CN104911579A - Electrolytic manganese passivation liquid recycling device and application thereof - Google Patents
Electrolytic manganese passivation liquid recycling device and application thereof Download PDFInfo
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- CN104911579A CN104911579A CN201510380577.4A CN201510380577A CN104911579A CN 104911579 A CN104911579 A CN 104911579A CN 201510380577 A CN201510380577 A CN 201510380577A CN 104911579 A CN104911579 A CN 104911579A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention relates to an electrolytic manganese passivation liquid recycling device and application thereof. The electrolytic manganese passivation liquid recycling device comprises a shell, wherein a purification liquid inlet pipe, an exhausting pipe and a waste liquid inlet pipe are arranged on the upper end face of the shell, and a liquid discharging pipe is arranged on the lower end face of the shell; the purification liquid inlet pipe and the waste liquid inlet pipe are communicated with two liquid storage tanks arranged in the shell respectively; nozzles are fully distributed on the opposite faces of the liquid storage tanks; an adsorption layer and a filtering layer are arranged at the lower part of each liquid storage tank. The application of the electrolytic manganese passivation liquid recycling device comprises the steps of removing manganese ions, adjusting the pH value and adjusting regenerated liquid. With the adoption of the technical scheme, Cr<6+> and Cr<3+> in the waste liquid are basically completely eliminated, and generated sodium dichromate or potassium dichromate can be recycled and repeatedly used as electrolytic manganese passivation liquid. According to the application provided by the invention, steps are fewer so that a lot of time can be saved and the industrial production is facilitated.
Description
Technical field
The present invention relates to a kind of electrolytic manganese passivating liquid retrieving arrangement, and the application of this device in recycling passivating solution.
Background technology
Pure manganese at home obtains and obtains mainly through electrolytic process, and the electrolytic manganese enterprise of more than 95% take manganese carbonate ore as raw material, and manganese processed is carried out in employing acidleach, double salt electrolysis process; Because the production technique of electrolytic manganese limits, can produce more Mn-bearing waste water in the production process of electrolytic manganese, this primary pollution source is wherein passivating wastewater, washes plate waste water, mill floor flushing waste water, filter cloth Cleaning Wastewater, sheet frame Cleaning Wastewater, clear groove waste water, slag storehouse percolate, plant area's rainwash, electrolyzer water coolant etc.
Following content is disclosed in the treatment process " 201310411067.8 " of chromate waste water in producing electrolytic manganese metal recycle; The chromate waste water of self-passivation groove adds potassium bichromate solution in the future, obtains mixed liquor A after mixing, by mixed liquor A, again sends into deactivation slot and recycles; When in chromate waste water, foreign matter content is more, then chromate waste water need be removed after impurity through Filter Press, adds electrolysis cathode liquid, Cr6+ is reduced to Cr3+, after reacting completely, obtains mixed liquid B, with pump, mixed liquid B is sent into manganous sulfate leaching vat and recycles.Though Cr3+ is low stain, but still need individual curing and recovery.
The application's correlation technique content has no disclosure.
Summary of the invention
The object of this invention is to provide one and can make the reusable device of electrolytic manganese passivating liquid, and the application of this device in recycling passivating solution.
The object of the present invention is achieved like this: electrolytic manganese passivating liquid retrieving arrangement, it comprises housing, scavenging solution inlet pipe, vapor pipe and waste liquid inlet pipe is provided with in housing upper surface, lower surface is provided with liquid discharge pipe, scavenging solution inlet pipe, waste liquid inlet pipe are communicated with two container for storing liquids be arranged in housing respectively, container for storing liquid opposite face spreads all over shower nozzle, and container for storing liquid bottom is provided with adsorption layer and filtering layer.
The application of electrolytic manganese passivating liquid retrieving arrangement comprises the following steps:
1. mn ion is removed: by adding 6wt% sodium hydroxide in chrome waste water, pH is adjusted to 8.5 ~ 9.5, precipitation 30min, chrome waste water enters electrolytic manganese passivating liquid retrieving arrangement by waste liquid inlet pipe, by Cr3+ and Cr6+ in the replaceable chrome waste water of aforementioned rare precious metal coating, Cr3+ and Cr6+ in chrome waste water can be made to generate chromium hydroxide precipitation further by scavenging solution again, Cr3+ and Cr6+ removes by adsorption layer further, is filtered by mn ion by filtering layer, and after filtering, solution is discharged by liquid discharge pipe;
2. pH value is regulated: utilize whipping device to stir solution after filtration, add 5wt% sulfuric acid while stirring, adjustment pH is 3-3.2, now generates potassium bichromate, dilutes chromium ion further, obtain regenerated liquid;
3. regulate regenerated liquid: the Sodium chromate and the sodium dichromate 99 that comprise high density in regenerated liquid, chromium ion concentration can reach 15g/L, adds sulfuric acid and water in regenerated liquid, can again as the second stage employ that passivating solution reclaims after regulating regenerated liquid pH and Cr6+ concentration; Concrete pH and Cr6+ look production requirement determine.
