CN102502915A - Method for thoroughly removing Hg(II) in water by virtue of in situ generation of new ecological nano manganese dioxide - Google Patents
Method for thoroughly removing Hg(II) in water by virtue of in situ generation of new ecological nano manganese dioxide Download PDFInfo
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- CN102502915A CN102502915A CN2011104557947A CN201110455794A CN102502915A CN 102502915 A CN102502915 A CN 102502915A CN 2011104557947 A CN2011104557947 A CN 2011104557947A CN 201110455794 A CN201110455794 A CN 201110455794A CN 102502915 A CN102502915 A CN 102502915A
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Abstract
The invention discloses a method for thoroughly removing Hg(II) in water by virtue of in situ generation of new ecological nano manganese dioxide and relates to a method for removing Hg(II) in water. By using the method, the problems that the existing Hg(II) removal process is complex, is extremely low in removal rate and causes secondary pollution are solved. The method comprises the following steps: 1, adding permanganate and a reducing agent A or a reducing agent B into Hg(II)-containing water and stirring to obtain a mixed solution; and 2, adding a coagulant into the mixed solution, carrying out coagulation, filtration, precipitation and clearing through a conventional water treatment process in turn so as to complete the reaction. According to the invention, a nano manganese dioxide adsorbent is generated in situ through reaction of permanganate and the reducing agent, the content of trace Hg(II) in a drinking water source reaches the provision of standards for drinking water quality (GB5749-2006) when a water plant discharges water. The Hg(II) removal efficiency of the method disclosed by the invention reaches more than 99%; the method is simple in process, flexible and convenient to operate and low in operation cost; and the original treatment process in the water plant is not changed.
Description
Technical field
The present invention relates to remove the method for Hg in the water (II).
Background technology
Mercury (mercury) is commonly called as " mercury ", and silvery white has metalluster, is unique metal that is in a liquid state under the normal temperature.Mercury has very supervirulent pollutent as a kind of to human body and higher organism, is prevalent in occurring in nature.Environment mercury pollution problem by mercury and compound thereof caused is serious day by day, has become big public hazards of environment for human survival.The tap water mercury pollution is mainly the pollution of drinking water source, main path: the discharging of mercury-containing waste water; The unreasonable disposal of mercurous waste and stacking cause mercury to leak; Mercury ore area and mercury pollution be the area seriously, dissolves and wash away the pollution of waterhead that causes by rainwater; Cause the release of mercury in river and the bottom mud in lake by environment change.Mercury poisoning can cause that abalienation, mucous hyperemia, ulcer, kidney depletion, proteinuria, sexual function weaken, women's menoxenia or miscarriage and hyperthyroidism etc.China's " drinking water sanitary standard " (GB5749-2006) in the regulation tap water the ceiling value of mercury concentration be 1 μ g/L.Therefore, the method for highly economical, safety and environmental protection of needing badly is removed mercury in the water, solves mercury pollution problem in the water.
In recent years, China's mercury pollution is serious day by day, like ground such as Guizhou, Heilungkiang and Sprite mercury poisoning incident etc.Mercury pollution directly causes health of human body to be endangered, serious threat public health security.
There is not proven technique in China as yet to the mercury pollution water body at present; Domestic method is to add sulfide to carry out chemical precipitation; But a lot of sulfide are such as hydrogen sulfide, sodium sulphite itself or drop into the serious stink of meeting generation in the water; Extremely unfavorable to environment, and be used for dirty wastewater treatment mostly, be difficult to thoroughly remove mercury in the tap water.And conventional coagulating agent aluminium salt does not almost have any removal to mercury during up to 40mgAl/L, and simple molysite is also very low to the removal efficient of mercury.
Summary of the invention
The present invention seeks to remove Hg (II) complex process, secondary pollution and the extremely low problem of clearance, and provide original position to generate the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) in order to solve to have now.
