CN103357655A - Composite chemical leaching method for remediation of heavy metal contaminated soil - Google Patents
Composite chemical leaching method for remediation of heavy metal contaminated soil Download PDFInfo
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Abstract
The invention discloses a composite chemical leaching method for remediation of heavy metal contaminated soil. The method includes: leaching heavy metal contaminated soil 1-3 times by a composite leacheate prepared from ferric chloride and an organic acid, then further conducting leaching 1-3 time with distilled water, and finally separating the leacheate from soil. The method provided in the invention has the advantages of good treatment effect, short leaching time, no secondary pollution, simple operation, relative low cost, a highest cadmium removal rate of over 80%, and a highest lead removal rate of over 55%. The iron-containing compound involved in the invention is used as an improver of paddy soil. The residue of ferric chloride has a positive effect on chemical properties of soil, and cannot destroy the soil structure. The used organic acid is easy to degrade, and the degradation product can become nutrients of plants and is environment-friendly. The final leaching by water can reduce the content of metal ions and the leacheate residue in the remedied soil, thus being in favor of later crop tilling.
Description
Technical field
The present invention relates to heavy metal pollution of soil improvement technology, 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 the soil pollution problem becomes increasingly conspicuous, and move successively in the chemical plant in urban district, original place or suburbs, and it includes physical construction planning in with leaving over is inexorable trend.Industrial production activities has caused the enrichment of high concentration heavy metal in the 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 characteristics such as heavy metal has residence time length, disguise is strong, toxicity is large can not be microbial degradation, in case entered environment namely begins accumulation, expose or food chain transmission threat health with airborne dust.Therefore, to the chemical plant resettlement Site development recycling of leaving over, must carry out reparation and the regulation of contaminated soil.At present, the restorative procedure of heavy-metal contaminated soil mainly comprises the methods such as physics reparation, chemistry reparation and biological restoration.Compare with other restorative procedures, chemical repair method has stable treatment effect, the advantage such as thorough, and Soil leaching is effective chemical repair method.The Soil leaching technology typically refers to by liquid or other fluids that can promote soil pollutant dissolving migration comes the drip washing contaminated soil, and the pollutant desorption that adsorbs or be fixed on the soil particle is dissolved and the technology of removal.Soil leaching not only can remove pollutant fast from soil, finish the improvement of high density pollution soil 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, existing successful engineering is used abroad, and the earth elution method is to come the drip washing contaminated soil with leacheate, the heavy metal that makes absorption or be fixed on the soil particle dissolves, and then reclaims leacheate recycling.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 is finished in October, 1992 at N.J..According to the report of EPA in 2000, what have in the site remediation new and high technology demonstration project of more than 600 government-fundeds that 4.2% project adopts is exactly the Soil leaching technology.Elution method can be taked original position or dystopy mode of operation neatly, has bright application prospect.The key technology of drip washing reparation be select or develop pointed strong, environmental friendliness, cost is relatively low and pouring agent and the ELUTION METHOD of 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 because working concentration or acidity are larger, and is more serious to soil fail, or is difficult to reach the drip washing effect, so compound eluent is developed gradually and uses.Compound such as chelating agent-inorganic salts, organic acid-inorganic acid, organic acid-organic acid, can reach mutual supplement with each other's advantages, improve washout rate.
Summary of the invention
The object of the invention is to the above-mentioned deficiency for existing drip washing technology, overcome existingly use separately the method reagent cost of 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 objective of the invention is to be achieved through the following technical solutions:
The present invention adopts the compound leacheate drip washing heavy-metal contaminated soil 1～3 time that the configuration of iron chloride and organic acid obtains, then (3 heavy metal ion of test drip washing, iron chloride and organic acid residual quantity are smaller to continue drip washing 1～3 time with distilled water, increase number of times, the cost increase does not have practical significance), at last leacheate is separated with soil.Described organic acid is a kind of in citric acid, malic acid, the tartaric acid.The heavy metal that the present invention is directed to is cadmium, lead.
