CN103848523B - A kind of strengthening Mn oxide removes the method for the complexing agent of Hg (II) in water - Google Patents
A kind of strengthening Mn oxide removes the method for the complexing agent of Hg (II) in water Download PDFInfo
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- CN103848523B CN103848523B CN201410128711.7A CN201410128711A CN103848523B CN 103848523 B CN103848523 B CN 103848523B CN 201410128711 A CN201410128711 A CN 201410128711A CN 103848523 B CN103848523 B CN 103848523B
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Abstract
A kind of strengthening Mn oxide removes the method for the complexing agent of Hg (II) in water, and it relates to the method that Hg (II) in water is removed in strengthening.The present invention will solve the existing Hg (II) that removes and there is the extremely low problem of clearance.Method: one, add complexing agent A to containing in Hg (II) water, then add adsorbent B or C, obtain mixing solutions after stirring; Two, dosing coagulant in mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, namely completes.The present invention utilizes complexing agent A can change the character of sorbent material and Hg simultaneously, can ensure that in drinking water source, micro-Hg (II) reaches the regulation of " drinking water sanitary standard " (GB5749-2006) when water factory's water outlet, present invention process mercury removal efficiency up to more than 99%, technique is simple, flexible and convenient operation, do not change the original treatment process of water factory and running cost low.The present invention is applied to stain disease process field.
Description
Technical field
The present invention relates to the method that Hg (II) in water is removed in strengthening.
Background technology
Mercury (mercury), is commonly called as " mercury ", silvery white, has metalluster, is the metal be uniquely in a liquid state under normal temperature.Mercury has very supervirulent pollutent as one to human body and higher organism, is prevalent in occurring in nature.The environmental mercury problem caused by mercury and mercuric compounds is day by day serious, has become large public hazards of environment for human survival.Tap water mercury pollution is mainly the pollution of drinking water source, main path: the discharge of mercury-containing waste water; The unreasonable disposal of mercury-containing wastes and stacking cause mercury to leak; Mercury ore is regional and mercury pollution is seriously regional, is dissolved and wash away the pollution of waterhead caused by rainwater; The release of mercury in river and bottom mud in lake is caused by environment change.Mercury poisoning can cause abalienation, mucous hyperemia, ulcer, kidney failure, proteinuria, sexual function weaken, woman in menstrual period is lacked of proper care or miscarry and hyperthyroidism etc.The most ceiling value of China " drinking water sanitary standard " (GB5749-2006) regulation Mercury in Drinking Water concentration is 1 μ g/L.Therefore, need mercury in the method removal water of efficient economy, safety and environmental protection badly, solve mercury pollution problem in water.
In recent years, China's mercury pollution is day by day serious, as the ground such as Guizhou, Heilungkiang and Sprite mercury poisoning event etc.Mercury pollution directly causes health of human body to be endangered, serious threat public health security.
Not yet there is proven technique in current China to mercury pollution water body, common method adds sulfide to carry out chemical precipitation, but serious stink can be produced in a lot of sulfide such as hydrogen sulfide, sodium sulphite itself or input water, extremely unfavorable to environment, and be used for greatly stain disease process, be difficult to thoroughly remove Mercury in Drinking Water.And conventional coagulating agent aluminium salt up to during 40mgAl/L to mercury almost without any removal, simple molysite and Mn oxide also very low to the removal efficiency of mercury.
Summary of the invention
The present invention seeks to solve the existing problem extremely low except Hg (II) clearance, and provide a kind of strengthening Mn oxide to remove the method for the complexing agent of Hg (II) in water.
One strengthening Mn oxide of the present invention removes the method for the complexing agent of Hg (II) in water, realize according to the following steps: one, add complexing agent to containing in Hg (II) water, add sorbent material again, then with the speed stirring reaction 1 ~ 60min of 100 ~ 350r/min, mixing solutions is obtained; Two, to dosing coagulant in step one gained mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, the complexing agent that strengthening Mn oxide removes Hg (II) in water is namely completed;
The wherein mol ratio 2 ~ 10000: 1 of step one complexing agent and Hg; Sorbent material dosage counts 1 ~ 50mg/L with manganese; In step 2, the dosage of coagulating agent is 10mg/L.
The present invention comprises following beneficial effect:
The present invention utilizes Sulfothiorine as complexing agent, and this complexing agent is nontoxic, safety, can change the potentiometric properties of mercury in water, makes uncharged mercury electronegative, can also generate divalence Mn2+ simultaneously and be attracted to removal sorbent material increasing mercury as positively charged ion bridge.Remaining mercury concentration can ensure that in drinking water source, micro-Hg (II) reaches the regulation of " drinking water sanitary standard " (GB5749-2006) when water factory's water outlet, and mercury concentration is lower than 1 μ g/L.This technique mercury removal efficiency is high, technique is simple, flexible and convenient operation, do not change the original treatment process of water factory and running cost low, can be used for conventional processing and the emergency processing of mercury pollution in water.
