CN104004919B - The environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production - Google Patents
The environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production Download PDFInfo
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- CN104004919B CN104004919B CN201410257168.0A CN201410257168A CN104004919B CN 104004919 B CN104004919 B CN 104004919B CN 201410257168 A CN201410257168 A CN 201410257168A CN 104004919 B CN104004919 B CN 104004919B
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- waste residue
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production, comprise the steps: that (1) washs waste residue clear water, wash out water-soluble manganese, ammonia nitrogen, after press filtration, obtain slag washing liquid; (2) slag washing liquid treats next washery slag Reusability after collecting, until after in slag washing liquid, manganese and ammonia nitrogen reach finite concentration, slag washing liquid uses as feed liquid electrolysis manganese production fluid infusion; (3) in filter-press residues, add sulfurous iron ore, after high-temperature roasting, carry out separation of air from dust; (4) powder cooling is obtained cement clinker; SO
2gas is for the production of the vitriol oil, and exhaust gas utilization manganese oxide ore carries out Reducing and absorption, forms manganous sulfate; (5) vitriol oil in step (4) and manganous sulfate are all for the production of electrolytic manganese.The present invention not only can eliminate the harm that the waste residue in electrolytic manganese production brings environment protection and water resources protection, and can carry out cycling and reutilization to waste residue, avoids the loss of useful resources, improves economic worth.
Description
Technical field
The invention belongs to waste residue cycling and reutilization technical field, particularly the environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production.
Background technology
A large amount of harmful waste residues can be produced in production electrolytic metal Mn process.Along with manganese carbonate ore resource grade is more and more lower, the waste residue amount produced in production process is just increasing, and this causes harm and hidden danger greatly to environment, downstream water resource, groundwater pollution.But contain a large amount of valuable composition in waste residue simultaneously, as: metal etc. required in manganous sulfate, calcium sulfate, magnesium sulfate, ammonia nitrogen, silicon and other manufacture of cement.Therefore, the technology of carrying out environmental protection treatment and recycle to the waste residue in electrolytic manganese production is unusual exigence, to reduce the damage and pollution to ecotope, and avoids a large amount of losses of resource.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide the environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production, not only can eliminate pressure and harm that waste residue in electrolytic manganese production brings environment and water resources, and complete cycling and reutilization can be carried out to waste residue, the useful component of abundant extraction waste residue, avoids the loss of useful resources.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:. the environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production, comprises the steps:
(1) after first washing with clear water waste residue, through press filtration, the slag washing liquid containing manganese and ammonia nitrogen and filter-press residues is obtained;
(2) slag washing liquid treats next washery slag Reusability after collecting, until after in slag washing liquid, manganese and ammonia nitrogen reach finite concentration, slag washing liquid is as feed liquid for the electrolytic manganese production fluid infusion of front road, more supplementary new water carries out washery slag, so repeatedly;
(3) in the filter-press residues obtained after washery slag, proportioning adds sulfurous iron ore, through high-temperature roasting, then carries out separation of air from dust, the SO produced after powder and high-temperature roasting
2gas is separated respectively;
(4) cement clinker is obtained, by isolated SO by after isolated powder cooling
2gas obtains SO through cleaning section, catalyzed oxidation operation
3gas, obtain the vitriol oil through absorbing operation, the unabsorbed waste gas anolyte adding manganese oxide ore carries out absorbing and reducing reaction, forms manganous sulfate;
(5) vitriol oil obtained in step (4) and manganous sulfate one are used from the production of electrolytic manganese.
Further, the SO in step (4)
2gas after cleaning section, SO
2gas with powder be also collected as cement clinker.
Further, in step (4) output the vitriol oil can iterative cycles for absorbing SO
2the SO that gas obtains after purification and catalyzed oxidation
3gas.