Wherein, the concentration of iron chloride is 5～50mmol/L in the described compound leacheate, and organic acid concentration is 20～300mmol/L; Preferably, ferric chloride concn is 5～30mmol/L in the described compound leacheate, and organic acid concentration is 20～150mmol/L; Further preferred, ferric chloride concn is 10～30mmol/L in the described compound leacheate, and organic acid concentration is 50～150mmol/L.
A kind of ELUTION METHOD that adopts compound eluent restoration of soil polluted by heavy metal specifically comprises the steps:
(1), heavy-metal contaminated soil is levigate;
(2), configure the iron chloride and the compound leacheate of organic acid that obtain and mix constant temperature oscillation drip washing with the soil of step (1) porphyrize;
(3), the mixture of the compound leacheate processed through step (2) and soil is centrifugal, compound leacheate inclines;
(4), the soil processed through step (3) adds the distilled water that is equivalent to compound leacheate volume in the 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), supernatant inclines; Repeat with distilled water vibration drip washing 1～3 time, the soil that obtains repairing.
When the heavy-metal contaminated soil particle diameter is excessive, before the drip washing heavy-metal contaminated soil is crushed to particle diameter less than 2 cm.
Heavy-metal contaminated soil is crossed the 2mm sieve in the step (1).
The compound leacheate volume that adds during the middle drip washing of step (2) and the mass ratio of heavy-metal contaminated soil to be repaired are 1.5: 1～2.0: 1; The larger drip washing drip washing of the weight ratio of leacheate volume and soil effect is better, is not easy to be separated less than 1.5 leacheates, increase greater than 2.0 increase difficulty of construction and cost, thus arrange 1.5: 1～2.0: 1.
In the step (2), the drip washing of in the water bath with thermostatic control oscillator, vibrating, the drip washing temperature is 25～28 ℃, oscillation rate is 180～220 rev/mins, vibrates 20～28 hours.
In the step (3), 4500～5500 rev/mins of centrifugation rates, centrifugation time 3～8 minutes.
In the step (4), the drip washing of in the water bath with thermostatic control oscillator, vibrating, the drip washing temperature is 25～28 ℃, oscillation rate is 180～220 rev/mins, vibrates 20～28 hours; 4500～5500 rev/mins of centrifugation rates, 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 the compound leacheate of iron chloride leacheate and organic acid and distilled water drip washing, the further utilization of soil after repairing; The waste water of described iron chloride leacheate and the compound leacheate of organic acid and distilled water drip washing is processed through acid treatment and alkaline sedimentation, and content of beary metal reaches the restriction of " integrated wastewater discharge standard "; Heavy metal content in soil reaches the soil (being that available heavy metal content reaches national safety standard) of environmental protection standard after the described reparation, as required, adds N, P, K fertilizer.
In the restorative procedure of the present invention, for the difference of heavy metal in soil content, can carry out certain adjustment to parameters such as the concentration of eluent, drip washing number of times, liquid-solid ratioes, when the content of beary metal in the soil is higher, increase concentration and the solid-liquid mass ratio of eluent, otherwise can suitably reduce.
Compared with prior art, the present invention has advantages of:
(1), the invention provides that a kind for the treatment of effect is good, the drip washing time is short, non-secondary pollution, the chemical leaching method that simple to operate, cost is relatively low, the Cadium In Polluted Soil clearance can reach more than 80%, plumbous more than 55%, overcome the existing method reagent cost of the solution drip washing heavy-metal contaminated soils such as EDTA, organic acid, inorganic acid and inorganic salts that uses separately large, produce secondary pollution, the difficult problem large to soil fail, that subsequent treatment is cumbersome;
(2), the present invention is take the compound leacheate of ferric chloride solution and organic acid composition and distilled water as 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 positive impact to the chemical property of soil, can the spoiled soil structure; The organic acid that uses is easily degraded, and catabolite can become the nutriment of plant, and is environmentally friendly; Use at last distilled water drip washing, the content of metal ion and the residual quantity of leacheate in the soil after reduce repairing are conducive to the later stage to cultivate crop.
