CN106587430A - Treatment method of simultaneously removing multiple metal ions in manganiferous waste water - Google Patents

Treatment method of simultaneously removing multiple metal ions in manganiferous waste water Download PDF

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CN106587430A
CN106587430A CN201611174037.1A CN201611174037A CN106587430A CN 106587430 A CN106587430 A CN 106587430A CN 201611174037 A CN201611174037 A CN 201611174037A CN 106587430 A CN106587430 A CN 106587430A
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waste water
manganese dioxide
bearing waste
flco
manganese
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CN106587430B (en
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刘正乾
闫娅慧
吴晓晖
涂嘉玲
崔玉虹
邓琳
章北平
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Huazhong University of Science and Technology
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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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

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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)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses a treatment method of simultaneously removing multiple metal ions in manganiferous waste water. The treatment method comprises the following steps: first adding permanganate into the manganiferous waste water, oxidizing the manganese ions in the manganiferous waste water, and converting Mn<2+> into manganese dioxide floc; then adjusting the pH value of the manganiferous waste water to 7.0-10.0; then conducting stirring at a speed of 200r/min-400r/min to let the manganese dioxide floc mutually collide and enlarge, and conducting stirring at a speed of 10r/min-30r/min to fully adsorb the manganese ions and other coexisting metal ions in the manganiferous waste water; and finally allowing the manganiferous waste water to stand for 30min or above to settle the manganese dioxide floc. The treatment method uses the coagulation of the calcium ions and magnesium ions in the waste water on the manganese dioxide to remove the metal ions in the manganiferous waste water, without adding a coagulant.

Description

It is a kind of at the same remove Mn-bearing waste water in many kinds of metal ions processing method
Technical field
The invention belongs to water-treatment technology field, more particularly, to a kind of processing method of Mn-bearing waste water.
Background technology
In recent years, the water contamination accident that the heavy metal such as manganese, nickel, cadmium and chromium causes frequently occurs, and causes the height of various circles of society Degree is paid attention to.Manganese excessive concentration can cause the deterioration of water quality, produce " Heisui River " and " yellow fluid " phenomenon.The manganese of the long-term excess intake of human body The pathological changes of related organ can be caused, causes chronic poisoning.Equally, the intake of a small amount of nickel, chromium and cadmium can also make human body produce allergy Reaction, it is possible to cause serious pathological changes, or even cancer.Cadmium in people's body accumulation, and can be difficult to be discharged by metabolism In vitro.The valence state that manganese is present in nature is more, mainly there is+2 ,+3 ,+4 and+7 valencys, wherein+2 relatively stable with+4 valencys.
Chinese scholars have done substantial amounts of research to the process problem of the heavy metal pollution of Mn-bearing waste water, and current demanganization is commonly used Method has bioanalysises, contact oxidation method and chemical method.Chemical method generally utilizes chlorine dioxide, ozone, hydrogen peroxide and Gao Meng Divalent manganesetion is oxidized to manganese dioxide by the strong oxidizing property of hydrochlorate, is removed by flocculation sediment or filtration.It is high due to its Production run expense, Ozonation is less to be used；Chlorine dioxide easily generates sterilization pair with the Organic substance reaction in water body Product, therefore the method is also gradually eliminated；Permanganate still has in neutral conditions stronger oxidability, Ke Yihe Manganese dioxide generated and comproportionation reaction in bivalent manganese there is.
By often heavy metal ion complicated component in the water body of heavy metal pollution, such as in manganese ore exploitation and smelting wastewater not only Manganese containing high concentration, while the contents of many kinds of heavy metal ion such as nickel, chromium, cadmium and copper have also coexisted.And generated in-situ manganese dioxide With larger specific surface area, while abundant oh group is contained on its surface, this causes generated in-situ manganese dioxide to have Good absorption property, can be used for the heavy metals such as the manganese, nickel, cadmium and the chromium that coexist in Adsorption water.For compared with other oxidants, Permanganate oxidation divalent manganesetion can generate more manganese dioxide, so as to be conducive to the synchronous of many kinds of metal ions to remove.
