CN104261584A - Processing method for waste residues produced by electrolyzing manganese - Google Patents
Processing method for waste residues produced by electrolyzing manganese Download PDFInfo
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- CN104261584A CN104261584A CN201410335685.5A CN201410335685A CN104261584A CN 104261584 A CN104261584 A CN 104261584A CN 201410335685 A CN201410335685 A CN 201410335685A CN 104261584 A CN104261584 A CN 104261584A
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- CN
- China
- Prior art keywords
- sewage
- body refuse
- waste residue
- electrolytic manganese
- treatment process
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a processing method for waste residues produced by electrolyzing manganese. The processing method comprises the following steps of a) reducing Cr<6+> in sewage produced by electrolyzing manganese into Cr<3+>, precipitating and press-filtering to form first sludge; b) adjusting a pH value of the sewage after reducing treatment to an alkaline state by using a first neutralization reaction, precipitating and press-filtering to form second sludge; c) then carrying out stripping treatment on NH3-N and removing residual NH3-N from the sewage after the stripping treatment by adopting a breakpoint chlorination method; d) removing Mn<2+> and H2SO4 from the sewage through a second neutralization reaction by using calcium hydroxide, continuously adding a non-ionic polymer flocculant to remove suspended materials from the sewage, carrying out precipitation and filtration in a sand filter, precipitating and press-filtering to form third sludge. The processing method can effectively remove harmful substances such as Mn<2+>, H2SO4, Cr<6+>, Cr<2+> and NH3-N and heavy metal ions from the waste residues produced by electrolyzing manganese, and is simple to process and low in cost.
Description
Technical field
The present invention relates to a kind of industrial production waste slag treatment method, particularly relate to a kind for the treatment of process of electrolytic manganese production waste residue.
Background technology
The production of existing electrolytic manganese adopts " two-control region " technique, raw material pyrolusite powder and troilite powder are obtained the thick liquid of manganous sulfate with sulfuric acid leaching by a certain percentage, leach and purification time add iron in various different cleaner removing solution and the beavy metal impurity such as cobalt, nickel, lead, copper respectively, the very high manganese sulfate electrolyte of purity is obtained through multiple times of filtration, purification, enter electrolyzer again and carry out electrolysis, separate out electrolytic manganese (work in-process) at negative plate.Take out anode cathode plate, after washing, oven dry, work in-process are peeled off, then through product postprocessing working procedures such as packaging, detections, finally obtain electrolytic manganese product.
Therefore, can produce in the production process of electrolytic manganese in a large amount of waste water and waste residue containing Mn
2+, H
2sO
4, Cr
6+, Cd
2+, NH
3the objectionable impuritiess such as-N and heavy metal ion.Existing treatment process or there is Mn
2+, Cr
6+deng contaminant overstandard, or it is too complicated to there is technological process, the shortcoming that processing cost is very high.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind for the treatment of process of electrolytic manganese production waste residue, can effectively remove Mn in electrolytic manganese production waste residue
2+, H
2sO
4, Cr
6+, Cd
2+, NH
3the objectionable impuritiess such as-N and heavy metal ion, and process is simple, with low cost, be easy to apply.
The present invention solves the problems of the technologies described above the treatment process that the technical scheme adopted is to provide a kind of electrolytic manganese production waste residue, comprises the steps: a) first by Cr in electrolytic manganese production sewage
6+be reduced into Cr
3+, after precipitation, press filtration forms the first body refuse; B) utilize the sewage PH value after first time, neutralization reaction heightened reduction treatment to be alkalescence, after precipitation, press filtration forms the second body refuse; C) then at Ammonia blowing-out tower to NH
3-N carries out stripping process, and the sewage after stripping process adopts break point chlorination method to remove residue NH again
3-N; D) finally adopt calcium hydroxide to carry out neutralization reaction for the second time and remove the Mn in sewage
2+and H
2sO
4, continue to add the suspended substance in non-ionic type polymeric flocculant removal sewage, carry out sedimentation and filtration at sand filter, after precipitation, press filtration forms the 3rd body refuse.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, it is 4.5 ~ 6.5 that described step a) also comprises the PH value controlling sewage, adds iron filings and carries out prereduction reaction.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described step a) in reduction process as follows: add sulfuric acid and regulate behind sewage PH value to 2 ~ 3, drip concentration be 10% copperas solution carry out reduction reaction, the copperas solution of described dropping and the mass ratio of hexavalent chromium are 20 ~ 25:1, and the reaction times is 40 ~ 50 minutes.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described copperas solution dropping consumption hourly m is calculated as follows: m=22.6346 × C × Q/1000, in formula: m is FeSO
4.7H
2o measures, and unit is kg, C is Cr
6+content, unit is mg/l, Q is wastewater flow, and unit is m
3/ h.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described step b) be that 10% caustic soda soln heightens sewage PH value to 7.5 ~ 11 by adding concentration.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described step b) middle NH
3-N stripping treating processes is as follows: regulate sewage PH value to be 11, and the gas-water ratio controlling air and sewage is that 50:1 carries out NH
3-N stripping.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, the water content of described first body refuse, the second body refuse and the 3rd body refuse is all less than 40%, described first body refuse, the second body refuse and the 3rd body refuse are formed by twice press filtration, body refuse after first time press filtration and scavenging solution clean by solid-to-liquid ratio 1:3 proportioning, then carry out secondary press filtration, the waste liquid after cleaning is through limestone vegetation sedimentation manganese ion.