(3), iron chloride and the compound leacheate of organic acid among the present invention, relative low price; Compound drip washing can reach the drip washing effect of higher concentration under the low concentration, reduce the working concentration of eluent, reduces rehabilitation cost;
(4), the selected ferric chloride solution of the present invention has preferably removal effect, remediation efficiency high to the cadmium in the soil, lead, can subdue the characteristics such as heavy metal in the soil;
(5), the present invention is suitable for original position drip washing and dystopy drip washing, adopts general water pump and rotary cultivator or sprinkling equipment, the save operation cost, operation sequence is simple.
The specific embodiment
Below the invention will be further described by case study on implementation, and unrestricted the present invention.
Embodiment 1
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76 mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take by weighing some parts of soil, every part 5 gram places centrifuge tube, and the concentration of iron chloride and citric acid as shown in Table 1 and Table 2 among the compound leacheate 10mL that every part of adding is obtained by iron chloride and citric acid preparation, every part of compound leacheate; Centrifuge tube is placed constant temperature oscillator, and the Non-leaching temperature is 25 ℃, and oscillation rate is 200 rev/mins, and vibration drip washing was taken out centrifuge tube after 24 hours; Place centrifuge, centrifugation is 5 minutes under 5000 rev/mins of speed, and compound leacheate inclines; Add distilled water 10mL in the centrifuge tube, drip washing temperature, oscillation rate and drip washing time are the same again, then centrifugation 5 minutes under 5000 rev/mins speed, and supernatant inclines; With distilled water again drip washing twice under similarity condition, the soil that obtains repairing.
Cd clearance (%) in table 1 lessivation
Pb clearance (%) in table 2 lessivation
Behind chemical leaching, the content of Cadmium in Soil can be reduced to 1.16mg/kg by original 6.68mg/kg at most, and the hydrolysate rate is up to 82.57%; Lead content can be reduced to 351.57mg/kg by 787.76 original mg/kg at most, and plumbous clearance is up to 55.37%.Soil after the drip washing reparation can reach (GB15618-2009) requirement of " standard of soil environment quality " (revision) (exposure draft).
Embodiment 2
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76 mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take by weighing some parts of soil, every part 5 gram places centrifuge tube, every part of compound leacheate 10mL that adding is obtained by iron chloride and citric acid preparation, and iron chloride and tartaric concentration are shown in table 3 and table 4 in every part of compound leacheate; Centrifuge tube is placed constant temperature oscillator, and the Non-leaching temperature is 25 ℃, and oscillation rate is 200 rev/mins, and vibration drip washing was taken out centrifuge tube after 24 hours; Place centrifuge, centrifugation is 5 minutes under 5000 rev/mins of speed, and compound leacheate inclines; Add distilled water 10mL in the centrifuge tube, drip washing temperature, oscillation rate and drip washing time are the same again, then centrifugation 5 minutes under 5000 rev/mins speed, and supernatant inclines; With distilled water again drip washing twice under similarity condition, the soil that obtains repairing.
Cd clearance (%) in table 3 lessivation
Pb clearance (%) in table 4 lessivation
Behind chemical leaching, the content of Cadmium in Soil can be reduced to 1.02mg/kg by original 6.68mg/kg at most, and the hydrolysate rate is up to 84.72%; Lead content can be reduced to 152.98mg/kg by 787.76 original mg/kg at most, and plumbous clearance is up to 80.58%.Soil after the drip washing reparation can reach (GB15618-2009) requirement of " standard of soil environment quality " (revision) (exposure draft).
