CN103357655B - A kind of composite chemical ELUTION METHOD for restoration of soil polluted by heavy metal - Google Patents
A kind of composite chemical ELUTION METHOD for restoration of soil polluted by heavy metal Download PDFInfo
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Abstract
The invention discloses a kind of composite chemical ELUTION METHOD for restoration of soil polluted by heavy metal, the compound leacheate drip washing heavy-metal contaminated soil adopting iron chloride and organic acid configuration to obtain 1 ~ 3 time, then continue drip washing 1 ~ 3 time with distilled water, finally leacheate is separated with soil.Treatment effect of the present invention is good, the drip washing time is short, non-secondary pollution, simple to operate, advantage of lower cost, and cadmium clearance can reach more than 80%, and plumbous more than 55%.In the present invention, iron containing compounds is used as the modifying agent of paddy soil in some countries, and the residue of iron chloride produces actively impact to the chemical property of soil, can not spoiled soil structure; The organic acid used easily is degraded, and catabolite can become the nutriment of plant, environmentally friendly; Finally use water wash, to reduce after repairing the content of metal ion and the residual quantity of leacheate in soil, being conducive to the later stage cultivates crop.<!--1-->
Description
Technical field
The present invention relates to heavy metal pollution of soil Treatment process, be specifically related to a kind of chemical leaching method for restoration of soil polluted by heavy metal.
Background technology
In decades recently, industrialization, urbanization process are constantly accelerated, and soil contamination problem becomes increasingly conspicuous, and the chemical plant in urban district, original place or suburbs is moved successively, and it includes physical construction planning in leaving over is inexorable trend.Industrial production activities result in the enrichment of high concentration heavy metal in place, chemical plant, and to underground water and neighbouring area diffusion, is the agricultural production of periphery and the huge hidden danger of resident living.The features such as heavy metal has residence time length, disguise is strong, toxicity is large can not be microbial degradation, once namely entered environment starts accumulation, with airborne dust exposure or food chain transmission threat health.Therefore, to the chemical plant resettlement Site development recycling left over, reparation and the regulation of contaminated soil must be carried out.At present, the restorative procedure of heavy-metal contaminated soil mainly comprises peripheral doses, chemical redemption and the method such as biological prosthetic.Compared with other restorative procedures, chemical repair method has stable treatment effect, the advantage such as thorough, and Soil leaching is effective chemical repair method.Soil leaching technology typically refers to by soil pollutant being promoted to dissolve the liquid of migration or other fluids carry out drip washing contaminated soil, makes absorption or be fixed on pollutant desorption on soil particle to dissolve and the technology removed.Pollutant not only can remove by Soil leaching fast from soil, the improvement of high density pollution soil is completed in short time, and control expense is relatively cheap, be particularly useful for the improvement of severe, small size contaminated soil, now become one of contaminated soil fast repair technique Main Means, abroad existing successful engineer applied, earth elution method carrys out drip washing contaminated soil with leacheate, make absorption or be fixed on the heavy metal dissolving on soil particle, then reclaim leacheate and recycle.The method of drip washing and leaching is better for the repairing effect in the area of small size, heavy metal severe contamination.First large-scale Soil leaching project completes in October, 1992 at New Jersey.According to the report of EPA in 2000, what in the site remediation new and high technology demonstration project of more than 600 government-fundeds, have the project of 4.2% to adopt is exactly Soil leaching technology.Elution method can take original position or dystopy mode of operation neatly, has bright application prospect.The key technology of drip washing reparation selects or develop pouring agent and the ELUTION METHOD of pointed strong, environmental friendliness, advantage of lower cost and non-secondary pollution, formulates cost-effective renovation technique program.
The eluent of current use mainly contains chelating agent, organic acid, organic acid, inorganic acid, inorganic salts and organic acid etc.Simple a kind of eluent is comparatively large due to working concentration or acidity, to soil fail relatively seriously, or is difficult to reach drip washing effect, so compound eluent is developed gradually and uses.As chelating agent-inorganic salts, organic acid-inorganic acid, organic acid-organic acid compound, can mutual supplement with each other's advantages be reached, improve washout rate.
