CN102531243B - Zero-emission production process of electrolytic manganese wastewater - Google Patents
Zero-emission production process of electrolytic manganese wastewater Download PDFInfo
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- CN102531243B CN102531243B CN 201210041704 CN201210041704A CN102531243B CN 102531243 B CN102531243 B CN 102531243B CN 201210041704 CN201210041704 CN 201210041704 CN 201210041704 A CN201210041704 A CN 201210041704A CN 102531243 B CN102531243 B CN 102531243B
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011572 manganese Substances 0.000 title claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000004744 fabric Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 7
- 238000005498 polishing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 238000002161 passivation Methods 0.000 claims description 9
- 238000004080 punching Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007494 plate polishing Methods 0.000 claims description 5
- 230000009849 deactivation Effects 0.000 claims description 4
- 238000005325 percolation Methods 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008237 rinsing water Substances 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 7
- 239000011651 chromium Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a zero-emission production process of electrolytic manganese wastewater. The process comprises processes such as grinding, slurrying, chemically combining, transferring, filter pressing, electrolyzing, passivating and rinsing and comprises the following steps of: (1) circularly utilizing filter cloth washing water; (2) circularly utilizing impact plate rinsing water; (3) circularly using polishing liquid washing water of a negative plate; and (4) carrying out other wastewater treatment processes: feeding filter reverse washing water and test water into a slag pool leachate treatment system for centralized treatment. According to the invention, manganese is produced by utilizing the process, no wastewater is emitted, no environment pollution is generated, and clean production can be realized and resource utilization rate is improved.
Description
Technical field
The present invention relates to a kind of zero-emission production process of electrolytic manganese wastewater, especially relate to a kind of zero-emission production process of electrolytic manganese wastewater be used to containing chromium passivating technique.
Background technology
The Electrolytic Manganese Wastewater Pollutant levels are high, and complicated component.At present, electrolytic manganese enterprise generally adopts " reduction-neutralization precipitation " method to process Electrolytic Manganese Wastewater, and the method is mainly for the manganese in the waste water and chromium, to the ammonia nitrogen in the waste water almost without any treatment effect.And in the electrolytic manganese production process, 1t electrolytic manganese product will consume about ammonia 83kg, and the 43kg that wherein has an appointment enters waste water, and 37kg enters waste residue, altogether in 96% the TAN entered environment.According to enterprise's field measurement data presentation, the ammonia nitrogen quantity discharged exceeds standard hundreds of even thousands of times, and average quality concentration is 1000～2000mg/L approximately, the highest 13000mg/L that unexpectedly reaches.It is this that present situation that directly discharge does not cause surface water and groundwater to be subject to severe contamination on the one hand to ammonia nitrogen is treated; Ammonia nitrogen is useful raw material in the electrolytic manganese production technique on the other hand, and directly discharging causes the waste of valuable resource, with cleaner production, improve resource utilization expectation departing from.
In addition, the manganese in the Electrolytic Manganese Wastewater and chromium form dangerous solid waste landfill, not only environment are produced potential harm, and are the huge waste of resource.According to statistics, 1t electrolytic manganese product produces at least 14kg manganese and enters waste water or solid waste, contaminate environment.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of environmentally safe, cleaner production, and the zero-emission production process of electrolytic manganese wastewater of raising resource utilization.
The technical solution adopted for the present invention to solve the technical problems is:
General planning is that the waste water enforcement recycle by with discharge of wastewater node in the electrolytic manganese production reaches the Electrolytic Manganese Wastewater zero release, especially press filtration operation and the electrowinning process of the manganese waste water that produces electrolysis is carried out cleaner production and resource recycling.
The press filtration operation: the sulfur acid manganese solution that produces is leached in the chemical combination workshop, and with being pumped to the plate-and-frame filter press coarse filtration, filter residue is delivered to the slag field through chute, and filtrate is delivered to purification tank, adds the SDD(Sodium dimethyldithiocarbamate 40min), remove heavy metal (Co, Ni etc.); Solution after purifying is delivered to the filter of pressure filter essence, and filter residue is delivered to the slag field, and filtrate is sent electrowinning process.Wherein, the filter cloth washing water that produces of flushing filter cloth is one of Electrolytic Manganese Wastewater.
