CN101786713B - Emergency restoring process for pollution of water body, substrate sludge and tidal flat by heavy metal - Google Patents
Emergency restoring process for pollution of water body, substrate sludge and tidal flat by heavy metal Download PDFInfo
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- CN101786713B CN101786713B CN2010101215430A CN201010121543A CN101786713B CN 101786713 B CN101786713 B CN 101786713B CN 2010101215430 A CN2010101215430 A CN 2010101215430A CN 201010121543 A CN201010121543 A CN 201010121543A CN 101786713 B CN101786713 B CN 101786713B
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Abstract
The invention discloses an emergency restoring process for pollution of a water body, substrate sludge and a mud flat by heavy metal. A complex agent is first added to the water body, and most heavy metal ions in ionized and absorbed states are converted into dissolved complex ions; short fibers and a heavy metal capturing agent are added to the water body so as to convert the heavy metal complex ions into suspended matters, and then a flocculating agent is added to flocculate the suspended matters; a flocculation assisting agent is added to the water body to form a fiber enhanced flocculating body; an Mg/magnetic composite material prepared by magnetic substances and magnesium powder in advance is thrown into the water body so as to lead the fiber enhanced flocculating body to capture air bubbles and float to the water surface; finally, the fiber enhanced flocculating body is captured to carry out emergency restoration. The emergency restoring process is convenient for in-situ emergency restoration of the stormy wavy water body in a large scale, so as to avoid the disadvantages that the present biological restoring method leads to slow treatment and is limited by the biological living environment in the aspect of the application range, thereby not only solving the problem of secondary sedimentation pollution caused by the present chemical restoring method, but also solving the bottleneck problem that the present dissolved air floatation process cannot carry out entire water-area pipe laying operation.
Description
Technical field
The present invention relates to the emergency repair process of a kind of heavy metal-polluted water, bed mud and beach.
Technical background
Heavy metal, particularly mercury, cadmium, lead, chromium etc. have significantly and bio-toxicity.They can not be degraded by microorganisms in water body, and can only take place that various forms transform each other and dispersion, enrichment process (i.e. migration).The characteristics of heavy metal contamination are: (1) is partially dissolved in the water less, and is most of except that being taken away by suspended substance, can be enriched near the bed mud the sewage draining exit because of effects such as adsorption precipitation hydrolysis, becomes secular secondary pollution source.(2) meeting of various inorganic ligands (cl ions, sulfate ion, hydroxide ion etc.) and organic ligand (matter etc. is planted in corruption) and its generation complex compound or inner complex in the water, the heavy metal that causes getting into bed mud possibly discharge again again.(3) valence state of heavy metal is different, and they are active different with toxicity; Its form transforms with pH and redox condition again.
The heavy metal pollution of water body repairing and treating adopts following two Basic Ways, and the one, reduce the transfer ability and the bioavailability of heavy metal in water body; The 2nd, heavy metal is thoroughly removed from contaminated water body.
Present treatment process mainly contains:
(1) coagulant sedimentation---with chemical agent heavy metal being precipitated, is the general main emergency processing method of natural water body heavy metal contamination of Environmental Protection in China circle.Problem is that the heavy metal precipitation thing can not remove from water, just slowed down the degree of polluting, and it is transferred in the bed mud, and the use nanometer iron reduction that environmental protection circle is recently paid close attention to is repaired the water body weight alloying technology and also had the problems referred to above.
(2) ion reduction method---for example use the heavy metal ion in the direct reductive water of Peng Qinghuana, utilize its hydrogen that decomposites and PAC acting in conjunction to emerge.The bed mud heavy metal ion directly is reduced into metallic state and is lost poison.The method of thunderously few admire, Chen Kaihan delivering at " chemical pollution and control " periodical in 2009.The defective not anti-stormy waves of flocs unit that is to float impacts, and has potential heavy metal simple substance such as mercury evaporable problem, and is not perfect.
(3) ionic adsorption and exchange process---be the principle of utilizing IX or adsorption coprecipitation, catch with resin or natural mineral (like zeolite, gypsum/magnesite).This type of technology is fine to the heavy metal ion treatment effect that is free in the water, and the technology that has can be held concurrently and handle suspended state heavy metal ion (like the said gypsum of patent of invention CN101274794/magnesite method), but can't handle bed mud.
