CN106587430B - Processing method that is a kind of while removing various metals ion in Mn-bearing waste water - Google Patents
Processing method that is a kind of while removing various metals ion in Mn-bearing waste water Download PDFInfo
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- CN106587430B CN106587430B CN201611174037.1A CN201611174037A CN106587430B CN 106587430 B CN106587430 B CN 106587430B CN 201611174037 A CN201611174037 A CN 201611174037A CN 106587430 B CN106587430 B CN 106587430B
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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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
- 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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- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
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Abstract
The invention discloses a kind of processing methods for removing various metals ion in Mn-bearing waste water simultaneously.The processing method includes: that permanganate is added in Mn-bearing waste water first, the manganese ion in Mn-bearing waste water is aoxidized, Mn2+Be converted to manganese dioxide wadding body；Then adjusting the pH value in Mn-bearing waste water is 7.0~10.0；Then it is stirred respectively with the revolving speed of 200r/min~400r/min and 10r/min~30r/min, so that manganese dioxide wadding body mutually collides and increases, and sufficiently adsorbs the manganese ion in Mn-bearing waste water and other metal ions coexisted；Mn-bearing waste water 30min or more is finally stood, so that manganese dioxide settling of floccus.The present invention removes the metal ion in Mn-bearing waste water under conditions of not dosing coagulant to the cohesion of manganese dioxide using itself existing calcium ion in waste water and magnesium ion.
Description
Technical field
The invention belongs to water-treatment technology fields, more particularly, to a kind of processing method of Mn-bearing waste water.
Background technique
In recent years, the water contamination accident that the heavy metals such as manganese, nickel, cadmium and chromium cause 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, generate " Heisui River " and " yellow water " phenomenon.The manganese of the long-term excess intake of human body
The lesion that will cause related organ, causes slow poisoning.Equally, the intake of a small amount of nickel, chromium and cadmium can also make human body generate allergy
Reaction, it is possible to cause serious lesion or even cancer.Cadmium can be accumulated in human body, and be difficult to be discharged by metabolism
In vitro.Valence state existing for manganese is more in nature, mainly there is+2 ,+3 ,+4 and+7 valences, wherein+2 is relatively stable with+4 valences.
Domestic and foreign scholars have done a large amount of research to the processing problem of the heavy metal pollution of Mn-bearing waste water, and demanganization is common at present
Method has bioanalysis, contact oxidation method and chemical method.Chemical method usually 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 sedimentation or filtering.Since its is high
Production run expense, Ozonation is less to be used；It is secondary that chlorine dioxide easily reacts generation disinfection with the organic matter in water body
Product, therefore this method is also gradually eliminated；Permanganate still has stronger oxidability, Ke Yihe in neutral conditions
Bivalent manganese occurs comproportionation reaction and generates manganese dioxide.
By often heavy metal ion complicated component in the water body of heavy metal pollution, 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 biggish specific surface area, while its surface hydroxyl group rich in, this has generated in-situ manganese dioxide
Good absorption property, the heavy metals such as the manganese that can be used for coexisting in Adsorption water, nickel, cadmium and chromium.For other oxidants,
Permanganate oxidation divalent manganesetion can generate more manganese dioxide, to be conducive to the synchronous removal of various metals ion.
Although effect is being tried than relatively limited however, the manganese dioxide itself in sewage has certain Coagulation aiding
The coagulating sedimentation for needing to add a certain amount of coagulant in research and practical engineering application to promote manganese dioxide is tested, shortening is reached
Hydraulic detention time, the purpose for reducing delivery turbidity.However due to needing dosing coagulant, the complexity of technique is increased, and
And also improve processing cost.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of processing method of Mn-bearing waste water,
Its object is to use permanganate oxidation Mn2+Generate more manganese dioxide, using itself existing calcium ion in waste water and
Magnesium ion is to the cohesion of manganese dioxide, under conditions of not dosing coagulant, the synchronous manganese removed in Mn-bearing waste water and
The nickel chromium triangle and cadmium metal ion coexisted.