Electrowinning process: during production electrolytic solution is constantly introduced in the electrolyzer from header tank, pass into direct current, when electrolytic manganese negative plate deposition reach 1.5～2.0mm thick after, regularly from electrolyzer, take out negative plate (put into simultaneously new negative plate and continue electrolysis), through after the short period of time passivation, then carry out rinsing, oven dry, peel off, namely get manganese metal product and negative plate.Major equipment has electrolyzer and silicon rectifier during electrolysis.Wherein, the punching rinse water that contain chromate ion, ammonia nitrogen and mn ion that rinsing produces are one of Electrolytic Manganese Wastewater.
Whole technical scheme is that a kind of zero-emission production process of electrolytic manganese wastewater comprises ore grinding, pulp, chemical combination, transfer, press filtration, electrolysis, passivation, rinsing process, it is characterized in that, also is provided with following steps:
(1) filter cloth washing water circulation use: after the filter cloth washing water that produces in the press filtration operation filtered by line strainer, be back to the water pond that washes cloth, recycle;
When the free manganese concentration of the filter cloth washing water in the water pond that washes cloth during at 10～15g/L, pump into and make pulp preparation water in the pulp bucket, recycle; And replenish the clear water of respective amount in the water pond that washes cloth;
(2) punching rinse water recycle: the punching rinse water that produce in the rinsing process are filtered first, process through anion exchange resin bed again, be back at last the rinse water pond, recycle;
When the free manganese concentration of punching rinse water in the rinse water pond reaches 5～10g/L, pump into and make pulp preparation water in the pulp bucket, recycle; And replenish the clear water of respective amount in the rinse water pond;
After anionite-exchange resin reached capacity capacity, by sodium hydroxide regeneration, again with pH 8～10, the regenerated liquid of concentration of chromate 5～10g/L was mixed with pH 5.5～6.5, behind concentration of chromate 2.5～3.5g/L, returned in the deactivation slot for passivation;
Described concentration of chromate is in potassium bichromate;
(3) the whole plate polishing fluid of negative plate rinse water recycles; After the polishing fluid that the whole plate with negative plate adheres to cleans up with rinse water, the pH value of used rinse water is adjusted into 6～9, through the processing of activated carbon adsorption post, then return in the rinse water pond recycle again;
(4) other wastewater treatment: filter backwash water and chemical examination water enter slag storehouse percolation liquid treating system and focus on.
The principle of zero-emission production process of electrolytic manganese wastewater of the present invention is as follows:
1. cleaner production is implemented in the production scene
The existing Electrolytic Manganese Wastewater discharging water yield and pollutant component are shown in Table 1.Zero-emission production process of electrolytic manganese wastewater of the present invention comprises three parts: by filter wash cloth water circulation utilization system recycle filter wash water distribution; By the passivator chromate ion in filtration and the anionresin technology recovery rinse water, simultaneously recycle ammonia nitrogen and mn ion; The recycle of the whole plate polishing fluid of negative plate rinse water.
The table 1 Electrolytic Manganese Wastewater discharging water yield and composition
2. reclaim the passivator chromate ion in the rinsing water and be cycled to used in passivation
By the rinsing water of mechanical filter and anion exchange process, after reducing suspended substance and chromate ion, return the rinse water pond; After anionite-exchange resin reaches capacity capacity, by sodium hydroxide regeneration, again with pH 8～10, concentration of chromate 5～10g/L regenerated liquid. be mixed with pH 5.5～6.5, behind concentration of chromate 2.5～3.5g/L, return deactivation slot circulation passivation;
3. the whole plate polishing fluid of negative plate rinse water recycles; After the polishing fluid that the whole plate with negative plate adheres to cleans up with rinse water, the pH value of used rinse water is adjusted into 6～9, through the processing of activated carbon adsorption post, then return in the rinse water pond recycle again;
4. mechanize filter backwash water and chemical examination water consumption are few, enter slag storehouse percolation liquid treating system and focus on.
The present invention merges by cleaner production thought and the ion-exchange isolation technique with the Electrolytic Manganese Wastewater zero-discharge technology, thereby pollutent is down to minimum on the impact of environment, and the resource of preciousness is re-used.
Compared with prior art, the present invention has following features: (1) produces non-wastewater discharge; (2) pollutent chromate ion, ammonia nitrogen and free manganese all return in the electrolytic manganese production system and recycle; (3) environmental friendliness is externally discharged without the poisonous and harmful solid waste.
Embodiment
The invention will be further described below in conjunction with embodiment.