Owing to carrying out technique scheme, Cr6+ and Cr3+ in waste liquid can reject by the application substantially completely, and the sodium dichromate 99 of generation or the recyclable repetition of potassium bichromate use as electrolytic manganese passivating liquid.In the application's application, step is less, and it can save the plenty of time, is conducive to suitability for industrialized production.
Accompanying drawing illustrates:
Fig. 1 is electrolytic manganese passivating liquid retrieving arrangement structural representation.
Legend: 1, scavenging solution inlet pipe, 2, vapor pipe, 3, waste liquid inlet pipe, 4, housing, 5, shower nozzle, 6, container for storing liquid, 7, adsorption layer, 8, filtering layer, 9, Sptting plate, 10, liquid discharge pipe
Embodiment: the present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and practical situation.
Embodiment: electrolytic manganese passivating liquid retrieving arrangement it comprise housing, be provided with scavenging solution inlet pipe 1, vapor pipe 2 and waste liquid inlet pipe 3 in housing upper surface, lower surface is provided with liquid discharge pipe 10.Scavenging solution inlet pipe 1, waste liquid inlet pipe 3 are communicated with two container for storing liquids 6 be arranged in housing 4 respectively, and two container for storing liquids 6 are arranged on opposite side in housing 4, and container for storing liquid 6 opposite face spreads all over shower nozzle 5, and container for storing liquid 6 bottom is provided with adsorption layer 7 and filtering layer 8.
In the container for storing liquid 6 be communicated with scavenging solution inlet pipe 1, be filled with alkali lye, described alkali lye is NaOH or KOH solution.
Described adsorption layer is chromium ion polymeric adsorbent, and it is prior art, and concrete component is not described in detail.
Described container for storing liquid 6 is titanium metal tank, with rare precious metal coating on container for storing liquid 6 inwall.
Be provided with Sptting plate 9 between two container for storing liquids 6, its surface scribbles rare precious metal coating, and described Sptting plate 9 is waviness, and material is titanium plate, and chromium ion can adsorb by further.
Described rare precious metal coating is made up of rare precious metal mixture and electroconductive resin.The mass percentage content of rare precious metal mixture and electroconductive resin is: rare precious metal mixture 15-20%, electroconductive resin 80-85%.Described rare precious metal mixture is made up of iridium dioxide, ruthenium dioxide, tantalum dioxide and rare earth oxide, and its mass percentage content is: iridium dioxide 75-85%, ruthenium dioxide 5-15%, tantalum dioxide 5-10%, rare earth oxide 0.8-1.5%.
The application of electrolytic manganese passivating liquid retrieving arrangement comprises the following steps:
1. mn ion is removed: by adding 6wt% sodium hydroxide in chrome waste water, pH is adjusted to 8.5 ~ 9.5, precipitation 30min, chrome waste water enters electrolytic manganese passivating liquid retrieving arrangement by waste liquid inlet pipe 3, by Cr3+ and Cr6+ in the replaceable chrome waste water of aforementioned rare precious metal coating, Cr3+ and Cr6+ in chrome waste water can be made to generate chromium hydroxide precipitation further by scavenging solution again, Cr3+ and Cr6+ removes by adsorption layer 7 further, is filtered by mn ion by filtering layer 8, and after filtering, solution is discharged by liquid discharge pipe 10; When adsorption layer 7 is after absorption Cr6+ reaches capacity, in scavenging solution, unreacted sodium hydroxide or potassium hydroxide are as regenerator, are to exchange with adsorption layer 7 under the condition of 1BV/h at flow;
2. pH value is regulated: utilize whipping device to stir solution after filtration, add 5wt% sulfuric acid while stirring, adjustment pH is 3-3.2, now generates potassium bichromate, dilutes chromium ion further, obtain regenerated liquid;
3. regulate regenerated liquid: the Sodium chromate and the sodium dichromate 99 that comprise high density in regenerated liquid, chromium ion concentration can reach 15g/L, adds sulfuric acid and water in regenerated liquid, can again as the second stage employ that passivating solution reclaims after regulating regenerated liquid pH and Cr6+ concentration; Concrete pH and Cr6+ look production requirement determine.
Above technical characteristic constitutes most preferred embodiment of the present invention, and it has stronger adaptability and best implementation result, can increase and decrease inessential technical characteristic according to actual needs, meet the needs of different situations.
Claims (10)
1. an electrolytic manganese passivating liquid retrieving arrangement, it comprises housing, it is characterized in that: be provided with scavenging solution inlet pipe, vapor pipe and waste liquid inlet pipe in housing upper surface, lower surface is provided with liquid discharge pipe, scavenging solution inlet pipe, waste liquid inlet pipe are communicated with two container for storing liquids be arranged in housing respectively, container for storing liquid opposite face spreads all over shower nozzle, and container for storing liquid bottom is provided with adsorption layer and filtering layer.
2. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 1, is characterized in that: two container for storing liquids are arranged on opposite side in housing.
3. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 2, is characterized in that: described container for storing liquid is titanium metal tank, with rare precious metal coating on container for storing liquid inwall.
4. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 3, is characterized in that: be provided with Sptting plate between two container for storing liquids.
5. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 4, is characterized in that: described Sptting plate is waviness, and its surface scribbles rare precious metal coating.
6. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 4, is characterized in that: described rare precious metal coating is made up of rare precious metal mixture and electroconductive resin.
7. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 6, is characterized in that: the mass percentage content of rare precious metal mixture and electroconductive resin is: rare precious metal mixture 15-20%, electroconductive resin 80-85%.
8. electrolytic manganese passivating liquid retrieving arrangement as claimed in claim 7, it is characterized in that: described rare precious metal mixture is made up of iridium dioxide, ruthenium dioxide, tantalum dioxide and rare earth oxide, its mass percentage content is: iridium dioxide 75-85%, ruthenium dioxide 5-15%, tantalum dioxide 5-10%, rare earth oxide 0.8-1.5%.
9. the application of electrolytic manganese passivating liquid retrieving arrangement, is characterized in that: comprise the following steps:
1. mn ion is removed: by adding 6wt% sodium hydroxide in chrome waste water, pH is adjusted to 8.5 ~ 9.5, precipitation 30min, chrome waste water enters electrolytic manganese passivating liquid retrieving arrangement by waste liquid inlet pipe, by Cr3+ and Cr6+ in the replaceable chrome waste water of aforementioned rare precious metal coating, Cr3+ and Cr6+ in chrome waste water can be made to generate chromium hydroxide precipitation further by scavenging solution again, Cr3+ and Cr6+ removes by adsorption layer further, is filtered by mn ion by filtering layer, and after filtering, solution is discharged by liquid discharge pipe;
2. pH value is regulated: utilize whipping device to stir solution after filtration, add 5wt% sulfuric acid while stirring, adjustment pH is 3-3.2, now generates potassium bichromate, dilutes chromium ion further, obtain regenerated liquid;
3. regulate regenerated liquid: the Sodium chromate and the sodium dichromate 99 that comprise high density in regenerated liquid, chromium ion concentration can reach 15g/L, adds sulfuric acid and water in regenerated liquid, can again as the second stage employ that passivating solution reclaims after regulating regenerated liquid pH and Cr6+ concentration.
10. the application of the solution manganese passivating solution retrieving arrangement as described in claim 1 or 9, it is characterized in that: in container for storing liquid, be filled with alkali lye, described alkali lye is NaOH or KOH solution, when adsorption layer is after absorption Cr6+ reaches capacity, in scavenging solution, unreacted sodium hydroxide or potassium hydroxide are as regenerator, are to exchange with adsorption layer under the condition of 1BV/h at flow.
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Citations (6)
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|---|---|---|---|---|
| JPH10183398A (en) * | 1996-12-20 | 1998-07-14 | Kawasaki Steel Corp | Method for regenerating waste plating liquid and apparatus therefor |
| JP2008045186A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| CN201770518U (en) * | 2010-07-30 | 2011-03-23 | 深圳东江华瑞科技有限公司 | Ion-exchange resin dearsenifying treatment system for acidic etching solution |
| CN102732875A (en) * | 2012-06-30 | 2012-10-17 | 广州大学 | Chromate passivating solution on-line recycling treatment method during electrolytic manganese production process and treatment system thereof |
| CN103498050A (en) * | 2013-09-11 | 2014-01-08 | 洛阳鼎力环保科技有限公司 | Chromium recovery method in electrolytic manganese chromium wastewater treatment process |
| CN204874739U (en) * | 2015-07-02 | 2015-12-16 | 阿克陶科邦锰业制造有限公司 | Electrolytic manganese passivation fluid recovery unit |
-
2015
- 2015-07-02 CN CN201510380577.4A patent/CN104911579A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10183398A (en) * | 1996-12-20 | 1998-07-14 | Kawasaki Steel Corp | Method for regenerating waste plating liquid and apparatus therefor |
| JP2008045186A (en) * | 2006-08-21 | 2008-02-28 | Jfe Steel Kk | Apparatus for regenerating plating solution and method for regenerating plating solution |
| CN201770518U (en) * | 2010-07-30 | 2011-03-23 | 深圳东江华瑞科技有限公司 | Ion-exchange resin dearsenifying treatment system for acidic etching solution |
| CN102732875A (en) * | 2012-06-30 | 2012-10-17 | 广州大学 | Chromate passivating solution on-line recycling treatment method during electrolytic manganese production process and treatment system thereof |
| CN103498050A (en) * | 2013-09-11 | 2014-01-08 | 洛阳鼎力环保科技有限公司 | Chromium recovery method in electrolytic manganese chromium wastewater treatment process |
| CN204874739U (en) * | 2015-07-02 | 2015-12-16 | 阿克陶科邦锰业制造有限公司 | Electrolytic manganese passivation fluid recovery unit |
Non-Patent Citations (2)
| Title |
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| 彭燕等: ""电解锰铬钝化液循环利用工艺技术研究"", 《华南师范大学学报》 * |
| 李响等: ""脂肪磺酸基阳离子交换树脂对Cr3+的吸附和解吸性能"", 《化工环保》 * |
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