But, although the manganese dioxide in sewage itself has certain Coagulation aiding, but effect than relatively limited, in examination Test needs to add coagulating sedimentation of a certain amount of coagulant to promote manganese dioxide in research and practical engineering application, reaches shortening Hydraulic detention time, the purpose for reducing delivery turbidity.Yet with dosing coagulant is needed, the complexity of technique is increased, and And also improve processing cost.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of processing method of Mn-bearing waste water, Its object is to using permanganate oxidation Mn2+Generate more manganese dioxide, using the calcium ion that itself is present in waste water and Cohesion of the magnesium ion to manganese dioxide, under conditions of not dosing coagulant, the synchronous manganese removed in Mn-bearing waste water and The nickel chromium triangle for coexisting and cadmium metal ion.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of processing method of Mn-bearing waste water, process Front Mn-bearing waste water includes Mn of the concentration more than 4mg/L2+, the treating method comprises following steps：
(1) permanganate is added in Mn-bearing waste water so that the Mn in the permanganate and Mn-bearing waste water2+Mol ratio For 2:3～2:5, by the Mn in Mn-bearing waste water2+Aoxidize and be converted to manganese dioxide flco；Then the pH value in Mn-bearing waste water is adjusted For 7.0～10.0 so that the electronegativity increment on manganese dioxide flco surface, strengthen absorption of the manganese dioxide flco to metal ion Ability；
(2) Mn-bearing waste water 10min～30min is stirred with the rotating speed of 200r/min～400r/min so that manganese dioxide is wadded a quilt with cotton The preliminary adsorbing metal ions of body, while so that manganese dioxide flco is mutually collided and increased；
(3) Mn-bearing waste water 2min～8min is stirred with the rotating speed of 10r/min～30r/min so that the manganese dioxide of increase Flco fully adsorbs the metal ion in Mn-bearing waste water；
(4) Mn-bearing waste water is stood into more than 30min so that adsorbed the manganese dioxide settling of floccus of metal ion.
Preferably, before the step (1), also including Ca in regulation Mn-bearing waste water2+Concentration a and Mg2+Concentration b, So that Ca2+And Mg2+Concentration meet 13.75a+b >=18.7.
As it is further preferred that adjust Mn-bearing waste water in, the Ca2+Concentration meet a >=1.36, or Mg2+'s Concentration meets b >=18.7.
Preferably, the metal ion is manganese ion, nickel ion, cadmium ion or chromium ion.
As it is further preferred that the Mn-bearing waste water of the before processing includes Mn of the concentration more than 100mg/L2+, the nickel The concentration of ion is below 3mg/L, and the concentration of the cadmium ion is below 8mg/L.
Preferably, also include in the step (1)：10s～5min is stirred with the rotating speed of 200r/min～400r/min.
Preferably, between the step (2) and step (3), also include：Stirred with the rotating speed of 40r/min～100r/min Mix 2min～10min so that manganese dioxide flco is mutually collided and continues increase, while preventing increased manganese dioxide from wadding a quilt with cotton Body is crushed.
As it is further preferred that the temperature of the stirring is more than 4 DEG C.
Preferably, also include after the step (4), remove the manganese dioxide flco of sedimentation.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect：
1st, the present invention is in processing procedure by adding permanganate, oxidation removal water middle and high concentration divalent manganesetion it is same Shi Shengcheng manganese dioxide, generated in-situ manganese dioxide has stronger absorption property, can remove in water body by the way that absorption is synchronous The heavy metals such as remaining manganese, nickel, cadmium and chromium；Empirical tests, to the removal effect of manganese and nickel respectively up to 98% and more than 79%, cadmium, The clearance of chromium is respectively up to 80% and more than 40%；
2nd, the present invention can make full use of itself is present in Mn-bearing waste water calcium ion and magnesium ion to effectively facilitate titanium dioxide The flocculation sediment of manganese, the specific surface area for reducing manganese dioxide, advantageously reduce process water turbidity；So as to the nothing in water treatment procedure Extra dosing coagulant is needed, adding of agent is saved, simplification of flowsheet reduces processing cost；Calcium ions and magnesium ions needed for the present invention Content is all fewer, it is adaptable to the contaminated water body of most Mn-bearing waste water, such as Manganese Ore District and electrolytic manganese industry waste water.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention Limit the present invention.As long as additionally, technical characteristic involved in invention described below each embodiment each other it Between do not constitute conflict just can be mutually combined.
The present invention dominant response principle be：2MnO4 -+3Mn2++2H2O=5MnO2+4H+, permanganate oxidation bivalent manganese Ion generates manganese dioxide, removes the remaining heavy metal such as manganese and nickel, cadmium and chromium in water body using the adsorptivity of manganese dioxide, together Calcium ion and magnesium ion present in Shi Liyong water bodys remarkably promote the flocculation sediment of manganese dioxide, reduce delivery turbidity.