The invention has the beneficial effects as follows: the waste residue in electrolytic manganese production treats next washery slag Reusability after carrying out the slag washing liquid collection of washery slag generation, until after in slag washing liquid, manganese, ammonia nitrogen reach finite concentration, slag washing liquid as feed liquid for the electrolytic manganese production fluid infusion of front road, supplement new water again and carry out washery slag, so repeatedly.Technique of the present invention by environment manganese and ammonia nitrogen separate from waste residue, and the slag washing liquid that will have certain density manganese and ammonia nitrogen is produced as feed liquid electrolysis manganese, thus achieves the object avoiding contaminate environment and resource reutilization; Filter-press residues after press filtration by after a certain proportion of sulfurous iron ore of characteristic proportioning of processing requirement and filter-press residues after high-temperature roasting, separation of air from dust, powder is produced for cement mill as cement clinker, and the SO that high-temperature roasting produces
2gas is then for the production of sulfuric acid, and waste gas can form manganous sulfate again after the manganese oxide ore absorption reduction adding anolyte.Thus the useful component in waste residue is all extracted, and is effectively recycled, and neither wastes resource, protects environment again.The present invention carries out environmental protection treatment and cycling and reutilization to the waste residue in electrolytic manganese production; realize electrolytic manganese production without scorification; while protection of the environment; bring again the output of byproduct sulfuric acid and cement clinker; also considerable economic benefit is created; significantly reduce the construction investment of electrolytic manganese engineering, reduce the unit cost of electrolytic manganese production, also improve the reserve strength of corporate sustainability and the market competitiveness of enterprise.
Accompanying drawing explanation
Fig. 1 is the schema of the environment-protective circulating recycling technique of waste residue in electrolytic manganese production of the present invention.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in detail, can be easier to make advantages and features of the invention be readily appreciated by one skilled in the art, thus more explicit defining is made to protection scope of the present invention.
As shown in Figure 1, in a kind of electrolytic manganese production, the environment-protective circulating recycling technique of waste residue, comprises the steps:
(1) after first washing with clear water waste residue, through press filtration, the slag washing liquid containing manganese and ammonia nitrogen and filter-press residues is obtained;
(2) slag washing liquid treats next washery refuse Reusability after collecting, until after in slag washing liquid, manganese and ammonia nitrogen reach finite concentration, slag washing liquid is as feed liquid for the electrolytic manganese production fluid infusion of front road, more supplementary new water carries out washery slag, so repeatedly;
(3) add sulfurous iron ore by the characteristic proportioning of process specifications and filter-press residues in the filter-press residues obtained after washery slag, through high-temperature roasting, then carry out separation of air from dust, the SO produced after powder and high-temperature roasting
2gas is separated respectively; In this step after filter-press residues proportioning sulfurous iron ore through high-temperature roasting, the iron contained in filter-press residues, calcium, magnesium, silicon etc. can be extracted, for manufacture of cement.During high-temperature roasting, the reaction formula of fractions is:
FeS
2+O
2→Fe
2O
3+SO
2↑
CaSO
4+O
2→CaO+SO
2↑
SiSO
4+O
2→SiO+SO
2↑
MgSO
4+O
2→MgO+SO
2↑
(4) by isolated powder (containing Fe
2o
3, the composition such as CaO, SiO, MgO) obtain cement clinker, by isolated SO after cooling
2gas obtains SO through cleaning section, catalyzed oxidation operation
3gas, obtain the vitriol oil through absorbing operation, the unabsorbed waste gas anolyte adding manganese oxide ore carries out absorbing and reducing reaction, forms manganous sulfate; Wherein cleaning section comprises cyclone dust collection purification and electronics dust cleaning;
(5) vitriol oil obtained in step (4) and manganous sulfate one are used from the production of electrolytic manganese.
Furtherly, the SO in step (4)
2gas after cleaning section, SO
2gas with powder be also collected as cement clinker.
Furtherly, in step (4) output the vitriol oil can iterative cycles for absorbing SO
2the SO that gas obtains after purification and catalyzed oxidation
3gas, by SO
3gas continues to generate the vitriol oil.