Embodiment 3
Zhuzhou,hunan heavy-metal contaminated soil (Cd content 6.68mg/kg, Pb content 787.76 mg/kg), contaminated soil is levigate, crosses the sieve of 2mm; Take by weighing some parts of soil, every part 5 gram places centrifuge tube, and the concentration of iron chloride and malic acid is shown in table 5 and table 6 among the compound leacheate 10mL that every part of adding is obtained by iron chloride and malic acid preparation, every part of compound leacheate; Other test method is with embodiment 1, the soil that obtains repairing.
Cd clearance (%) in table 5 lessivation
Pb clearance (%) in table 6 lessivation
Behind chemical leaching, the content of Cadmium in Soil can be reduced to 1.28mg/kg by original 6.68mg/kg at most, and the hydrolysate rate is up to 80.81%; Lead content can be reduced to 353.70mg/kg by 787.76 original mg/kg at most, and plumbous clearance is up to 55.10%.Soil after the drip washing reparation can reach (GB15618-2009) requirement of " standard of soil environment quality " (revision) (exposure draft).
After the drip washing of 3 kinds of composite chemical eluents, the content of Cadmium in Soil can be reduced to 1.28 mg/kg～1.02mg/kg respectively by original 6.68mg/kg at most, and the hydrolysate rate is up to 80.81% ~ 84.72%; Lead content can be reduced to 353.70 mg/kg～152.98mg/kg respectively by 787.76 original mg/kg at most, and plumbous clearance is up to 55.10% ~ 80.58%.Soil after the drip washing reparation can reach (GB15618-2009) requirement of " standard of soil environment quality " (revision) (exposure draft).
Claims (10)
1. chemical leaching method that is used for restoration of soil polluted by heavy metal, it is characterized in that adopting the compound leacheate drip washing heavy-metal contaminated soil 1～3 time that the configuration of iron chloride and organic acid obtains, then continue drip washing 1～3 time with distilled water, at last leacheate is separated with soil.
2. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 is characterized in that specifically comprising the steps:
(1), heavy-metal contaminated soil is levigate;
(2), configure the iron chloride and the compound leacheate of organic acid that obtain and mix constant temperature oscillation drip washing with the soil of step (1) porphyrize;
(3), the mixture of the compound leacheate processed through step (2) and soil is centrifugal, compound leacheate inclines;
(4), the soil processed through step (3) adds the distilled water that is equivalent to compound leacheate volume in the 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), supernatant inclines; Repeat with distilled water vibration drip washing 1～3 time, the soil that obtains repairing.
3. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 and 2 is characterized in that described organic acid is a kind of in citric acid, malic acid, the tartaric acid.
4. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 and 2 is characterized in that heavy-metal contaminated soil is crushed to particle diameter less than 2 cm.
5. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 4 is characterized in that heavy-metal contaminated soil crosses 2 mm sieve.
6. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 and 2 is characterized in that ferric chloride concn is 5～50mmol/L in the described compound leacheate, and organic acid concentration is 20～300mmol/L; The compound leacheate volume that adds during drip washing and the mass ratio of heavy-metal contaminated soil to be repaired are 1.5: 1～2.0: 1.
7. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 6 is characterized in that ferric chloride concn is 5～30mmol/L in the described compound leacheate, and organic acid concentration is 20～150mmol/L.
8. the chemical leaching method for repairing the severe heavy-metal contaminated soil according to claim 7 is characterized in that ferric chloride concn is 10～30mmol/L in the described compound leacheate, and organic acid concentration is 50～150mmol/L.
9. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 and 2, it is characterized in that step (2) drip washing of in the water bath with thermostatic control oscillator, vibrating, the drip washing temperature is 25～28 ℃, and oscillation rate is 180～220 rev/mins, vibrates 20～28 hours; In the step (3), 4500～5500 rev/mins of centrifugation rates, centrifugation time 3～8 minutes.
10. the chemical leaching method for restoration of soil polluted by heavy metal according to claim 1 and 2 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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