The invention provides a kind of processing method of Mn-bearing waste water, the Mn-bearing waste water of the before processing is more than including concentration The Mn of 4mg/L2+, the Ca of a mg/L2+And the Mg of b mg/L2+, and Ca2+Concentration meet a >=1.36, or Mg2+Concentration expire Sufficient b >=18.7, or both concentration meet 13.75a+b >=18.7 jointly, if the Mn-bearing waste water is unsatisfactory for above-mentioned condition, can It is set to meet 13.75a+b >=18.7 by adding appropriate calcium salt and/or magnesium salt；The treating method comprises following steps：
(1) permanganate is added in Mn-bearing waste water so that the permanganate and Mn2+Mol ratio be 2:3～2:5, By the heavy metal oxidation in Mn-bearing waste water, manganese ion is converted to manganese dioxide flco；Then the pH value in regulation Mn-bearing waste water is 7.0～10.0 so that the electronegativity increment on manganese dioxide flco surface, strengthen energy of adsorption of the manganese dioxide flco to metal ion Power；
(2) Mn-bearing waste water 10min～30min is stirred with the rotating speed of 200r/min～400r/min so that manganese dioxide is wadded a quilt with cotton Body phase is mutually collided and increased, and tentatively adsorbs the metal ion in Mn-bearing waste water, such as manganese, nickel and cadmium；
(3) Mn-bearing waste water 2min～8min is stirred with the rotating speed of 10r/min～30r/min so that the manganese dioxide of increase Flco further adsorbs the metal ion in Mn-bearing waste water, while preventing the manganese dioxide for increasing from crushing；
(4) Mn-bearing waste water is stood into more than 30min so that adsorbed the manganese dioxide settling of floccus of metal ion；Remove The manganese dioxide flco of sedimentation, completes the synchronization process of many kinds of metal ions in Mn-bearing waste water.
Wherein, in step (1), simultaneously 10s～5min can be stirred with the rotating speed of 200r/min～400r/min, to promote Enter permanganate fully to dissolve in Mn-bearing waste water, between step (2) and step (3), can also include：With 40r/min～ The rotating speed stirring 2min～10min of 100r/min so that manganese dioxide flco is mutually collided and continues to increase, while anti- Only increased manganese dioxide flco is crushed；Temperature during all stirrings is all higher than 4 DEG C, to ensure the wadding of manganese dioxide flco The solidifying and absorption to metal ion.
Embodiment 1
The present embodiment select the contaminated high manganese containing water in Guangxi mining area, in raw water calcium ion concentration be 324.5mg/L, magnesium Ion concentration is 53.9mg/L, and pH is 6.89, and other water quality parameters are shown in Table 1, using the demanganization process demanganization of the present invention, place Reason temperature is 14 DEG C.
S1. the potassium permanganate that 24.29mg/L is added in raw water adjusts pH be 8.0 (potassium permanganate and bivalence in theory simultaneously The mol ratio of manganese ion is 2:When 3 can by divalent manganesetion complete oxidation be insoluble manganese dioxide, i.e. 1mg manganese in theory Need 1.92mg potassium permanganate.Raw water manganese ion concentration is 15.1mg/L, and the potassium permanganate ability of 28.99mg/L is needed in theory Divalent manganesetion is completely oxidized to into manganese dioxide), while aoxidizing 2min to carry out pre- oxygen with the mixing speed of 300r/min Change；
S2. pre-oxidation quickly stirs 15min after terminating with 300r/min；
S3. with 50r/min moderate-speed mixer 2min；
S4. with 20r/min low rate mixing 5min, flocculated；
S5. the turbidity of supernatant is determined after flocculation terminates after quiet heavy 60min, after supernatant is with 0.45 μm of membrane filtration, ICP is used Each heavy metal concentration change is shown in Table 1 in water outlet after detection process, and wherein "-" is represented and do not detected.
Effluent quality parameter list after the raw water of table 1 and process
Water quality parameter Unit Raw water Water outlet after process Clearance (%)
Mn mg/L 15.10 0.001 >99
Ni mg/L 0.128 0.020 84
Cr mg/L 0.010 0.002 80
Cd mg/L 0.015 - >99
Turbidity NTU 0.67 1.53 -
Step described in embodiment 2 is as follows：
S1. the potassium permanganate that 24.29mg/L is added in raw water adjusts pH be 7.5 (potassium permanganate and bivalence in theory simultaneously The mol ratio of manganese ion is 2:When 3 can by divalent manganesetion complete oxidation be insoluble manganese dioxide, i.e. 1mg manganese in theory Need 1.92mg potassium permanganate.Raw water manganese ion concentration is 15.1mg/L, and the potassium permanganate ability of 28.99mg/L is needed in theory Divalent manganesetion is completely oxidized to into manganese dioxide), while aoxidizing 2min to be pre-oxidized with the mixing speed of 300r/min；
S2. after pre-oxidation terminates, 35.19mg/L aluminium polychlorid is added, 15min is quickly stirred with 300r/min；
S3. with 50r/min moderate-speed mixer 2min；
S4. with 20r/min low rate mixing 5min, flocculated；
S5. the turbidity of supernatant is determined after flocculation terminates after quiet heavy 60min, after supernatant is with 0.45 μm of membrane filtration, ICP is used Each heavy metal concentration change in water outlet after detection process.