The present invention strengthens the complexing agent that Mn oxide thoroughly removes Hg in water (II), and the clearance that Hg (II) is removed in strengthening reaches more than 99%.
Accompanying drawing explanation
Fig. 1 is the design sketch removing Hg in water (II) in embodiment 2, and wherein ▽ represents clearance, ● represent mercury concentration.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the one strengthening Mn oxide of present embodiment removes the method for the complexing agent of Hg (II) in water, realize according to the following steps: one, add complexing agent to containing in Hg (II) water, add sorbent material again, then with the speed stirring reaction 1 ~ 60min of 100 ~ 350r/min, mixing solutions is obtained; Two, to dosing coagulant in step one gained mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, the complexing agent that strengthening Mn oxide removes Hg (II) in water is namely completed;
The wherein mol ratio 2 ~ 10000: 1 of step one complexing agent and Hg; Sorbent material dosage counts 1 ~ 50mg/L with manganese; In step 2, the dosage of coagulating agent is 10mg/L.
Embodiment two: present embodiment and embodiment one unlike: the complexing agent described in step one is Sulfothiorine.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the sorbent material described in step one is nascent state ferrimanganic or nanometer nascent state manganese.Nascent state ferrimanganic preparation method is permanganate oxidation ferrous sulfate or iron protochloride gained solid matter; The solid matter that nanometer nascent state manganese preparation method obtains for permanganate oxidation manganous sulfate, Manganous chloride tetrahydrate, Sulfothiorine or S-WAT.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 9000: 1, sorbent material dosage counts 1 ~ 45mg/L with manganese.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 8000: 1, sorbent material dosage counts 1 ~ 40mg/L with manganese.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 6000: 1, sorbent material dosage counts 1 ~ 30mg/L with manganese.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 5000: 1, sorbent material dosage counts 1 ~ 30mg/L with manganese.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 3000: 1, sorbent material dosage counts 1 ~ 25mg/L with manganese.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 2000: 1, sorbent material dosage counts 1 ~ 20mg/L with manganese.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 1000: 1, sorbent material dosage counts 1 ~ 20mg/L with manganese.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 800: 1, sorbent material dosage counts 1 ~ 15mg/L with manganese.Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 600: 1, sorbent material dosage counts 1 ~ 15mg/L with manganese.Other step and parameter identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 10 ~ 500: 1, sorbent material dosage counts 1 ~ 10mg/L with manganese.Other step and parameter identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 100 ~ 400: 1, sorbent material dosage counts 1 ~ 8mg/L with manganese.Other step and parameter identical with one of embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 200 ~ 400: 1, sorbent material dosage counts 2 ~ 6mg/L with manganese.Other step and parameter identical with one of embodiment one to ten four.
Embodiment 16: one of present embodiment and embodiment one to ten five unlike: step one complexing agent is Sulfothiorine, and Sulfothiorine and Hg mol ratio 300: 1, sorbent material dosage counts 4mg/L with manganese.Other step and parameter identical with one of embodiment one to ten five.
Embodiment 17: one of present embodiment and embodiment one to ten six unlike: with the speed stirring reaction 2 ~ 30min of 120 ~ 300r/min in step one, obtain mixing solutions.Other step and parameter identical with one of embodiment one to ten six.
Embodiment 18: one of present embodiment and embodiment one to ten seven unlike: with the speed stirring reaction 15min of 250r/min in step one, obtain mixing solutions.Other step and parameter identical with one of embodiment one to ten seven.
Embodiment 19: one of present embodiment and embodiment one to ten eight unlike: in step 2, coagulating agent is Tai-Ace S 150, polymerize aluminum chloride, iron(ic) chloride or ferric sulfate.Other step and parameter identical with one of embodiment one to ten eight.
Embodiment 20: one of present embodiment and embodiment one to ten nine unlike: in step one, nascent state ferrimanganic is permanganate oxidation ferrous sulfate or iron protochloride gained solid matter; Nanometer nascent state manganese is permanganate oxidation manganous sulfate, Manganous chloride tetrahydrate, Sulfothiorine or S-WAT gained solid matter.Other step and parameter identical with one of embodiment one to ten nine.
Beneficial effect of the present invention is verified by following examples:
Embodiment 1:
The one strengthening Mn oxide of the present embodiment removes the method for the complexing agent of Hg (II) in water, realize according to the following steps: one, add complexing agent A to containing in Hg (II) water, add adsorbent B again, then with the speed stirring reaction 40min of 250r/min, mixing solutions is obtained; Two, to dosing coagulant in step one gained mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, namely complete in-situ preparation nascent state nano-manganese dioxide and thoroughly remove Hg in water (II);
Wherein the mol ratio of step one complexing agent A and Hg is 300: 1, and sorbent material dosage counts 4mg/L with manganese; Step one complexing agent A is Sulfothiorine, and adsorbent B is nascent state ferrimanganic; In step 2, the dosage of coagulating agent is 10mg/L.