To achieve the above object, according to one aspect of the present invention, a kind of processing method of Mn-bearing waste water is provided, is handled
Preceding Mn-bearing waste water includes the Mn that concentration is greater than 4mg/L2+, it 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+Molar ratio
For 2:3~2:5, by the Mn in Mn-bearing waste water2+It aoxidizes and is converted to manganese dioxide wadding body；Then the pH value in Mn-bearing waste water is adjusted
It is 7.0~10.0, so that the electronegativity increment on manganese dioxide wadding body surface, enhances absorption of the manganese dioxide wadding body to metal ion
Ability；
(2) Mn-bearing waste water 10min~30min is stirred with the revolving speed of 200r/min~400r/min, so that manganese dioxide is wadded a quilt with cotton
The preliminary adsorbing metal ions of body, while manganese dioxide wadding body being made mutually to collide and increase；
(3) Mn-bearing waste water 2min~8min is stirred with the revolving speed of 10r/min~30r/min, so that the manganese dioxide increased
Wadding body sufficiently adsorbs the metal ion in Mn-bearing waste water；
(4) Mn-bearing waste water is stood into 30min or more, so that having adsorbed the manganese dioxide settling of floccus of metal ion.
It preferably, further include adjusting Ca in Mn-bearing waste water before the step (1)2+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 before the processing includes the Mn that concentration is greater than 100mg/L2+, the nickel
The concentration of ion is 3mg/L hereinafter, the concentration of the cadmium ion is 8mg/L or less.
Preferably, in the step (1) further include: stir 10s~5min with the revolving speed of 200r/min~400r/min.
Preferably, between the step (2) and step (3), further includes: stirred with the revolving speed of 40r/min~100r/min
2min~10min is mixed, so that manganese dioxide wadding body mutually collides and continues to increase, while preventing increased manganese dioxide from wadding a quilt with cotton
Body is broken.
As it is further preferred that the temperature of the stirring is greater than 4 DEG C.
It preferably, further include the manganese dioxide wadding body for removing sedimentation after the step (4).
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
1, the present invention is by being added permanganate during processing, oxidation removal water middle and high concentration divalent manganesetion it is same
Shi Shengcheng manganese dioxide, generated in-situ manganese dioxide have stronger absorption property, can be by the synchronous removal water body of absorption
The heavy metals such as remaining manganese, nickel, cadmium and chromium；It is verified, 98% and 79% or more is up to respectively to the removal effect of manganese and nickel, cadmium,
The removal rate of chromium is respectively up to 80% and 40% or more；
2, the present invention can make full use of existing calcium ion itself and magnesium ion in Mn-bearing waste water to effectively facilitate titanium dioxide
The flocculation sedimentation of manganese, the specific surface area for reducing manganese dioxide, advantageously reduce processing water turbidity；To the nothing in water treatment procedure
Additional dosing coagulant is needed, adding of agent is saved, simplification of flowsheet reduces processing cost；The required calcium ions and magnesium ions of the present invention
Content is all fewer, is suitable for most of Mn-bearing waste water, such as the contaminated water body in Manganese Ore District and electrolytic manganese industry waste water.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below each other it
Between do not constitute conflict and can be combined with each other.
Key reaction principle of the invention are as follows: 2MnO4 -+3Mn2++2H2O=5MnO2+4H+, permanganate oxidation bivalent manganese
Ion generates manganese dioxide, using the remaining heavy metals such as manganese and nickel, cadmium and chromium in the adsorptivity removal water body of manganese dioxide, together
Calcium ion present in Shi Liyong water body and magnesium ion remarkably promote the flocculation sedimentation of manganese dioxide, reduce delivery turbidity.