In electrolytic manganese production of the present invention, the environment-protective circulating recycling technique of waste residue has the following advantages:
1, main production and the main equipment of the original production of electrolytic metal Mn manufacturer is not changed;
2, process completely and recycle useless press filtration manganese slag, electrolytic manganese production forms cyclic production;
3, waste residue is also the main raw material that our cycling and reutilization is produced, and surmounts national correlative link guaranteed request;
4, reduce production cost (sulfuric acid is cycling and reutilization) widely, improve market competitiveness of enterprises;
5, drop into little, technical maturity, reliable, simple, practical;
6, most manganese, ammonia nitrogen in recyclable waste residue, and all expenses that byproduct brings new benefit to be greater than this technology to be produced; Significantly reduce construction investment; Realize electrolytic manganese production without scorification, there is revolutionary environment protection significance and social value.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (3)
1. the environment-protective circulating recycling technique of waste residue in electrolytic manganese production, is characterized in that, comprise the steps:
(1) after first washing with clear water waste residue, through press filtration, the slag washing liquid containing manganese and ammonia nitrogen and filter-press residues is obtained;
(2) slag washing liquid treats next washery slag Reusability after collecting, until after in slag washing liquid, manganese and ammonia nitrogen reach finite concentration, slag washing liquid is as feed liquid for the electrolytic manganese production fluid infusion of front road, more supplementary new water carries out washery slag, so repeatedly;
(3) in the filter-press residues obtained after washery slag, proportioning adds sulfurous iron ore, through high-temperature roasting, then carries out separation of air from dust, the SO produced after powder and high-temperature roasting
2gas is separated respectively;
(4) cement clinker is obtained, by isolated SO by after isolated powder cooling
2gas obtains SO through cleaning section, catalyzed oxidation operation
3gas, obtain the vitriol oil through absorbing operation, the unabsorbed waste gas anolyte adding manganese oxide ore carries out absorbing and reducing reaction, forms manganous sulfate;
(5) vitriol oil obtained in step (4) and manganous sulfate one are used from the production of electrolytic manganese.
2. the environment-protective circulating recycling technique of waste residue in electrolytic manganese production according to claim 1, is characterized in that: the SO in step (4)
2gas after cleaning section, SO
2gas with powder be also collected as cement clinker.
3. the environment-protective circulating recycling technique of waste residue in electrolytic manganese production according to claim 1, is characterized in that: in step (4) output the vitriol oil can iterative cycles for absorbing SO
2the SO that gas obtains after purification and catalyzed oxidation
3gas.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105525311B (en) * | 2014-10-21 | 2018-05-04 | 彭勇达 | Qualified electrolyte directly elutes recovery process technical method in a kind of electrolytic manganese leached mud |
| CN104946890A (en) * | 2015-07-15 | 2015-09-30 | 贵州红星发展大龙锰业有限责任公司 | Method for synchronously recycling ammonia and manganese in manganese metal chemical combination slag |
| CN108251863A (en) * | 2017-12-07 | 2018-07-06 | 宁夏天元锰业有限公司 | A kind of method for comprehensively utilizing liquid and waste slag produced Joint Production electrolytic manganese and cement |
| CN108689671B (en) * | 2018-06-07 | 2020-12-04 | 广西壮族自治区环境保护科学研究院 | Method for treating and recovering manganese and ammonium sulfate in electrolytic manganese slag |
| CN110735154B (en) * | 2018-09-27 | 2021-09-24 | 庞炼红 | Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal |
| CN110735040B (en) * | 2018-10-18 | 2021-04-30 | 庞炼红 | Electrolytic manganese metal waste residue treatment method |
| CN114250488A (en) * | 2021-12-31 | 2022-03-29 | 宁夏天元锰材料研究院(有限公司) | Method for producing manganese sulfate electrolyte |
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Effective date of registration: 20150710 Address after: 215002 -2-403 room, No. 68 vinegar lane, Suzhou District, Jiangsu, Suzhou, China Applicant after: Zhang Anliang Applicant after: Pang Lianhong Address before: 215002 -2-403 room, No. 68 vinegar lane, Suzhou District, Jiangsu, Suzhou, China Applicant before: Zhang Anliang |
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