(4) electromigration remediating heavy metal ion method---utilize heavy metal ion in the electric field migration enrichment, be fit to heavy metal processing in water and the suspended substance, but efficient is low, electric field is serious to the water body biological hazard.
(5) biological prosthetic heavy metal method---utilize animal, higher plant, the microbial enrichment heavy metal is removed then.This technical costs is cheap, but but receive the restriction of biology living environment, and treatment effect is very slow.
Summary of the invention
The object of the present invention is to provide the emergency repair process of a kind of heavy metal-polluted water, bed mud and beach; So that carry out the emergent reparation of original position on a large scale; Avoid the defective that existing biological prosthetic method is handled slowly, the scope of application receives the habitable environment restriction, solve existing chemical repairing method and cause secondary pollution problem.
In order to reach above-mentioned purpose, solution of the present invention is:
The emergency repair process of heavy metal-polluted water, bed mud and beach, its step is following:
The first step; In contaminated by heavy metals water body, drop into complexing agent in advance; Consumption is that calcium, mg ion and heavy metal ion all by the 1-5 of the Theoretical Calculation amount of complexing agent complexing doubly are converted into the The dissolved complexing ion with fixed free state in water body suspended substance and the bed mud and ADSORPTION STATE heavy metal ion major part in the hypothesis water body;
Second step; After carrying out 1～72 hour complexing stripping; Drop into the staple fibre of water body weight 0.005～1% earlier; Drop into excessive heavy metal chelating agent again, consumption be in the hypothesis water body calcium, mg ion and heavy metal complexing ion all be captured the sedimentary Theoretical Calculation amount of agent 1-5 doubly, the heavy metal complexing ion is converted into suspended substance; Aluminium salt or the molysite or the magnesium salts flocculation agent that drop into water body weight 0.01%～0.5% then flocculate it, and this moment, unnecessary heavy metal chelating agent also was converted into the deposition flocculation simultaneously;
The 3rd step; Add in water body that to help wadding agent, consumption be water body weight 0.001～0.2%, kind can select conventional commerce such as SEPIGEL 305, microbial flocculant or chitosan to help the wadding agent; Drop into again after helping wadding agent water in advance to disperse, form the fiber reinforcement flocs unit in the water this moment;
The 4th step; Mix with magnetisable material and magnesium powder in advance and stir mill; Make Mg/ magnetic material composite; To generate hydrogen gas bubbles with water in its input water body; When making time is chosen in step 3 enforcement or after the step 3 enforcement; Make the fiber reinforcement floccule body catch bubble floating to the water surface, its consumption is decided based on actual needs, and selecting usually is that conversion is the 0.001%-0.05% of water body total amount for the amount of magnesium;
The 5th step, fish for the fiber reinforcement flocs unit, promptly accomplish emergent the reparation.Remaining under water Mg/ magneticsubstance matrix material can be caught with magnet and reclaimed, and need not reclaim also passable; In the time need not catching, also can use Mg/ sand matrix material for reducing cost.
Above-mentioned complexing agent is preferentially selected Hydrocerol A, SAP 73, glycocoll, lactic acid, oxysuccinic acid, NTA-3Na or EDDS biodegradable complexing agent classes such as (EDDSs), when less demanding, also can use HEDPA (hydroxy ethylene diphosphonic acid) and EDTA carboxylic Ammonias such as (EDTA Disodiums) to be difficult for biodegradable complexing agent.
Above-mentioned heavy metal chelating agent is the commercialization heavy metal chelating agent of Na3T-15, DTCR or insoluble starch xanthogenic acid magnesium sodium and so on.
Above-mentioned magneticsubstance is magnetite or iron filings.
The method that above-mentioned Mg/ magneticsubstance matrix material grinds except available stirring also can adopt methods such as spraying plating or vapour deposition to produce being compound to MAGNESIUM METAL 99 on iron powder, the magnetite.
After adopting such scheme, the present invention through complexing reach whole water body purification before make demands, in water body, produce a large amount of hydrogen microbubbles through Mg/ magneticsubstance matrix material with the water reaction, produce Mg (OH) simultaneously
2Stablize water pH value, this air supporting medicament and staple fibre, flocculation agent, help wadding agent acting in conjunction,, fish for flocs unit and promptly reach the emergent purifying functions of repairing floating to the water surface on the fiber reinforcement flocs unit.