The treatment process of above-mentioned electrolytic manganese production waste residue; wherein; described first body refuse, the second body refuse and the 3rd body refuse adopt dry type layering heap to build; often heap waste residue is 1:3 to the gradient in downstream; the gradient to spoil area water port is 1:80 ~ 120; described spoil area is equipped with anti seepage membrane, described anti seepage membrane covers the clay protective layer that 0.2m ~ 0.5m is thick, and the thickness of the clay protective layer at described first body refuse place is higher than the thickness of the clay protective layer at described second body refuse or the 3rd body refuse place.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described spoil area water port is that 10% milk of lime reacts 0.5 hour by interpolation ferrous sulfate and concentration, controls pH value to 6 ~ 9 in sewage, Mn
2+concentration is outer row after being less than 2.0mg/L.
The treatment process of above-mentioned electrolytic manganese production waste residue, wherein, described non-ionic type polymeric flocculant is polyacrylamide.
The present invention contrasts prior art following beneficial effect: the treatment process of electrolytic manganese production waste residue provided by the invention, first by Cr in electrolytic manganese production sewage
6+be reduced into Cr
3+, then the Mn in sewage is removed by the treatment process of twice neutralization precipitation
2+and H
2sO
4, by three precipitation formation, three body refuses, thus effectively remove Mn in electrolytic manganese production waste residue
2+, H
2sO
4, Cr
6+, Cd
2+, NH
3the objectionable impuritiess such as-N and heavy metal ion, and treating processes is simple, with low cost, be easy to apply.
Accompanying drawing explanation
Fig. 1 is the treatment scheme schematic diagram of electrolytic manganese production waste residue of the present invention;
Fig. 2 is the detailed process schematic diagram of electrolytic manganese production waste residue of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the treatment scheme schematic diagram that electrolytic manganese production of the present invention produces waste residue; Fig. 2 is the detailed process schematic diagram that electrolytic manganese production of the present invention produces waste residue.
Refer to Fig. 1 and Fig. 2, the treatment process that electrolytic manganese production provided by the invention produces waste residue comprises the steps:
Step S1: first by Cr in electrolytic manganese production sewage
6+be reduced into Cr
3+, after precipitation, press filtration forms the first body refuse; In order to carry out Cr better
6+reduction, the pH value that first can control sewage is 4.5 ~ 6.5, adds iron filings and carries out prereduction reaction.Concrete reduction process is as follows:
Add sulfuric acid to regulate behind sewage PH value to 2 ~ 3, drip concentration be 10% copperas solution carry out reduction reaction, the copperas solution of described dropping and the mass ratio of hexavalent chromium are 20 ~ 25:1, and the reaction times is 40 ~ 50 minutes.Described copperas solution dropping consumption hourly m is calculated as follows:
m＝22.6346×C×Q/1000；
In formula: m is FeSO
4.7H
2o measures, and unit is kg, C is Cr
6+content, unit is mg/l, Q is wastewater flow, and unit is m
3/ h.
Step S2: utilize the sewage PH value after first time, neutralization reaction heightened reduction treatment to be alkalescence, after precipitation, press filtration forms the second body refuse;
Step S3: then at Ammonia blowing-out tower to NH
3-N carries out stripping process, and the sewage after stripping process adopts break point chlorination method to remove residue NH again
3-N; As by interpolation concentration be that 10% caustic soda soln heightens sewage PH value to 7.5 ~ 11; In order to ensure better stripping effect: preferably regulate sewage PH value to be 11, the air water volume ratio controlling air and sewage is that 50:1 carries out NH
3-N stripping, as air capacity 100 cubic metres/h, sewage quantity 2 cubic metres/h, then air water volume ratio is 50:1.