The method that original position generation nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) realizes according to the following steps: one, in containing Hg (II) water, add permanganate and reductive agent A or reductive agent B; Then with speed stirring reaction 1～5min of 100～250r/min; With speed stirring reaction 10～20min of 20～60r/min, obtain mixing solutions again; Two, dosing coagulant in step 1 gained mixing solutions, pass through conventional water treatment process coagulation, filtration, deposition and clarification successively then after, promptly accomplish original position and generate the nascent state nano-manganese dioxide and thoroughly remove Hg in the water (II);
Wherein the mol ratio of permanganate and reductive agent A is 0.1～1.0: 1 in the step 1, and the mol ratio of permanganate and reductive agent B is 0.5～2.66: 1, and the permanganate dosage is counted 0.5～10mg/L with manganese; Permanganate is potassium permanganate or sodium permanganate in the step 1; Reductive agent A is a manganous sulfate in the step 1; Reductive agent B is a Sulfothiorine in the step 1; The dosage of coagulating agent is 10mg/L in the step 2.
The present invention utilizes permanganate and reductive agent reaction original position to generate the nano-manganese dioxide sorbent material; This sorbent material have that particle is tiny, specific surface area is big, electronegativity is big and to conventional coagulating agent help coagulate about, be easy to characteristics such as precipitate and separate; Can effectively remove micro-Hg (II) in the water; Can guarantee that micro-Hg (II) reaches " drinking water sanitary standard " regulation (GB5749-2006) in the drinking water source when water factory's water outlet, mercury concentration is lower than 1 μ g/L.This technology removal of mercury efficient is high, technology is simple, flexible and convenient operation, do not change the original treatment process of water factory and running cost low, can be used for the conventional processing and the emergency processing of mercury pollution in the water.
Original position of the present invention generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II), and the clearance of Hg (II) is reached more than 99%.
Description of drawings
Fig. 1 is a design sketch of removing Hg (II) in the water among the embodiment 2; Wherein
representes clearance, ● expression mercury concentration.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method that this embodiment original position generation nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) realizes according to the following steps: one, in containing Hg (II) water, add permanganate and reductive agent A or reductive agent B; Then with speed stirring reaction 1～5min of 100～250r/min; With speed stirring reaction 10～20min of 20～60r/min, obtain mixing solutions again; Two, dosing coagulant in step 2 gained mixing solutions, pass through conventional water treatment process coagulation, filtration, deposition and clarification successively then after, promptly accomplish original position and generate the nascent state nano-manganese dioxide and thoroughly remove Hg in the water (II);
Wherein the mol ratio of permanganate and reductive agent A is 0.1～1.0: 1 in the step 1, and the mol ratio of permanganate and reductive agent B is 0.5～2.66: 1, and the permanganate dosage is counted 0.5～10mg/L with manganese; Permanganate is potassium permanganate or sodium permanganate in the step 1; Reductive agent A is a manganous sulfate in the step 1; Reductive agent B is a Sulfothiorine in the step 1; The dosage of coagulating agent is 10mg/L in the step 2.
Embodiment two: this embodiment and embodiment one are different is that the mol ratio of permanganate and reductive agent A is 0.2～0.8: 1 in the step 1; The mol ratio of permanganate and reductive agent B is 0.8～2.5: 1, and the permanganate dosage is counted 1～8mg/L with manganese.Other step and parameter are identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is that the mol ratio of permanganate and reductive agent A is 0.67: 1 in the step 1, and the mol ratio of permanganate and reductive agent B is 2: 1, and the permanganate dosage is counted 4mg/L with manganese.Other step and parameter are identical with embodiment one.
Embodiment four: this embodiment is different with one of embodiment one to three be in the step 1 with speed stirring reaction 2～4min of 120～220r/min, with speed stirring reaction 12～18min of 30～50r/min, obtain mixing solutions again.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: this embodiment is different with one of embodiment one to three be in the step 1 with the speed stirring reaction 3min of 200r/min, with the speed stirring reaction 15min of 40r/min, obtain mixing solutions again.Other step and parameter are identical with one of embodiment one to three.