The present invention provides a kind of processing method of Mn-bearing waste water, the Mn-bearing waste water before the processing includes that concentration is greater than
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 it is full
Sufficient b >=18.7, or both concentration meet 13.75a+b >=18.7 jointly, can if the Mn-bearing waste water is unsatisfactory for above-mentioned condition
It is set to meet 13.75a+b >=18.7 by the way that appropriate calcium salt and/or magnesium salts is added；It the treating method comprises following steps:
(1) permanganate is added in Mn-bearing waste water, so that the permanganate and Mn2+Molar ratio be 2:3~2:5,
By the heavy metal oxidation in Mn-bearing waste water, manganese ion is converted to manganese dioxide wadding body；Then the pH value in adjusting Mn-bearing waste water is
7.0~10.0, so that the electronegativity increment on manganese dioxide wadding body surface, adsorption energy of the enhancing manganese dioxide wadding body to metal ion
Power；
(2) Mn-bearing waste water 10min~30min is stirred with the revolving speed of 200r/min~400r/min, so that manganese dioxide is wadded a quilt with cotton
Body mutually collides and increases, 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 revolving speed of 10r/min~30r/min, so that the manganese dioxide increased
Wadding body further adsorbs the metal ion in Mn-bearing waste water, while preventing the manganese dioxide increased broken；
(4) Mn-bearing waste water is stood into 30min or more, so that having adsorbed the manganese dioxide settling of floccus of metal ion；It removes
The manganese dioxide wadding body of sedimentation completes the synchronization process of various metals ion in Mn-bearing waste water.
Wherein, in step (1), 10s~5min can be stirred with the revolving speed of 200r/min~400r/min simultaneously, to promote
Sufficiently dissolved in Mn-bearing waste water into permanganate, between step (2) and step (3), can also include: with 40r/min~
The revolving speed of 100r/min stirs 2min~10min, so that manganese dioxide wadding body mutually collides and continues to increase, prevents simultaneously
Only increased manganese dioxide wadding body is broken；Temperature when all stirrings is all larger than 4 DEG C, to guarantee the wadding of manganese dioxide wadding body
The solidifying and absorption to metal ion.
Embodiment 1
The present embodiment selects the contaminated high manganese containing water in Guangxi mining area, and calcium ion concentration is 324.5mg/L, magnesium in raw water
Ion concentration is 53.9mg/L, and pH 6.89, other water quality parameters are shown in Table 1, using demanganization process demanganization of the invention, place
Managing temperature is 14 DEG C.
S1. adding the potassium permanganate of 24.29mg/L in raw water while adjusting pH is 8.0 (theoretically potassium permanganate and divalent
The molar ratio of manganese ion can be by divalent manganesetion complete oxidation when being 2:3 insoluble manganese dioxide, i.e. 1mg manganese theoretically
Need 1.92mg potassium permanganate.Raw water manganese ion concentration is 15.1mg/L, theoretically needs the potassium permanganate ability of 28.99mg/L
Divalent manganesetion is completely oxidized to manganese dioxide), while with the mixing speed of 300r/min oxidation 2min to be pre-oxidized；
S2. 15min is stirred quickly with 300r/min after pre-oxidizing；
S3. with 50r/min moderate-speed mixer 2min；
S4. 5min is mixed slowly with 20r/min, flocculated；
S5. the turbidity for measuring supernatant after flocculating after quiet heavy 60min uses ICP after supernatant is filtered with 0.45 μm of film
Each heavy metal concentration variation is shown in Table 1 in water outlet after detection processing, and wherein "-" expression is not detected.
Effluent quality parameter list after 1 raw water of table and processing
| Water quality parameter | Unit | Raw water | It is discharged after processing | Removal rate (%) |
| 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 | - |
Steps are as follows described in embodiment 2:
S1. adding the potassium permanganate of 24.29mg/L in raw water while adjusting pH is 7.5 (theoretically potassium permanganate and divalent
The molar ratio of manganese ion can be by divalent manganesetion complete oxidation when being 2:3 insoluble manganese dioxide, i.e. 1mg manganese theoretically
Need 1.92mg potassium permanganate.Raw water manganese ion concentration is 15.1mg/L, theoretically needs the potassium permanganate ability of 28.99mg/L
Divalent manganesetion is completely oxidized to manganese dioxide), while with the mixing speed of 300r/min oxidation 2min to be pre-oxidized；
S2. after pre-oxidizing, 35.19mg/L aluminium polychloride is added, 15min is stirred quickly with 300r/min；
S3. with 50r/min moderate-speed mixer 2min；
S4. 5min is mixed slowly with 20r/min, flocculated；
S5. the turbidity for measuring supernatant after flocculating after quiet heavy 60min uses ICP after supernatant is filtered with 0.45 μm of film
Each heavy metal concentration variation in water outlet after detection processing.
