CN101786713A - Emergency restoring process for pollution of water body, substrate sludge and mud flat by heavy metal - Google Patents
Emergency restoring process for pollution of water body, substrate sludge and mud flat by heavy metal Download PDFInfo
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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 mutually and dispersion, enrichment process (i.e. migration).The characteristics of heavy metal contamination are: (1) small part is dissolved in the water, and is most of except that being taken away by suspended substance, can be enriched near the sewage draining exit the bed mud because of effects such as adsorption precipitation hydrolysis, becomes secular secondary pollution source.(2) meeting of various inorganic ligands (chlorion, 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 entering bed mud may discharge again again.(3) the valence state difference of heavy metal, 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 sodium borohydride, 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 ion-exchange or adsorption coprecipitation, catch with resin or natural mineral (as 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 (as gypsum/magnesite method as described in the patent of invention CN101274794), 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 restoration heavy metal method---utilize animal, higher plant, the microbial enrichment heavy metal is removed then.This technical costs is cheap, but but be subjected to 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 restoration method is handled slowly, the scope of application is subjected to 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 as follows:
The first step, in contaminated by heavy metals water body, drop into complexing agent in advance, consumption is that calcium, magnesium ion and heavy metal ion all by the 1-5 of the Theoretical Calculation amount of complexing agent complexing doubly are converted into the solubilised state 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, magnesium 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, drop into the aluminium salt of water body weight 0.01%～0.5% or molysite or magnesium salts flocculation agent then it is flocculated, this moment, unnecessary heavy metal chelating agent also was converted into the precipitation 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 polyacrylamide, 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 magnetic substance and magnesium powder in advance and stir mill, make Mg/ magneticsubstance matrix material, 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 flocs unit catch bubble floating to the water surface, its consumption is decided according to the actual requirements, 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 finish emergent the reparation.Remaining under water Mg/ magneticsubstance matrix material can be caught with magnet and be reclaimed, and does not need to reclaim also passable; When not needing to catch, also can use Mg/ sand matrix material for reducing cost.
Above-mentioned complexing agent is preferentially selected citric acid, poly aspartic acid, glycine, lactic acid, oxysuccinic acid, NTA-3Na or EDDS biodegradable complexing agent classes such as (ethylenediamine disuccinic acid), also can use HEDPA (hydroxy ethylene diphosphonic acid) and EDTA carboxylic Ammonias such as (disodium ethylene diamine tetraacetate) to be difficult for biodegradable complexing agent when less demanding.
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 on iron powder, the magnetite.
After adopting such scheme, the present invention by complexing reach whole water body purification before make demands, in water body, produce a large amount of hydrogen microbubbles by 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, will float to the water surface on the fiber reinforcement flocs unit, fish for flocs unit and promptly reach the emergent purifying functions of repairing.
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 does not need to 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 substantially 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, having solved the general air supporting in present countries in the world first fishes for, the magnetic kind is fished for, and fine-structure mesh such as fishes at the unavoidable technical bottleneck of technology---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, a large amount of fragmentations in the time of can being broken up by stormy waves or collect and be difficult to effective collection.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.
Catch recovery as not needing that foaming agent is carried out magnetic, 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 restoration method to handle slowly, the scope of application is subjected to 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 standby, 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 citric acid 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 enter 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 (polyacrylamide) 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 will float 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 that use fiber reinforcement/air-float technology is arranged, discovery greater than 95% flocs unit come-up and do not dispelled substantially 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 substantially and are difficult to measure, and the result shows that whole water body is effectively repaired.
As changing citric acid into glycine, to assist to make water body that sufficient dissolved oxygen be 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 standby, 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 not to need to regulate the pH value with lime) with lime then.Produce a large amount of magnesium hydroxide flocs units in the water and catch various suspended substances in the water this moment.
Stir mill with cast iron filing and magnesium powder, making 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 substantially, bed mud lead content 13mg/l, the demonstration water body is repaired.
Embodiment 3
At somewhere, blood clam river, gulf, Quanzhou beach mud sample, record copper content 331mg/l, 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 substantially 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 sample 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-precipitation 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, enter 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 as follows:
The first step, in contaminated by heavy metals water body, drop into complexing agent in advance, consumption is that calcium, magnesium ion and heavy metal ion all by the 1-5 of the Theoretical Calculation amount of complexing agent complexing doubly are converted into the solubilised state 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, magnesium 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, drop into the aluminium salt of water body weight 0.01%～0.5% or molysite or magnesium salts flocculation agent then it is flocculated, 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 magnetite or other ferromagnetic materials and the mixing of magnesium powder, make Mg/ magneticsubstance matrix material, 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 flocs unit catch behind the bubble progressively compression and on float to the water surface, its consumption is decided according to the actual requirements, 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 can be few more;
The 5th step, fish for the fiber reinforcement flocs unit, promptly finish 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 biodegradable complexing agent classes such as citric acid, poly aspartic acid, glycine, lactic acid, oxysuccinic acid, NTA-3Na or EDDS, uses carboxylic Ammonias such as HEDPA and EDTA to be difficult for biodegradable complexing agent when less demanding.
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 on iron powder, the magnetite, or adopts spraying plating, CVD (Chemical Vapor Deposition) 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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