Embodiment 3
Repeat embodiment 2 with described same steps, difference is that gathering for 40.39mg/L is added in step S2 Close iron sulfate.
Embodiment 4
Repeat embodiment 2 with described same steps, difference is to be added without any medicament in step S2, directly 15min is quickly stirred with 300r/min.
For raw water same as Example 1, the delivery turbidity of embodiment 2 and embodiment 3 be respectively 21.2NTU and 7.17NTU, and the delivery turbidity of embodiment 4 is 1.78NTU；The clearance embodiment 2 of Ni has reached more than 70%, embodiment 3 For 61%, embodiment 4 is 75%；The clearance of remaining Mn, Cr and Cd is roughly the same with embodiment 1.
Embodiment 5- embodiment 7 repeats embodiment 1 with described same steps, and is implemented with the parameter change shown in table 2 The reaction condition of example 1；For raw water same as Example 1, the delivery turbidity of embodiment 5 is reduced to 1.13NTU, and embodiment The delivery turbidity of 6-7 is in 1NTU or so；The clearance embodiment 5 of Ni has reached more than 75%, and embodiment 6 is 75%, is implemented Example 7 is 91%；The clearance of remaining Mn, Cr and Cd is roughly the same with embodiment 1.
The reaction condition of the embodiment 5- embodiment 7 of table 2
Reaction condition Embodiment 2 Embodiment 3 Embodiment 4
Treatment temperature 24℃ 14℃ 14℃
The pH adjusted in step (1) 8.0 7.5 8.5
By the way that Kaolin is added in the raw water of embodiment 1 to adjust turbidity, Ni (NO are added3)2To change the initial Ni of water sample Concentration, adds Cd (NO3)2To change the initial Cd concentration of water sample, the water quality parameter of the raw water of the embodiment 8- embodiment 22 of acquisition is such as Shown in table 3.
The water quality parameter of the raw water of the embodiment 8- embodiment 22 of table 3
Water quality parameter Mn Ni Cr Cd Turbidity
Embodiment 8 15.10mg/L 0.128mg/L 0.010mg/L 0.015mg/L 5NTU
Embodiment 9 15.10mg/L 0.128mg/L 0.010mg/L 0.015mg/L 10NTU
Embodiment 10 15.10mg/L 0.128mg/L 0.010mg/L 0.015mg/L 20NTU
Embodiment 11 15.10mg/L 0.128mg/L 0.010mg/L 0.015mg/L 50NTU
Embodiment 12 15.10mg/L 0.15mg/L 0.010mg/L 0.015mg/L 0.67NTU
Embodiment 13 15.10mg/L 0.20mg/L 0.010mg/L 0.015mg/L 0.67NTU
Embodiment 14 15.10mg/L 0.30mg/L 0.010mg/L 0.015mg/L 0.67NTU
Embodiment 15 15.10mg/L 0.40mg/L 0.010mg/L 0.015mg/L 0.67NTU
Embodiment 16 15.10mg/L 0.128mg/L 0.010mg/L 0.2mg/L 0.67NTU
Embodiment 17 15.10mg/L 0.128mg/L 0.010mg/L 0.4mg/L 0.67NTU
Embodiment 18 15.10mg/L 0.128mg/L 0.010mg/L 0.6mg/L 0.67NTU
Embodiment 19 15.10mg/L 0.128mg/L 0.010mg/L 0.9mg/L 0.67NTU
Embodiment 20 15.10mg/L 0.128mg/L 0.010mg/L 1.2mg/L 0.67NTU
Embodiment 21 15.10mg/L 0.128mg/L 0.010mg/L 1.5mg/L 0.67NTU
Embodiment 22 15.10mg/L 0.128mg/L 0.010mg/L 1.8mg/L 0.67NTU
Repeat embodiment 1 in the same way, and the raw water to embodiment 8- embodiment 22 is processed, the clearance of Mn More than 99%, the turbidity of water outlet is 1NTU or so.
Jing after processing, the clearance of Ni is that more than 85%, Cr is more than 70% to the raw water of 8～embodiment of embodiment 11, is gone out Water concentration is less than 0.003mg/L, and the clearance of Cd is more than 99%,
The raw water of embodiment 12-15 Jing after processing, the clearance of Ni be 79%～84% and with the initial concentration negative of Ni Close, the clearance of Cd is 40%～70% for the clearance of more than 80%, Cr.