Embodiment six: what this embodiment was different with one of embodiment one to five is that coagulating agent is Tai-Ace S 150, Poly aluminum Chloride (PAC), iron(ic)chloride or ferric sulfate in the step 2.Other step and parameter are identical with one of embodiment one to five.
Embodiment 1:
The method that original position generation nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) realizes according to the following steps: one, in containing Hg (II) water, add permanganate and reductive agent A; Then with the speed stirring reaction 2min of 120r/min; With the speed stirring reaction 15min of 40r/min, obtain mixing solutions again; Two, dosing coagulant in step 2 gained mixing solutions, pass through conventional water treatment process coagulation, filtration, deposition and clarification successively then after, promptly accomplish original position and generate the nascent state nano-manganese dioxide and thoroughly remove Hg in the water (II);
Wherein the mol ratio of permanganate and reductive agent A is 0.67: 1 in the step 1, and the permanganate dosage is counted 4mg/L with manganese; Permanganate is potassium permanganate or sodium permanganate in the step 1; Reductive agent A is a manganous sulfate in the step 1; The dosage of coagulating agent is 10mg/L in the step 2.
The content that the present embodiment step 1 contains Hg (II) in Hg (II) water is 30 μ g/L; Coagulating agent is a Tai-Ace S 150 in the step 2.
Original position generates the nascent state nano-manganese dioxide and thoroughly removes Hg in the water (II) in the present embodiment, and through detecting, the efficient of removing Hg (II) in the water is 99.9%.
Embodiment 2:
The method that original position generation nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) realizes according to the following steps: one, in containing Hg (II) water, add permanganate and reductive agent B; Then with the speed stirring reaction 2min of 120r/min; With the speed stirring reaction 15min of 40r/min, obtain mixing solutions again; Two, dosing coagulant in step 2 gained mixing solutions, pass through conventional water treatment process coagulation, filtration, deposition and clarification successively then after, promptly accomplish original position and generate the nascent state nano-manganese dioxide and thoroughly remove Hg in the water (II);
Wherein the mol ratio of permanganate and reductive agent B is 2: 1 in the step 1, and the permanganate dosage is counted 4mg/L with manganese; Permanganate is potassium permanganate or sodium permanganate in the step 1; Reductive agent B is a Sulfothiorine in the step 1; The dosage of coagulating agent is 10mg/L in the step 2.
The content that the present embodiment step 1 contains Hg (II) in Hg (II) water is 30 μ g/L; Coagulating agent is a Poly aluminum Chloride (PAC) in the step 2.
Original position generates the nascent state nano-manganese dioxide and thoroughly removes Hg in the water (II) in the present embodiment, and through detecting, the result is as shown in Figure 1, and the visible efficient of removing Hg (II) in the water is 99.99%, and the mercury residual concentration is lower than 1 μ g/L.
Claims (6)
1. original position generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II); It is characterized in that original position generates the nascent state nano-manganese dioxide and thoroughly removes the method for Hg in the water (II) and realize according to the following steps: one, in containing Hg (II) water, add permanganate and reductive agent A or reductive agent B; Then with speed stirring reaction 1～5min of 100～250r/min; With speed stirring reaction 10～20min of 20～60r/min, obtain mixing solutions again; Two, dosing coagulant in step 2 gained mixing solutions, pass through conventional water treatment process coagulation, filtration, deposition and clarification successively then after, promptly accomplish original position and generate the nascent state nano-manganese dioxide and thoroughly remove Hg in the water (II);
Wherein the mol ratio of permanganate and reductive agent A is 0.1～1.0: 1 in the step 1, and the mol ratio of permanganate and reductive agent B is 0.5～2.66: 1, and the permanganate dosage is counted 0.5～10mg/L with manganese; Permanganate is potassium permanganate or sodium permanganate in the step 1; Reductive agent A is a manganous sulfate in the step 1; Reductive agent B is a Sulfothiorine in the step 1; The dosage of coagulating agent is 10mg/L in the step 2.