Air supporting matrix material among the present invention is nontoxic, but magnetic is caught recovery and used where necessary.Use the advantage of Mg/ magneticsubstance matrix material to be: the airfloat equipment that need not install and use trouble; Available method of broadcasting sowing directly produces the air supporting function; Reduced cost significantly, also can use at the too late water body from far-off regions of electric power, but also commercial production deposit.
The present invention is at 1m
3In the pilot experiment of volume, handle copper staining water body and bed mud, adopt the eddy oscillating device to be put in the wave that shakes in the water with plastics bag; And with hair dryer adjoined water surface simulation wind-force, the water body of use fiber reinforcement/air-float technology is arranged, find greater than 95% flocs unit come-up and do not dispelled basically in 8 hours by stormy waves heavy; Available mesh screen is fished for; Do not use the water body of fiber reinforcement/air-float technology, mesh screen is caught 10% of flocs unit quantity not sufficient total amount, and the Mg/ magnetic composite can be fished for recovery with magnet.
Characteristics of the present invention be to use the Mg/ magnetic composite as the pH value stabilization agent foaming agent of holding concurrently; But big area is broadcasted sowing; On vast waters, purify simultaneously; Solved the general air supporting in present countries in the world first and fished for, the magnetic kind is fished for, and fine-structure mesh such as fishes at technological unavoidable technical bottleneck---and cause fishing for the drainage flow of not fished for again in the waters after the cleaning and pollute because of can't big area using; Having adopted flocs unit fiber reinforcement/air flotation technology simultaneously, solved another technical bottleneck of present puzzlement water body recovery technique first---pollutent flocs unit come-up back intensity is too low, can be broken up or a large amount of fragmentations and be difficult to effective collection when collecting by stormy waves.Look into rope on all not various as yet at present documents of these two technical solutions at home and abroad and arrive, in addition, complexing-precipitation transformation method generally is used for the synthetic of matrix material at present, and combination is not also looked into rope on the document at home and abroad as the treatment of heavy metal polluted water body technique and arrived.
As need not carry out magnetic and catch recovery foaming agent; The solid particulate (conventional sandstone mineral, pottery, metal) of then available magnesium powder and routine etc. carries out compound; Wherein the material raising rate with metal composite increases owing to having generated the galvanic cell effect; With the obvious advantage when requiring quick air supporting, but for example have both the function that high speed is got angry and magnetic is caught with cheap magnesium/iron composite material.
The advantage of this invention is and can carries out the emergent reparation of original position on a large scale to heavy metal-polluted water, bed mud and beach etc. that avoided existing biological prosthetic method to handle slowly, the scope of application receives the defective of habitable environment restriction; Solve existing chemical repairing method and caused secondary pollution problem.
Embodiment
Embodiment 1
Muddiness band mud river with copper sulfate 20g and sampling is configured to simulate heavy metal-polluted water 1000L, place 72 hours subsequent use, the water body bottom have thicker mud layer with the simulation bed mud.Record the about 2mg/l of free copper content in the water after the filtration.The about 61mg/l of copper content in the suspended substance, bed mud copper contains 135mg/l.
Adopt the eddy oscillating device to be put in the wave that shakes in the water, in water body, add Hydrocerol A 100 grams earlier, preserve 24h, make the cupric ion that is adsorbed on water body suspended impurity and the bed mud be converted into the citric acid complex cupric ion and get in the water with plastics bag.The aqueous dispersions that adds rock wool fibers 0.05-0.1% (water gross weight) then; Amount according to 5 times of copper mole numbers drops into Na3T-15 (a kind of heavy metal chelating agent; Korea S open country KCC produces) make complex copper ion be converted into small brown suspended substance, the bodied ferric sulfate that drops into water body amount 0.05% after 10 minutes flocculates.
Get PAM (SEPIGEL 305) 0.01% in advance with water-dispersion, add then in the entry, generate a large amount of large-scale fiber reinforcement flocs units this moment in the water.
Stir mill with iron ore and the mixing of magnesium powder, make Mg/Fe
3O
4Matrix material also drops into it in water.This moment, matrix material produced a large amount of hydrogen microbubbles with the water reaction in water, produced Mg (OH) simultaneously
2Stablize water pH value.This air supporting medicament is with floating to the water surface on the flocs unit.