Embodiment 3
Embodiment 2 is repeated with the same steps, difference is, the poly- of 40.39mg/L is added in the step S2
Close ferric sulfate.
Embodiment 4
Embodiment 2 is repeated with the same steps, difference is, is added without any medicament in the 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 removal rate embodiment 2 of Ni has reached 70% or more, embodiment 3
It is 61%, embodiment 4 is 75%；The removal rate of remaining Mn, Cr and Cd are roughly the same with embodiment 1.
Embodiment 5- embodiment 7 repeats embodiment 1 with the same steps, and with the implementation of 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 removal rate embodiment 5 of Ni has reached 75% or more, and embodiment 6 is 75%, implements
Example 7 is 91%；The removal rate of remaining Mn, Cr and Cd are roughly the same with embodiment 1.
The reaction condition of 2 embodiment 5- embodiment 7 of table
| 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 kaolin being added in the raw water of embodiment 1 to adjust turbidity, Ni (NO is added3)2To change the initial Ni of water sample
Cd (NO is added in concentration3)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 3 embodiment 8- embodiment 22 of table
| 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 |
Embodiment 1 is repeated in the same way, and the raw water of embodiment 8- embodiment 22 is handled, the removal rate of Mn
More than 99%, the turbidity of water outlet is 1NTU or so.
After processing, the removal rate of Ni is that 85% or more, Cr is 70% or more to the raw water of 8~embodiment of embodiment 11, out
Water concentration is lower than 0.003mg/L, and the removal rate of Cd is 99% or more,
After processing, the removal rate of Ni is 79%~84% and the initial concentration negative with Ni to the raw water of embodiment 12-15
It closes, the removal rate that the removal rate of Cd is 80% or more, Cr is 40%~70%.
After processing, the removal rate that the removal rate of Ni is 84% or more, Cd is 85% or more to the raw water of embodiment 16-22,
The removal rate of Cr is 50% or more.
It is 15.1mg/L that comparative example 1-4 and embodiment 23-36, which selects Mn concentration, and Ni concentration is the simulation of 0.128mg/L
Water makes the pH=8.0 for simulating water as raw water, and by adding 126mg/L sodium bicarbonate, contaminated with practical Manganese Ore District
The ingredient of high manganese containing water is consistent.Different amounts of CaSO is added simultaneously4Change initial calcium concentration in raw water, is added not same amount
MgSO4To change initial magnesium density in water body.
Embodiment 1 is repeated with the same steps, obtains the water quality of the raw water of comparative example 1-4 and embodiment 23-37
Parameter and processing result are as shown in table 4, and wherein "-" expression is not detected, it can be seen that works as Ca2+Concentration a mg/L and Mg2 +Concentration b mg/L when meeting 13.75a+b >=18.7, raw water has preferable processing result；Wherein, work as Ca2+Concentration be greater than
When 128mg/L, accounts for some scripts in manganese dioxide wadding body surface since calcium ion is robbed and can adsorb the adsorption site of nickel ion, because
The removal rate of this nickel is declined slightly.
The water quality parameter and processing result of the raw water of table 4 comparative example 1-4 and embodiment 23-37
The water quality parameter and processing result (Continued) of the raw water of table 4 comparative example 1-4 and embodiment 23-37
Embodiment 38- embodiment 40 repeats embodiment 1 with the same steps, and with the reality of parameter change shown in table 5
The reaction condition of example 1 is applied, unlisted parameter is same as Example 1 in table, also can get detection knot similar to Example 1
Fruit.
The reaction condition of 5 embodiment 38- embodiment 40 of table
| Reaction condition | Embodiment 38 | Embodiment 39 | Embodiment 40 |
| Treatment temperature | 4℃ | 15℃ | 20℃ |
| The pH adjusted in step (1) | 7.0 | 8.0 | 10.0 |
| The stirring condition of S1 | 200r/min, 20min | 300r/min, 30min | 400r/min, 10min |
| The stirring condition of S2 | 100r/min, 2min | The step without | 40r/min, 8min |
| The stirring condition of S3 | 30r/min, 2min | 20r/min, 8min | 10r/min, 6min |
| The quiet heavy time | 30min | 40min | 50min |
Embodiment 41- embodiment 42 selects the high manganese containing water body of not calcium-magnesium-containing, and wherein manganese content is 8.4mg/L, is being added
Before permanganate, the calcium ion of 1.36mg/L is added in embodiment 41, and the magnesium ion of 18.7mg/L is added in embodiment 42, other steps
Suddenly with embodiment 1, testing result similar to Example 1 is also obtained.