Step S4: finally adopt calcium hydroxide to carry out neutralization reaction for the second time and remove the Mn in sewage
2+and H
2sO
4, in order to remove the suspended substance in sewage further, continue to add the suspended substance in non-ionic type polymeric flocculant removal sewage; As adopted polyacrylamide PAM as non-ionic type polymeric flocculant; Carry out sedimentation and filtration at sand filter, after precipitation, press filtration forms the 3rd body refuse.
Through actual measurement comparison, it is as shown in the table to enter pretreated chromate waste water water quality:
The water primary quality measure of reuse after chromium pre-treatment sees the following form:
To produce leached mud 130,000 t/a (ton/year, water ratio 30 ~ 40%) in electrolytic manganese dioxide production process, major ingredient is ironic hydroxide, silicon-dioxide, vitriol etc.; The nearly 2000t/a of manganese body refuse that wastewater treatment produces, all belong to the Ith class general industrial solid waste, generation state is wet slag.Manganse Dioxide factory chemical combination workshop is provided with waste residue secondary press filteration system, leach the waste residue of chemical combination generation after a press filtration, moisture high (water ratio 30 ~ 40%) in slag, it becomes in one's duty vitriol to have solubility, by quality solid-to-liquid ratio 1:3, the waste residue after a press filtration is cleaned, then carry out secondary press filtration, reduce soluble sulphate in slag, produce waste residue amount about 300 tons every day, the waste water that cleaning waste residue produces 500m altogether
3, a press filtration filtrate scavenging solution is through limestone vegetation sedimentation manganese ion, and the middle water obtained after press filtration can reuse, and filter residue can add leaching chemical combination as neutralizing agent, namely reclaims mn ion, reduces again its pollution to environment.Secondary filter-press residues is transported to slag field, may be used for material of construction brickmaking, reaches comprehensive utilization.
The treatment process of electrolytic manganese production waste residue provided by the invention, being that 10% milk of lime reacts 0.5 hour in spoil area water port by adding ferrous sulfate and concentration, controlling pH value to 6 ~ 9 in sewage, Mn
2+concentration is outer row after being less than 2.0mg/L, as shown in the table:
| Sewage type | PH | Mn 2+(mg/l) |
| Slag field water from diffusion | 6-7 | 1500-2500 |
The treatment process of electrolytic manganese production waste residue provided by the invention; described first body refuse, the second body refuse and the 3rd body refuse adopt dry type layering heap to build; often heap waste residue is 1:3 to the gradient in downstream; the gradient to spoil area water port is 1:80 ~ 120; described spoil area is equipped with anti seepage membrane; described anti seepage membrane covers the clay protective layer that 0.2m ~ 0.5m is thick, the thickness of the clay protective layer at described first body refuse place is higher than the thickness of the clay protective layer at described second body refuse or the 3rd body refuse place.Last sewage effluent index is as following table, and Wastewater Pollutant meets GB8978-1996 " integrated wastewater discharge standard " primary standard completely.
| Pollutent title | Standard limited value | Pollutent title | Standard limited value |
| PH value | 6～9 | Ammonia nitrogen | 15mg/L |
| Suspended substance (SS) | 70mg/L | Sexavalent chrome | 0.5mg/L |
| BOD | 20mg/L | Total manganese | 2.0mg/L |
| COD | 100mg/L | Total chromium | 1.5mg/L |
Although the present invention discloses as above with preferred embodiment; so itself and be not used to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little amendment and perfect, therefore protection scope of the present invention is when being as the criterion of defining with claims.
Claims (10)
1. a treatment process for electrolytic manganese production waste residue, is characterized in that, comprises the steps:
A) first by Cr in electrolytic manganese production sewage
6+be reduced into Cr
3+, after precipitation, press filtration forms the first body refuse;
B) utilize the sewage PH value after first time, neutralization reaction heightened reduction treatment to be alkalescence, after precipitation, press filtration forms the second body refuse;
C) then at Ammonia blowing-out tower to NH
3-N carries out stripping process, and the sewage after stripping process adopts break point chlorination method to remove residue NH again
3-N;
D) finally adopt calcium hydroxide to carry out neutralization reaction for the second time and remove the Mn in sewage
2+and H
2sO
4, continue to add the suspended substance in non-ionic type polymeric flocculant removal sewage, carry out sedimentation and filtration at sand filter, after precipitation, press filtration forms the 3rd body refuse.
2. the treatment process of electrolytic manganese production waste residue as claimed in claim 1, is characterized in that, it is 4.5 ~ 6.5 that described step a) also comprises the pH value controlling sewage, adds iron filings and carries out prereduction reaction.