The present embodiment comprises ore grinding, pulp, chemical combination, transfer, press filtration, electrolysis, passivation, rinsing process, it is characterized in that, also is provided with following steps:
(1) filter cloth washing water circulation use: after the filter cloth washing water that produces in the press filtration operation filtered by line strainer, be back to the water pond that washes cloth, recycle;
When the free manganese concentration of filter cloth washing water in the water pond that washes cloth during at 12g/L, pump into and make pulp preparation water in the pulp bucket, recycle; And replenish the clear water of respective amount in the water pond that washes cloth;
(2) punching rinse water recycle: the rinse water that produce in the rinsing process (are contained [Cr
2O
7 2-] 50～120mg/L, [NH
3-N] 900～1800mg/L, [Mn
2+] 900～3000mg/L, SS50～300mg/L) being filtered first, the turbidity＜5NTU of filtrate processes to [Cr through anion exchange resin bed again
2O
7 2-]＜10 μ g/L, the SS inspection does not measure, and is back at last the rinse water pond, recycle;
When the free manganese concentration of punching rinse water in the rinse water pond reaches 7g/L, pump into and make pulp preparation water in the pulp bucket, recycle; And replenish the clear water of respective amount in the water pond that washes cloth;
After anionite-exchange resin reached capacity capacity, by sodium hydroxide regeneration, again with pH9, concentration of chromate 7g/L regenerated liquid was mixed with pH 6, behind the concentration of chromate 3g/L, returns deactivation slot circulation passivation;
(3) the whole plate polishing fluid of negative plate recycles: after the polishing fluid that the whole plate with negative plate adheres to cleans up with rinse water, the pH value of used rinse water is adjusted into 7, through the processing of activated carbon adsorption post, then returns in the rinse water pond recycle again;
(4) other wastewater treatment: filter backwash water and chemical examination water enter slag storehouse percolation liquid treating system and focus on.
Claims (1)
1. a zero-emission production process of electrolytic manganese wastewater comprises ore grinding, pulp, chemical combination, transfer, press filtration, electrolysis, passivation, rinsing process, it is characterized in that, also is provided with following steps:
(1) filter cloth washing water circulation use: after the filter cloth washing water that produces in the press filtration operation filtered by line strainer, be back to the water pond that washes cloth, recycle;
When the free manganese concentration of filter cloth washing water in the water pond that washes cloth reaches 10～15g/L, pump into and make pulp preparation water in the pulp bucket, and replenish the clear water of respective amount in the water pond that washes cloth;
(2) punching rinse water recycle: the punching rinse water that produce in the rinsing process are filtered first, process through anion exchange resin bed again, be back at last the rinse water pond, recycle;
When the free manganese concentration of punching rinse water in the rinse water pond reaches 5～10g/L, pump into and make pulp preparation water in the pulp bucket, and replenish the clear water of respective amount in the rinse water pond;
After anionite-exchange resin reached capacity capacity, by sodium hydroxide regeneration, again with pH8～10, the regenerated liquid of concentration of chromate 5～10g/L was mixed with pH5.5～6.5, behind concentration of chromate 2.5～3.5g/L, returned in the deactivation slot for passivation;
Described concentration of chromate is in potassium bichromate;
(3) the whole plate polishing fluid of negative plate rinse water recycles: after the polishing fluid that the whole plate with negative plate adheres to cleans up with rinse water, the pH value of used rinse water is adjusted into 6～9, process through the activated carbon adsorption post again, then return in the rinse water pond recycle;
(4) other wastewater treatment: filter backwash water and chemical examination water enter slag storehouse percolation liquid treating system and focus on.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201210041704 CN102531243B (en) | 2012-02-23 | 2012-02-23 | Zero-emission production process of electrolytic manganese wastewater |
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|---|---|---|---|
| CN 201210041704 CN102531243B (en) | 2012-02-23 | 2012-02-23 | Zero-emission production process of electrolytic manganese wastewater |
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| CN102531243A CN102531243A (en) | 2012-07-04 |
| CN102531243B true CN102531243B (en) | 2013-09-18 |
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| CN103614741A (en) * | 2013-11-22 | 2014-03-05 | 中国环境科学研究院 | Method of decreasing, reutilizing and circulating heavy metal wastewater in subsequent section of electrolytic manganese electrolysis |
| CN104726719B (en) * | 2015-03-11 | 2017-01-25 | 北京矿冶研究总院 | Washing and recycling method of heavy metal waste residues |
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| 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 |
| CN102358645B (en) * | 2011-08-05 | 2013-01-30 | 金瑞新材料科技股份有限公司贵州分公司 | Fully-closed circulation treatment method for water used by electrolytic manganese metal production |
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