Embodiment 43- embodiment 44 selects high manganese containing water body, and wherein manganese content is 11.3mg/L, and calcium ion concentration is
0.28mg/L, magnesium ion concentration are 5.6mg/L before permanganate is added, and the calcium ion of 0.69mg/L is added in embodiment 43,
The magnesium ion of 9.25mg/L is added in embodiment 44, other steps also obtain detection knot similar to Example 1 with embodiment 1
Fruit.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. the processing method of metal ion, the Mn-bearing waste water include the Mn that concentration is greater than 4mg/L in a kind of removal Mn-bearing waste water2 +, which is characterized in that it 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+Molar ratio be 2:
3~2:5, by the Mn in Mn-bearing waste water2+It aoxidizes and is converted to manganese dioxide wadding body；Then the pH value in adjusting Mn-bearing waste water is
7.0~10.0, so that the electronegativity increment on manganese dioxide wadding body surface, adsorption energy of the enhancing manganese dioxide wadding body to metal ion
Power；
(2) Mn-bearing waste water 10min~30min is stirred with the revolving speed of 200r/min~400r/min, so that at the beginning of manganese dioxide wadding body
Adsorbing metal ions are walked, while manganese dioxide wadding body being made mutually to collide and increase；
(3) Mn-bearing waste water 2min~8min is stirred with the revolving speed of 10r/min~30r/min, so that the manganese dioxide wadding body increased
Metal ion sufficiently in absorption Mn-bearing waste water；
(4) Mn-bearing waste water is stood into 30min or more, so that having adsorbed the manganese dioxide settling of floccus of metal ion；
It further include adjusting Ca in Mn-bearing waste water before the step (1)2+Concentration a and Mg2+Concentration b, so that Ca2+And
Mg2+Concentration meet 13.75a+b >=18.7.
2. processing method as described in claim 1, which is characterized in that in the step (1) further include with 200r/min~
The revolving speed of 400r/min stirs 10s~5min.
3. processing method as described in claim 1, which is characterized in that between the step (2) and step (3), further includes:
2min~10min is stirred with the revolving speed of 40r/min~100r/min, so that manganese dioxide wadding body mutually collides and continues to increase,
Prevent increased manganese dioxide wadding body broken simultaneously.
4. processing method as claimed in any one of claims 1-3, which is characterized in that the temperature of the stirring is greater than 4 DEG C.
5. processing method as claimed in claim 4, which is characterized in that after the step (4) further include: remove sedimentation
Manganese dioxide wadding body.
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 described in claim 1, which is characterized in that in the Mn-bearing waste water of adjusting, the Ca2+Concentration meet
A >=1.36 or Mg2+Concentration meet b >=18.7.
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| JP2003063826A (en) * | 2001-08-24 | 2003-03-05 | Kurita Water Ind Ltd | Method for recovering chromic acid and bichromic acid |
| CN105236636A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Gold ore manganese-containing wastewater treatment method |
| CN105236637A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Manganese ore wastewater comprehensive treatment method |
| CN105236635A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Manganese ore wastewater treatment method |
| CN105293791A (en) * | 2015-10-10 | 2016-02-03 | 贵州万山兴隆锰业有限公司 | Treatment method for manganese ore wastewater |
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| JP2003063826A (en) * | 2001-08-24 | 2003-03-05 | Kurita Water Ind Ltd | Method for recovering chromic acid and bichromic acid |
| CN105236636A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Gold ore manganese-containing wastewater treatment method |
| CN105236637A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Manganese ore wastewater comprehensive treatment method |
| CN105236635A (en) * | 2015-10-10 | 2016-01-13 | 贵州万山兴隆锰业有限公司 | Manganese ore wastewater treatment method |
| CN105293791A (en) * | 2015-10-10 | 2016-02-03 | 贵州万山兴隆锰业有限公司 | Treatment method for manganese ore wastewater |
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