Summary of the invention
The object of the invention is to the above-mentioned deficiency for existing elution technique, overcome the existing method reagent cost being used alone the solution drip washing heavy-metal contaminated soils such as EDTA, organic acid, inorganic acid and inorganic salts large, produce secondary pollution, the difficult problem that large to soil fail, subsequent treatment is cumbersome, a kind of chemical leaching method for remediating heavy metal (cadmium, lead) contaminated soil is provided.
The object of the invention is to be achieved through the following technical solutions:
The compound leacheate drip washing heavy-metal contaminated soil that the present invention adopts iron chloride and organic acid configuration to obtain 1 ~ 3 time, then (test drip washing 3 heavy metal ion, iron chloride and organic acid residual quantity are smaller to continue drip washing 1 ~ 3 time with distilled water, increase number of times, cost increase does not have practical significance), finally leacheate is separated with soil.Described organic acid is the one in citric acid, malic acid, tartaric acid.The heavy metal that the present invention is directed to is cadmium, lead.
Wherein, in described compound leacheate, the concentration of iron chloride is 5 ~ 50mmol/L, and organic acid concentration is 20 ~ 300mmol/L; Preferably, in described compound leacheate, ferric chloride concn is 5 ~ 30mmol/L, and organic acid concentration is 20 ~ 150mmol/L; Preferred further, in described compound leacheate, ferric chloride concn is 10 ~ 30mmol/L, and organic acid concentration is 50 ~ 150mmol/L.
Adopt an ELUTION METHOD for compound eluent restoration of soil polluted by heavy metal, specifically comprise the steps:
(1), heavy-metal contaminated soil is levigate;
(2), the iron chloride that obtains is configured and organic acid compound leacheate mixes with the soil of step (1) porphyrize, constant temperature oscillation drip washing;
(3) the compound leacheate, through step (2) processed and the mixture of soil centrifugal, compound of inclining leacheate;
(4) soil, through step (3) processed adds the distilled water being equivalent to compound leacheate volume in step (2), constant temperature oscillation drip washing, the same step of temperature, time and oscillation rate (2), and centrifugal according to the method for step (3), incline supernatant; Repeat, with distilled water vibration drip washing 1 ~ 3 time, to obtain the soil repaired.
When heavy-metal contaminated soil particle diameter is excessive, before drip washing, heavy-metal contaminated soil is crushed to particle diameter and is less than 2cm.
In step (1), heavy-metal contaminated soil crosses 2mm sieve.
The compound leacheate volume added during drip washing in step (2) and the mass ratio of heavy-metal contaminated soil to be repaired are 1.5: 1 ~ 2.0: 1; The weight ratio larger drip washing drip washing effect of leacheate volume and soil is better, is less than 1.5 leacheates and is not easy to be separated, and is greater than 2.0 increase difficulty of construction and cost increase, therefore arranges 1.5: 1 ~ 2.0: 1.
In step (2), drip washing of vibrating in water bath with thermostatic control oscillator, drip washing temperature is 25 ~ 28 DEG C, and oscillation rate is 180 ~ 220 revs/min, vibrates 20 ~ 28 hours.
In step (3), centrifugation rate 4500 ~ 5500 revs/min, centrifugation time 3 ~ 8 minutes.
In step (4), drip washing of vibrating in water bath with thermostatic control oscillator, drip washing temperature is 25 ~ 28 DEG C, and oscillation rate is 180 ~ 220 revs/min, vibrates 20 ~ 28 hours; Centrifugation rate 4500 ~ 5500 revs/min, centrifugation time 3 ~ 8 minutes.
The present invention is used for the chemical leaching method of restoration of soil polluted by heavy metal, also comprises the wastewater treatment of iron chloride leacheate and organic acid compound leacheate and distilled water drip washing, the further utilization of soil after repairing; Described iron chloride leacheate and the waste water of organic acid compound leacheate and distilled water drip washing through acid treatment and alkaline sedimentation process, the restriction that content of beary metal reaches " integrated wastewater discharge standard "; After described reparation, heavy metal content in soil reaches the soil (namely available heavy metal content reaches national safety standard) of environmental protection standard, as required, adds N, P, K fertilizer.