3. the treatment process of electrolytic manganese production waste residue as claimed in claim 2, is characterized in that, described step a) in reduction process as follows:
Add sulfuric acid to regulate behind sewage PH value to 2 ~ 3, drip concentration be 10% copperas solution carry out reduction reaction, the copperas solution of described dropping and the mass ratio of hexavalent chromium are 20 ~ 25:1, and the reaction times is 40 ~ 50 minutes.
4. the treatment process of electrolytic manganese production waste residue as claimed in claim 3, it is characterized in that, described copperas solution dropping consumption hourly m is calculated as follows: m=22.6346 × C × Q/1000, in formula: m is FeSO
4.7H
2o measures, and unit is kg, C is Cr
6+content, unit is mg/l, Q is wastewater flow, and unit is m
3/ h.
5. the treatment process of electrolytic manganese production waste residue as claimed in claim 1, is characterized in that, described step b) be that 10% caustic soda soln heightens sewage PH value to 7.5 ~ 11 by interpolation concentration.
6. the treatment process of electrolytic manganese production waste residue as claimed in claim 5, is characterized in that, described step b) middle NH
3-N stripping treating processes is as follows: regulate sewage PH value to be 11, and the gas-water ratio controlling air and sewage is that 50:1 carries out NH
3-N stripping.
7. the treatment process of electrolytic manganese production waste residue as claimed in claim 1, it is characterized in that, the water content of described first body refuse, the second body refuse and the 3rd body refuse is all less than 40%, described first body refuse, the second body refuse and the 3rd body refuse are formed by twice press filtration, body refuse after first time press filtration and scavenging solution clean by solid-to-liquid ratio 1:3 proportioning, then carry out secondary press filtration, the waste liquid after cleaning is through limestone vegetation sedimentation manganese ion.
8. the treatment process of electrolytic manganese production waste residue as claimed in claim 7; it is characterized in that; described first body refuse, the second body refuse and the 3rd body refuse adopt dry type layering heap to build; often heap waste residue is 1:3 to the gradient in downstream; the gradient to spoil area water port is 1:80 ~ 120; described spoil area is equipped with anti seepage membrane; described anti seepage membrane covers the clay protective layer that 0.2m ~ 0.5m is thick, the thickness of the clay protective layer at described first body refuse place is higher than the thickness of the clay protective layer at described second body refuse or the 3rd body refuse place.
9. the treatment process of electrolytic manganese production waste residue as claimed in claim 5, is characterized in that, described spoil area water port is that 10% milk of lime reacts 0.5 hour by interpolation ferrous sulfate and concentration, controls pH value to 6 ~ 9 in sewage, Mn
2+concentration is outer row after being less than 2.0mg/L.
10. the treatment process of electrolytic manganese production waste residue as claimed in claim 1, it is characterized in that, described non-ionic type polymeric flocculant is polyacrylamide.
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| CN201410335685.5A CN104261584A (en) | 2014-07-15 | 2014-07-15 | Processing method for waste residues produced by electrolyzing manganese |
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|---|---|---|---|
| CN201410335685.5A CN104261584A (en) | 2014-07-15 | 2014-07-15 | Processing method for waste residues produced by electrolyzing manganese |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242180A (en) * | 2016-08-29 | 2016-12-21 | 湖南艾布鲁环保科技有限公司 | A kind of electrolytic manganese residues percolate advanced treating and reclamation set and method |
| CN110052483A (en) * | 2019-03-26 | 2019-07-26 | 山东省鲁南地质工程勘察院(山东省地勘局第二地质大队) | Dystopy wet reducing-stabilisation joint repairs chromium-polluted soil and underground water method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242180A (en) * | 2016-08-29 | 2016-12-21 | 湖南艾布鲁环保科技有限公司 | A kind of electrolytic manganese residues percolate advanced treating and reclamation set and method |
| CN110052483A (en) * | 2019-03-26 | 2019-07-26 | 山东省鲁南地质工程勘察院(山东省地勘局第二地质大队) | Dystopy wet reducing-stabilisation joint repairs chromium-polluted soil and underground water method |
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Inventor after: Chen Qizhi Inventor after: He Min Inventor after: Zeng Dechao Inventor after: Wei Jiageng Inventor after: Lu Yanyue Inventor after: Wan Weihua Inventor after: Wei Guozhu Inventor after: Zhou Baojin Inventor after: Lin Yan Inventor after: Shi Lei Inventor after: Su Guangyuan Inventor after: Lu Chao Inventor before: Chen Qizhi Inventor before: Wei Jiageng Inventor before: Lu Yanyue Inventor before: Wan Weihua Inventor before: Wei Guozhu Inventor before: Shi Lei Inventor before: Su Guangyuan Inventor before: Lu Chao Inventor before: He Min Inventor before: Zeng Dechao |
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Application publication date: 20150107 |