At above-mentioned 1m
3The pilot scale of volume; With hair dryer adjoined water surface simulation wind-force, the water body of use fiber reinforcement/air-float technology is arranged, find greater than 95% flocs unit come-up and do not dispelled basically in 8 hours by stormy waves heavy; Available mesh screen is fished for; Do not use the water body of fiber reinforcement/air-float technology, mesh screen is caught 10% of flocs unit quantity not sufficient total amount, Mg/Fe
3O
4Matrix material can be fished for recovery with magnet.
Record after the processing that free copper content is lower than 0.5mg/l in the water, bed mud copper content 59.3mg/l, suspended substance disappear basically and are difficult to measure, and the result shows that whole water body is by effective reparation.
As changing Hydrocerol A into glycocoll, to assist to make water body that sufficient dissolved oxygen arranged to press close to the bed mud aeration, all the other conditions are identical, and free copper content is lower than 0.5mg/l, bed mud copper content 13.2mg/l in the water of processing back.The existence that sulfonium ion in the bed mud is described can suppress the heavy metal stripping, and the ability of the bed mud of strong complex reparation simultaneously is better.
Embodiment 2
Be configured to simulate heavy metal-polluted water 1000L with lead sulfate 6g and muddy seawater, with the fish jar aerator pump keep the aeration state place 72 hours subsequent use, record the free about 2.3mg/l of lead content in the water after the filtration, leaded 35mg/l in the suspended substance, the leaded about 17g/l of bed mud.
In water body, drop into EDTA100g, stir 0.5h dissolving back and preserved 24 hours, add aluminosilicate glass fiber 0.2% then earlier, drop into excessive Tong Shiji (heavy metal chelating agent) (C again
5H
10NaS
23H
2O) make complexing lead be converted into the white suspension thing, directly in seawater, add the bittern of weight 0.5% after 30 minutes, get cationic PAM 0.02% in advance and water-dispersion, drop in the water.Regulate pH to 11 (this embodiment also can use molysite and aluminium salt, uses molysite or aluminium salt need not regulate the pH value with lime) with lime then.Produce a large amount of Marinco H flocs units in the water and catch various suspended substances in the water this moment.
Stir mill with cast iron filing and magnesium powder; Processing the Mg/Fe matrix material drops in the water; Flocs unit floated to the water surface on all and can fish in the water body in 1 hour, and water quality is very limpid, the come-up flocs unit can the disturbance of anti-water body aeration and hair dryer pressed close to blowing 6 hours and not broken sinking.
Handle the back water pH value and slowly fall back 8.5-9, (the also available method that adds acid is directly regulated back and is lower than 9), measure the about 0.1mg/l of lead content in the water body, suspended substance disappears basically, bed mud lead content 13mg/l, the demonstration water body is repaired.
Embodiment 3
The beach mud appearance in somewhere, blood clam river, gulf, Quanzhou records copper content 331mg/l, and lead contains 35mg/l, sulfonium ion 217mg/l.Be that the beach of 3*3 rice inserts in the mud of beach with plastic film and rod and surrounds as repair coverage to area.
At first on the beach mud layer, step on the hole, the about deeply 30cm in hole, the about 200cm of hole area
2, every square metre of about 9 holes.In surrounding scope, drop into seawater and make it not have beach 10cm approximately, add the sulfonium ion in 2 kilograms of oxidized sludges of hydrogen peroxide in the water in batches.Flood that bubble disappears basically after 0.5 hour, begin the water of offeing medicine this moment.The liquid medicine consumption, kind is identical with embodiment 2 except the bracket content with operation.(EDTA solution does not stir after adding, and only keeps promptly beginning to drop in 2 hours Tong Shiji)
Handle beach surface, back mud appearance and record copper content 10.9mg/l, lead content 11mg/l.Sulfonium ion can not detect.The dark sampling of 50cm records copper content 182.9mg/l, lead content 21mg/l, sulfonium ion 83mg/l under the beach plane.
Test confirms that complexing-deposition conversion process can carry out the beach reparation.If do not take the method for this direct impregnation, make it slowly settlement separate and beach mud layer and complexing agent liquid medicine direct mechanical stirred, can remove the total metals more than 85% in the lab scale.In view of the above experiment judge this beach restorative procedure also portable in the reparation of general mining area heavy-metal contaminated soil; But need squeeze into gas in the depth of soils and keep certain air pressure; Add liquid medicine dipping back again with this technology removing heavy metals, get into the deep soil polluted underground water because of strong excessively wicking action in order to avoid repair medicament.