In restorative procedure of the present invention, for the difference of heavy metal in soil content, certain adjustment can be carried out, when the content of beary metal in soil is higher to parameters such as the concentration of eluent, drip washing number of times, liquid-solid ratioes, increase concentration and the solid-liquid mass ratio of eluent, otherwise can suitably reduce.
Compared with prior art, the advantage that has of the present invention:
(1), the invention provides that a kind for the treatment of effect is good, the drip washing time is short, the chemical leaching method of non-secondary pollution, simple to operate, advantage of lower cost, Cadium In Polluted Soil clearance can reach more than 80%, plumbous more than 55%, overcome the existing method reagent cost being used alone the solution drip washing heavy-metal contaminated soils such as EDTA, organic acid, inorganic acid and inorganic salts large, produce secondary pollution, the difficult problem that, subsequent treatment large to soil fail is cumbersome;
(2), the present invention with ferric chloride solution and organic acid composition compound leacheate and distilled water for leached soil solutions, wherein iron containing compounds is used as the modifying agent of paddy soil in some countries, the residue of iron chloride produces actively impact to the chemical property of soil, can not spoiled soil structure; The organic acid used easily is degraded, and catabolite can become the nutriment of plant, environmentally friendly; Finally use distilled water drip washing, to reduce after repairing the content of metal ion and the residual quantity of leacheate in soil, being conducive to the later stage cultivates crop.
(3), iron chloride and organic acid compound leacheate in the present invention, relative low price; Compound drip washing, can reach the drip washing effect of higher concentration under low concentration, reduce the working concentration of eluent, reduces rehabilitation cost;
(4), ferric chloride solution selected by the present invention has good removal effect, remediation efficiency high to the cadmium in soil, lead, can cut down the features such as the heavy metal in soil;
(5), the present invention is suitable for original position drip washing and dystopy drip washing, and adopt general water pump and rotary cultivator or sprinkling equipment, save running cost, operation sequence is simple.
Detailed description of the invention
Below by way of case study on implementation, the invention will be further described, and unrestricted the present invention.
Embodiment 1
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take some parts of soil, 5 grams every part, be placed in centrifuge tube, every part adds and prepares by iron chloride and citric acid the compound leacheate 10mL obtained, and in every part of compound leacheate, the concentration of iron chloride and citric acid as shown in Table 1 and Table 2; Centrifuge tube is placed in constant temperature oscillator, and Non-leaching temperature is 25 DEG C, and oscillation rate is 200 revs/min, and vibration drip washing, after 24 hours, takes out centrifuge tube; Be placed in centrifuge, centrifugation 5 minutes under 5000 revs/min of speed, compound of inclining leacheate; In centrifuge tube, add distilled water 10mL again, drip washing temperature, oscillation rate and drip washing time are the same, then centrifugation 5 minutes under the speed of 5000 revs/min, and incline supernatant; With distilled water drip washing twice again under similarity condition, obtain the soil repaired.
Cd clearance (%) in table 1 lessivation
Pb clearance (%) in table 2 lessivation
After chemical leaching, the content of Cadmium in Soil can be reduced to 1.16mg/kg by original 6.68mg/kg at most, and the clearance of cadmium is up to 82.57%; Lead content can be reduced to 351.57mg/kg by original 787.76mg/kg at most, and plumbous clearance is up to 55.37%.Soil after drip washing reparation can reach " standard of soil environment quality " (revision) (exposure draft) (GB15618-2009) requirement.
Embodiment 2
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take some parts of soil, 5 grams every part, be placed in centrifuge tube, every part adds and prepares by iron chloride and citric acid the compound leacheate 10mL obtained, and in every part of compound leacheate, iron chloride and tartaric concentration are as shown in Table 3 and Table 4; Centrifuge tube is placed in constant temperature oscillator, and Non-leaching temperature is 25 DEG C, and oscillation rate is 200 revs/min, and vibration drip washing, after 24 hours, takes out centrifuge tube; Be placed in centrifuge, centrifugation 5 minutes under 5000 revs/min of speed, compound of inclining leacheate; In centrifuge tube, add distilled water 10mL again, drip washing temperature, oscillation rate and drip washing time are the same, then centrifugation 5 minutes under the speed of 5000 revs/min, and incline supernatant; With distilled water drip washing twice again under similarity condition, obtain the soil repaired.