Jing after processing, the clearance of Ni is more than 85% for the clearance of more than 84%, Cd to the raw water of embodiment 16-22, The clearance of Cr is more than 50%.
Comparative example 1-4 and embodiment 23-36 are 15.1mg/L from Mn concentration, and Ni concentration is the simulation of 0.128mg/L Water causes the pH=8.0 of simulation water as raw water by addition 126mg/L sodium bicarbonate, contaminated with actual Manganese Ore District The composition of high manganese containing water is consistent.Add different amounts of CaSO simultaneously4Initial calcium concentration in change raw water, adds not commensurability MgSO4Initial magnesium density in change water body.
Repeat embodiment 1 with described same steps, obtain the water quality of the raw water of comparative example 1-4 and embodiment 23-37 As shown in table 4, wherein "-" is represented and not detected, it can be seen that work as Ca for parameter and result2+Concentration a mg/L and Mg2 +Concentration b mg/L when meeting 13.75a+b >=18.7, raw water has preferable result；Wherein, Ca is worked as2+Concentration be more than During 128mg/L, account for manganese dioxide flco surface some can adsorb the adsorption site of nickel ion originally because calcium ion is robbed, because The clearance of this nickel is declined slightly.
The water quality parameter and result of the raw water of comparative example 1-4 of table 4 and embodiment 23-37
The water quality parameter and result (Continued) of the raw water of comparative example 1-4 of table 4 and embodiment 23-37

Claims (8)

1. it is a kind of remove Mn-bearing waste water in metal ion processing method, the Mn-bearing waste water include concentration more than 4mg/L Mn2 +, it is characterised in that the treating method comprises following steps：
(1) permanganate is added in Mn-bearing waste water so that the Mn in the permanganate and Mn-bearing waste water2+Mol ratio be 2: 3～2:5, by the Mn in Mn-bearing waste water2+Aoxidize and be converted to manganese dioxide flco；Then the pH value in regulation Mn-bearing waste water is 7.0～10.0 so that the electronegativity increment on manganese dioxide flco surface, strengthen energy of adsorption of the manganese dioxide flco to metal ion Power；
(2) Mn-bearing waste water 10min～30min is stirred with the rotating speed of 200r/min～400r/min so that at the beginning of manganese dioxide flco Step adsorbing metal ions, while so that manganese dioxide flco is mutually collided and increased；
(3) Mn-bearing waste water 2min～8min is stirred with the rotating speed of 10r/min～30r/min so that the manganese dioxide flco of increase Metal ion fully in absorption Mn-bearing waste water；
(4) Mn-bearing waste water is stood into more than 30min so that adsorbed the manganese dioxide settling of floccus of metal ion.
2. processing method as claimed in claim 1, it is characterised in that also include in the step (1) with 200r/min～ The rotating speed stirring 10s～5min of 400r/min.
3. processing method as claimed in claim 1, it is characterised in that between the step (2) and step (3), also include： 2min～10min is stirred with the rotating speed of 40r/min～100r/min so that manganese dioxide flco is mutually collided and continues increase, Prevent increased manganese dioxide flco from crushing simultaneously.
4. the processing method as described in claim 1-3 any one, it is characterised in that the temperature of the stirring is more than 4 DEG C.
5. processing method as claimed in claim 4, it is characterised in that also include after the step (4)：Remove sedimentation Manganese dioxide flco.
6. processing method as claimed in claim 5, it is characterised in that：The metal ion is manganese ion, nickel ion, cadmium ion Or chromium ion.
7. processing method as claimed in claim 1, it is characterised in that before the step (1), it is also useless containing manganese including adjusting Ca in water2+Concentration a and Mg2+Concentration b so that Ca2+And Mg2+Concentration meet 13.75a+b >=18.7.
8. processing method as claimed in claim 6, it is characterised in that in the Mn-bearing waste water of regulation, the Ca2+Concentration meet A >=1.36, or Mg2+Concentration meet b >=18.7.
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CN108046480A (en) * 2018-01-26 2018-05-18 福建欣宇卫浴科技股份有限公司 Stainless steel acid cleaning waste water processing system
CN113860560A (en) * 2021-10-26 2021-12-31 四川大学 Method for removing organic pollutants in high-salinity wastewater
CN114162841A (en) * 2022-01-17 2022-03-11 山东金利特新材料有限责任公司 Comprehensive treatment method for graphene oxide waste acid

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