Adsorbent B described in the present embodiment is the solid matter of nascent state ferrimanganic.
The present embodiment step one is 30 μ g/L containing the content of Hg (II) in Hg (II) water; In step 2, coagulating agent is polymerize aluminum chloride.
The present embodiment situ generates nascent state nano-manganese dioxide and thoroughly removes Hg in water (II), and after testing, the efficiency removing Hg (II) in water is 99.9%.
Embodiment 2:
The one strengthening Mn oxide of the present embodiment removes the method for the complexing agent of Hg (II) in water, realize according to the following steps: one, to containing Hg (II) water complexing agent A, add sorbent material C again, then with the speed stirring reaction 15min of 250r/min, obtain mixing solutions; Two, to dosing coagulant in step one gained mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, namely complete in-situ preparation nascent state nano-manganese dioxide and thoroughly remove Hg in water (II);
Wherein the mol ratio of step one complexing agent A and Hg is 300: 1, and sorbent material dosage counts 4mg/L with manganese; Step one complexing agent A is Sulfothiorine, and sorbent material C is nascent state manganese; In step 2, the dosage of coagulating agent is 10mg/L.
The present embodiment step one is 30 μ g/L containing the content of Hg (II) in Hg (II) water; In step 2, coagulating agent is polymerize aluminum chloride.
Adsorbent B described in the present embodiment is the solid matter of nascent state manganese.
The present embodiment situ generates nascent state nano-manganese dioxide and thoroughly removes Hg in water (II), and after testing, as shown in Figure 1, the visible efficiency removing Hg (II) in water is 99.99% to result, and mercury residual concentration is lower than 1 μ g/L.
Claims (6)
1. strengthen the method that Mn oxide removes the complexing agent of Hg (II) in water for one kind, it is characterized in that strengthening the method that Mn oxide thoroughly removes Hg in water (II) to realize according to the following steps: one, add complexing agent to containing in Hg (II) water, add sorbent material again, then with the speed stirring reaction 1 ~ 60min of 100 ~ 350r/min, mixing solutions is obtained; Two, to dosing coagulant in step one gained mixing solutions, then successively after conventional water treatment process coagulation, filtration, precipitation and clarification, the complexing agent that strengthening Mn oxide removes Hg (II) in water is namely completed;
Wherein in step 2, the dosage of coagulating agent is 10mg/L;
Step one complexing agent is Sulfothiorine, Sulfothiorine and Hg mol ratio 10 ~ 5000: 1, and sorbent material dosage counts 1 ~ 30mg/L with manganese;
Sorbent material described in step one is nascent state ferrimanganic or nanometer nascent state manganese;
In step one, nascent state ferrimanganic is permanganate oxidation ferrous sulfate or iron protochloride gained solid matter; Nanometer nascent state manganese is permanganate oxidation manganous sulfate, Manganous chloride tetrahydrate, Sulfothiorine or S-WAT gained solid matter.
2. one strengthening Mn oxide according to claim 1 removes the method for the complexing agent of Hg (II) in water, it is characterized in that step one complexing agent is Sulfothiorine, Sulfothiorine and Hg mol ratio 10 ~ 1000: 1, sorbent material dosage counts 1 ~ 20mg/L with manganese.
3. one strengthening Mn oxide according to claim 2 removes the method for the complexing agent of Hg (II) in water, it is characterized in that step one complexing agent is Sulfothiorine, Sulfothiorine and Hg mol ratio 10 ~ 500: 1, sorbent material dosage counts 1 ~ 10mg/L with manganese.
4. one strengthening Mn oxide according to claim 1 removes the method for the complexing agent of Hg (II) in water, to it is characterized in that in step one, with the speed stirring reaction 2 ~ 30min of 120 ~ 300r/min, obtaining mixing solutions.
5. one strengthening Mn oxide according to claim 1 removes the method for the complexing agent of Hg (II) in water, to it is characterized in that in step one, with the speed stirring reaction 15min of 250r/min, obtaining mixing solutions.
6. one strengthening Mn oxide according to claim 1 removes the method for the complexing agent of Hg (II) in water, it is characterized in that in step 2, coagulating agent is Tai-Ace S 150, polymerize aluminum chloride, iron(ic) chloride or ferric sulfate.
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| CN102502915A (en) * | 2011-12-31 | 2012-06-20 | 哈尔滨工业大学 | Method for thoroughly removing Hg(II) in water by virtue of in situ generation of new ecological nano manganese dioxide |
| CN103249814A (en) * | 2010-11-19 | 2013-08-14 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
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| CN103249814A (en) * | 2010-11-19 | 2013-08-14 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| CN102502915A (en) * | 2011-12-31 | 2012-06-20 | 哈尔滨工业大学 | Method for thoroughly removing Hg(II) in water by virtue of in situ generation of new ecological nano manganese dioxide |
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