Cd clearance (%) in table 3 lessivation
Pb clearance (%) in table 4 lessivation
After chemical leaching, the content of Cadmium in Soil can be reduced to 1.02mg/kg by original 6.68mg/kg at most, and the clearance of cadmium is up to 84.72%; Lead content can be reduced to 152.98mg/kg by original 787.76mg/kg at most, and plumbous clearance is up to 80.58%.Soil after drip washing reparation can reach " standard of soil environment quality " (revision) (exposure draft) (GB15618-2009) requirement.
Embodiment 3
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take some parts of soil, 5 grams every part, be placed in centrifuge tube, every part adds and prepares by iron chloride and malic acid the compound leacheate 10mL obtained, and in every part of compound leacheate, the concentration of iron chloride and malic acid as shown in table 5 and table 6; Other test method, with embodiment 1, obtains the soil repaired.
Cd clearance (%) in table 5 lessivation
Pb clearance (%) in table 6 lessivation
After chemical leaching, the content of Cadmium in Soil can be reduced to 1.28mg/kg by original 6.68mg/kg at most, and the clearance of cadmium is up to 80.81%; Lead content can be reduced to 353.70mg/kg by original 787.76mg/kg at most, and plumbous clearance is up to 55.10%.Soil after drip washing reparation can reach " standard of soil environment quality " (revision) (exposure draft) (GB15618-2009) requirement.
After the drip washing of 3 kinds of composite chemical eluents, the content of Cadmium in Soil can be reduced to 1.28mg/kg ~ 1.02mg/kg by original 6.68mg/kg at most respectively, and the clearance of cadmium is up to 80.81% ~ 84.72%; Lead content can be reduced to 353.70mg/kg ~ 152.98mg/kg by original 787.76mg/kg at most respectively, and plumbous clearance is up to 55.10% ~ 80.58%.Soil after drip washing reparation can reach " standard of soil environment quality " (revision) (exposure draft) (GB15618-2009) requirement.
Claims (5)
1. the chemical leaching method for restoration of soil polluted by heavy metal, the compound leacheate drip washing heavy-metal contaminated soil that it is characterized in that adopting iron chloride and organic acid to configure and obtain 1 ~ 3 time, then continue drip washing 1 ~ 3 time with distilled water, finally leacheate is separated with soil; Specifically comprise the steps:
(1), heavy-metal contaminated soil is levigate;
(2), the iron chloride that obtains is configured and organic acid compound leacheate mixes with the soil of step (1) porphyrize, the compound leacheate volume added during drip washing and the mass ratio of heavy-metal contaminated soil to be repaired are 1.5: 1 ~ 2.0: 1, to vibrate in water bath with thermostatic control oscillator drip washing, drip washing temperature is 25 ~ 28 DEG C, oscillation rate is 180 ~ 220 revs/min, vibrates 20 ~ 28 hours; In described compound leacheate, ferric chloride concn is 5 ~ 30mmol/L, and organic acid concentration is 20 ~ 150mmol/L; Described organic acid is the one in citric acid, malic acid, tartaric acid;
(3) the compound leacheate, through step (2) processed and the mixture of soil centrifugal, centrifugation rate 4500 ~ 5500 revs/min, centrifugation time 3 ~ 8 minutes, compound of inclining leacheate;
(4) soil, processed through step (3) adds the distilled water being equivalent to compound leacheate volume in step (2), constant temperature oscillation drip washing, the same step of temperature, time and oscillation rate (2), centrifugal according to the method for step (3), incline supernatant; Repeat, with distilled water vibration drip washing 1 ~ 3 time, to obtain the soil repaired.
2. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1, is characterized in that heavy-metal contaminated soil is crushed to particle diameter is less than 2cm.
3. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 2, is characterized in that heavy-metal contaminated soil crosses 2mm sieve.
4. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1, it is characterized in that in described compound leacheate, ferric chloride concn is 10 ~ 30mmol/L, organic acid concentration is 50 ~ 150mmol/L.
5. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1, is characterized in that the method also comprises the wastewater treatment of compound leacheate and distilled water drip washing, the further utilization of soil after repairing.
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