Claims (5)
1. the emergency repair process of heavy metal-polluted water, bed mud and beach is characterized in that step is following:
The first step; In contaminated by heavy metals water body, drop into complexing agent in advance; Consumption is that calcium, mg ion and heavy metal ion all by the 1-5 of the Theoretical Calculation amount of complexing agent complexing doubly are converted into the The dissolved complexing ion with fixed free state in water body suspended substance and the bed mud and ADSORPTION STATE heavy metal ion major part in the hypothesis water body;
Second step; After carrying out 1～72 hour complexing stripping; Drop into the staple fibre of water body weight 0.005～1% earlier; Drop into excessive heavy metal chelating agent again, consumption be in the hypothesis water body calcium, mg ion and heavy metal complexing ion all be captured the sedimentary Theoretical Calculation amount of agent 1-5 doubly, the heavy metal complexing ion is converted into suspended substance; Aluminium salt or the molysite or the magnesium salts flocculation agent that drop into water body weight 0.01%～0.5% then flocculate it, and this moment, unnecessary heavy metal chelating agent also was converted into flocs unit simultaneously;
The 3rd step added in water body and helps the wadding agent, and consumption is a water body weight 0.001～0.2%, dropped into after helping wadding agent water in advance to disperse again, and formed the fiber reinforcement flocs unit in the water this moment;
The 4th step; In advance with magnetic iron ore or other ferromagnetic materials and the mixing of magnesium powder; Make Mg/ magnetic material composite; To generate hydrogen gas bubbles with water in its input water body; After making time is chosen in step 3 when implementing or step 3 implements, make the fiber reinforcement floccule body catch behind the bubble progressively compression and on float to the water surface, its consumption is decided based on actual needs; Usually selecting is that conversion is the 0.001%-0.05% of water body total amount for the amount of magnesium, and the more little consumption of stormy waves is few more;
The 5th step, fish for the fiber reinforcement flocs unit, promptly accomplish emergent the reparation.
2. the emergency repair process of heavy metal-polluted water as claimed in claim 1, bed mud and beach; It is characterized in that: above-mentioned complexing agent is selected Hydrocerol A, SAP 73, glycocoll, lactic acid, oxysuccinic acid, NTA-3Na or the EDDS of biodegradable complexing agent class, when less demanding, uses the carboxylic Ammonia to be difficult for biodegradable complexing agent HEDPA and EDTA.
3. the emergency repair process of heavy metal-polluted water as claimed in claim 1, bed mud and beach is characterized in that: above-mentioned heavy metal chelating agent is the commercialization heavy metal chelating agent of Na3T-15, DTCR or insoluble starch xanthogenic acid magnesium sodium and so on.
4. the emergency repair process of heavy metal-polluted water as claimed in claim 1, bed mud and beach; It is characterized in that: the method that above-mentioned Mg/ magneticsubstance composite material by adopting stirs mill is compound to MAGNESIUM METAL 99 on iron powder, the magnetite, or adopts spraying plating, CVD method to produce.
5. the emergency repair process of heavy metal-polluted water as claimed in claim 1, bed mud and beach is characterized in that: above-mentioned magneticsubstance is magnetite or iron filings.
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| CN2010101215430A CN101786713B (en) | 2010-03-05 | 2010-03-05 | Emergency restoring process for pollution of water body, substrate sludge and tidal flat by heavy metal |
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| CN2010101215430A CN101786713B (en) | 2010-03-05 | 2010-03-05 | Emergency restoring process for pollution of water body, substrate sludge and tidal flat by heavy metal |
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| CN101786713B true CN101786713B (en) | 2012-01-11 |
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| CN100551840C (en) * | 2007-11-06 | 2009-10-21 | 苏州市普林生态环境经济研究所 | The purifying treatment method of natural water |
| CN101274794B (en) * | 2008-04-24 | 2010-12-29 | 泉州师范学院 | Fast no-damage method for rehabilitating heavy metal-polluted water |
| CN101306847B (en) * | 2008-07-02 | 2011-03-02 | 泉州师范学院 | Emergency repairing method for natural water body by self-air-float method |
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