaching vat, the manganous sulfate leaching vat will contain Cr for the preparation of the electrolytic solution manganous sulfate
3+Manganese solution send over, and use it for catholyte and recycle.
Embodiment two
Total chromium concn of self-passivation groove obtains the mixed liquor A that total chromium concn is 13g/L for the 5g/L chromate waste water joins the potassium bichromate solution that total chromium concn is 30g/L after the mixing in the future, with mixed liquor A, sends into deactivation slot again and recycles;
In from the chromate waste water of deactivation slot foreign matter content more for a long time, then chromate waste water need through pressure filter filter remove most of impurity after, add electrolysis cathode liquid, with Cr
6+Be reduced to Cr
3+, after reacting completely, obtain mixed liquid B, with pump mixed liquid B is sent into the manganous sulfate leaching vat, the manganous sulfate leaching vat will contain Cr for the preparation of the electrolytic solution manganous sulfate
3+Manganese solution send over, and use it for catholyte and recycle.
Embodiment three
Total chromium concn of self-passivation groove obtains the mixed liquor A that total chromium concn is 17g/L for the 9g/L chromate waste water joins the potassium bichromate solution that total chromium concn is 35g/L after the mixing in the future, with mixed liquor A, sends into deactivation slot again and recycles;
In from the chromate waste water of deactivation slot foreign matter content more for a long time, then chromate waste water need through pressure filter filter remove most of impurity after, add electrolysis cathode liquid, with Cr
6+Be reduced to Cr
3+, after reacting completely, obtain mixed liquid B, with pump mixed liquid B is sent into the manganous sulfate leaching vat, the manganous sulfate leaching vat will contain Cr for the preparation of the electrolytic solution manganous sulfate
3+Manganese solution send over, and use it for catholyte and recycle.
The present invention is not limited to above-mentioned preferred forms, and other any identical with the present invention or akin products that anyone draws under enlightenment of the present invention all drop within protection scope of the present invention.
Claims (1)
1. the treatment process of chromate waste water recycle during an electrolytic metal Mn is produced is characterized in that:
Be that to add concentration in the chromate waste water of 5～9g/L be the potassium bichromate solution of 30～35g/L at the total chromium concn from deactivation slot, make the total chromium concn that mixes in the solution of back reach 13～17g/L, obtain mixed liquor A, then mixed liquor A is sent into deactivation slot again and recycle;
Foreign matter content filters by pressure filter and to obtain filtrate after removing impurity more for a long time in from the chromate waste water of deactivation slot, adds electrolysis cathode liquid in filtrate, makes Cr
6+Be reduced to Cr
3+, behind the question response, obtain mixed liquid B, with pump mixed liquid B to be sent into the manganous sulfate leaching vat and recycle, described electrolysis cathode liquid is manganese sulfate solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103254773A CN102424490B (en) | 2011-10-24 | 2011-10-24 | Treatment process for recycling chromate waste water in producing electrolytic manganese metal |
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|---|---|---|---|
| CN2011103254773A CN102424490B (en) | 2011-10-24 | 2011-10-24 | Treatment process for recycling chromate waste water in producing electrolytic manganese metal |
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| CN102424490A CN102424490A (en) | 2012-04-25 |
| CN102424490B true CN102424490B (en) | 2013-07-10 |
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| CN2011103254773A Active CN102424490B (en) | 2011-10-24 | 2011-10-24 | Treatment process for recycling chromate waste water in producing electrolytic manganese metal |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103669032A (en) * | 2012-09-19 | 2014-03-26 | 浙江中辉皮草有限公司 | Recycling method of fur oxidation dyeing chrome mordant dye liquor |
| CN104829135A (en) * | 2015-03-31 | 2015-08-12 | 济南大学 | Application of waste adsorbent as coloring agent and coloring agent and coloring agent preparation and application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB535246A (en) * | 1939-04-03 | 1941-04-02 | Consolidating Mining & Smeltin | Electrolytic manganese process |
| US5770090A (en) * | 1989-07-28 | 1998-06-23 | Lewis, Iii; Tom | Method for recovery of heavy metal from waste water |
| CN100590080C (en) * | 2005-10-05 | 2010-02-17 | 湘西自治州清源环保实业有限责任公司 | Process for treating waste water from electrolytic metal manganese production |
| CN1752286A (en) * | 2005-10-10 | 2006-03-29 | 北京科技大学 | Metal Mn passivating liquid and use method thereof |
| CN101481164B (en) * | 2009-02-23 | 2011-02-09 | 武汉钢铁(集团)公司 | Method for processing chrome wastewater from steel surface passivation process |
| CN101838065B (en) * | 2010-01-26 | 2012-06-27 | 中国环境科学研究院 | Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater |
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