2. original position according to claim 1 generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II); It is characterized in that the mol ratio of permanganate and reductive agent A is 0.2～0.8: 1 in the step 1; The mol ratio of permanganate and reductive agent B is 0.8～2.5: 1, and the permanganate dosage is counted 1～8mg/L with manganese.
3. original position according to claim 1 generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II); It is characterized in that the mol ratio of permanganate and reductive agent A is 0.67: 1 in the step 1; The mol ratio of permanganate and reductive agent B is 2: 1, and the permanganate dosage is counted 4mg/L with manganese.
4. generate the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II) according to claim 1,2 or 3 described original positions; It is characterized in that in the step 1 speed stirring reaction 2～4min with 120～220r/min; With speed stirring reaction 12～18min of 30～50r/min, obtain mixing solutions again.
5. original position according to claim 4 generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II); It is characterized in that in the step 1 speed stirring reaction 3min with 200r/min; With the speed stirring reaction 15min of 40r/min, obtain mixing solutions again.
6. original position according to claim 5 generates the method that the nascent state nano-manganese dioxide is thoroughly removed Hg in the water (II), it is characterized in that coagulating agent is Tai-Ace S 150, Poly aluminum Chloride (PAC), iron(ic)chloride or ferric sulfate in the step 2.
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Cited By (6)
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| CN103723815A (en) * | 2012-10-15 | 2014-04-16 | 南开大学 | Method used for high efficient removing of trichloroethylene with nascent state MnO2 combining Fe(II) |
| CN103848523A (en) * | 2014-04-01 | 2014-06-11 | 哈尔滨工业大学 | Method for removing complexing agent of Hg (II) from water by using strengthened manganese oxide |
| CN103922512A (en) * | 2014-05-05 | 2014-07-16 | 哈尔滨工业大学 | Method for removing trace antimony in water |
| CN105324340A (en) * | 2013-06-24 | 2016-02-10 | 环球油品公司 | Manganese oxide-based and metallomanganese oxide-based ion-exchangers for removing mercury (+2) ions from liquid streams |
| CN106512972A (en) * | 2016-12-19 | 2017-03-22 | 唐山华顺环保科技有限公司 | Preparation method, preparation system, application and regeneration method of polypyrrole composite newly formed manganese dioxide adsorbent |
| CN110028141A (en) * | 2019-04-24 | 2019-07-19 | 中国科学技术大学 | Resistant gene deep treatment method in a kind of sewage |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103723815A (en) * | 2012-10-15 | 2014-04-16 | 南开大学 | Method used for high efficient removing of trichloroethylene with nascent state MnO2 combining Fe(II) |
| CN105324340A (en) * | 2013-06-24 | 2016-02-10 | 环球油品公司 | Manganese oxide-based and metallomanganese oxide-based ion-exchangers for removing mercury (+2) ions from liquid streams |
| CN103848523A (en) * | 2014-04-01 | 2014-06-11 | 哈尔滨工业大学 | Method for removing complexing agent of Hg (II) from water by using strengthened manganese oxide |
| CN103848523B (en) * | 2014-04-01 | 2016-01-13 | 哈尔滨工业大学 | A kind of strengthening Mn oxide removes the method for the complexing agent of Hg (II) in water |
| CN103922512A (en) * | 2014-05-05 | 2014-07-16 | 哈尔滨工业大学 | Method for removing trace antimony in water |
| CN106512972A (en) * | 2016-12-19 | 2017-03-22 | 唐山华顺环保科技有限公司 | Preparation method, preparation system, application and regeneration method of polypyrrole composite newly formed manganese dioxide adsorbent |
| CN110028141A (en) * | 2019-04-24 | 2019-07-19 | 中国科学技术大学 | Resistant gene deep treatment method in a kind of sewage |
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Application publication date: 20120620 |