CN104668281B - Chemical washing-plant absorbing combined repair method for cadmium heavy pollution acid soil of non-ferrous metal mining area of south China - Google Patents
Chemical washing-plant absorbing combined repair method for cadmium heavy pollution acid soil of non-ferrous metal mining area of south China Download PDFInfo
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Abstract
The invention discloses a chemical washing-plant absorbing combined repair method for cadmium heavy pollution acid soil of a non-ferrous metal mining area of south China. The method comprises the following steps: grinding and sieving heavy metal polluted soil and filling the ground and sieved heavy metal polluted soil into an earth pillar; pouring a solution of ferric chloride into the upper part of a soil body, so that the solution flows out from the bottom of the earth pillar naturally along with the gravity, and most part of active cadmium can be removed; after a washing liquid in the upper part of the soil body completely seeps into the soil, pouring deionized water into the upper part of the soil body, so that the liquid flows out from the bottom of the earth pillar naturally along with the gravity, and residual cadmium and washing agent are removed; drying, grinding and sieving the washed soil; adding quicklime, sepiolite, a commercial organic fertilizer and the 0.2 to 1.2 g kg＜-1＞ of total nutrient (N+P2O5+K2O) for improvement; continuously planting sedum plumbizincicola for 1 to 5 seasons, and harvesting over-ground parts to complete repair.
Description
Technical field
The present invention relates to the Treatment process of heavy-metal contaminated soil, and in particular to a kind of southern china non-ferrous metal mining and metallurgy area
The chemical leaching of cadmium heavily contaminated acid soil-Phytoextraction combined remediation method
Background technology
In decades recently, with China's industrialization, the fast development of urbanization process, heavy metal pollution of soil problem day
Benefit is prominent.There is substantial amounts of heavy metal serious pollution soil in the peripheries such as non-ferrous metal mining and metallurgy area, wherein cadmium pollution is of greatest concern
One of problem.Heavy metal have the residence time it is long, it is disguised it is strong, the features such as toxicity is big.Heavy metal can not be degraded by microorganisms,
Once being to start accumulation into environment, health is threatened with the approach such as airborne dust exposure or food chain transmission.South China area
It is acidity that soil is most, and heavy metal in soil activity is high, and south is the important paddy rice producing region of China, and paddy rice is to cadmium (Cd)
Absorb accumulation ability strong, serious threat is produced to health.
Currently, the reparation of Cd serious pollutions acid soil mainly uses chemical passivation technology, with reference to replanting plant non-grain crop.
Chemical passivation is mainly by improving soil acidity or alkalinity (pH), improves absorption, the Precipitation Potential of soil heavy metal, to reduce weight
Metal active, reduces plant absorption.Because removing heavy metals are not removed in chemical passivation thoroughly, over time and environmental condition changes
Become, the heavy metal of passivation has the risk for discharging again.
As the heavy metal that can thoroughly remove in soil, reach permanent reparation purpose technology, chemical leaching and Phytoextraction
Recovery technique receives the favor of numerous researchers.Soil chemistry drip washing recovery technique (Soil washing), refers to utilize chela
Mixture, inorganic acid, organic acid and surfactant etc., quickly remove pollutant from soil, and high concentration is completed in the short time
The improvement of contaminated soil, the technology is mainly used in the reparation of small area heavy metal serious pollution industrial sites.But in order to reach compared with
Good heavy metals removal effect, the drip washing agent concentration that chemical leaching is used is often higher, thus to the destruction of soil property compared with
For serious, and majority, by the way of mud stirring, power consumption is big, solid-liquid separation process is complicated, thus rehabilitation cost compared with
It is high.Phytoextraction recovery technique (Phytoextraction), mainly using heavy metal hyperaccumulative plant, the technology have green,
Inexpensively, unique superiority such as soil property is not destroyed, it is adaptable to low stain soil in heavy metal, severe contaminated soil is difficult
Complete to repair in the short time.
The content of the invention
The technical problem of solution：The present invention is directed to cadmium serious pollution acid soil, there is provided a kind of southern china non-ferrous metal
Chemical leaching-Phytoextraction the combined remediation method of mining and metallurgy area cadmium heavily contaminated acid soil, is first carried out certainly using ferric chloride solution
Right leaching formula drip washing, then the rinsing of nature leaching formula is carried out with water；Farming area in Zuogong is carried out to the soil after drip washing, then continuous plantation
Cadmium hyperaccumulator plant Sedum plumbizincicola, harvests plant shoot and safe disposal, thoroughly to remove Cadmium in Soil.The present invention is using relatively low
The chemical leaching of concentration, influences small to soil property, and eluate is easily handled and reuse；Using nature leaching formula drip washing side
Formula, quantities is small and destroys small to soil texture；Soil recovers to promote while soil property by farming area in Zuogong technology after drip washing
Enter plant growth；Plantation cadmium hyperaccumulator plant Sedum plumbizincicola can remove the cadmium of pedo relict, and soil physical chemistry and life can be recovered again
Thing property.The present invention overcomes simple on the low problem of pure chemistry drip washing later stage heavy metal removing rate and serious pollution soil
Phytoextraction repairing efficiency deficiency long, can substantially reduce the consumption of eluent and washings, reduce Phytoextraction and repair week
Phase, rehabilitation cost and environmental risk.The technology is in south China non-ferrous metal mining and metallurgy area and periphery large area cadmium serious pollution
The aspects such as acid agricultural land soil reparation have broad application prospects.
Technical scheme：The chemical leaching of southern china non-ferrous metal mining and metallurgy area cadmium heavily contaminated acid soil-Phytoextraction connection
Restorative procedure is closed, step is：(1) levigate 2~5mm of the mistake sieves of heavy-metal contaminated soil, and be filled into earth pillar, soil body thickness is 10
~20cm, unit weight is 1.0~1.2g cm-1；(2) by 2~50mmol L-1Ferric chloride solution be poured on the soil body top, leacheate
Water layer thickness is maintained at 2~5cm, and liquid flows out with gravity from earth pillar bottom natural, leacheate volume used and soil quality it
Than 1.5:1~4:1, to remove the most active cadmium of soil；(3) treat that step (2) soil body top leacheate all penetrates into soil
Afterwards, deionized water is poured into soil body top, water layer thickness is maintained at 2~5cm, and liquid is with gravity from earth pillar bottom natural stream
Go out, the ratio between deionization volume used and soil quality 1.5:1~2.5:1, to remove the cadmium and eluent that are remained in the soil body；(4)
Soil after above-mentioned drip washing is dried, it is levigate, cross 2~5mm sieve, addition account for the quick lime of soil weight 0.05~0.2%, 0.5~
2% sepiolite, 0.2~1% organic commercial fertilizer and the total nutrient (N for accounting for soil weight 0.02~0.12% is applied by chemical fertilizer
+P2O5+K2O), improved；(5) continuous plantation is with the season of ore deposit red-spotted stonecrop 1~5, and harvests overground part completion reparation.
The ratio between above-mentioned leacheate volume and soil quality preferably 3:1.
The ratio between above-mentioned deionized water volume and soil quality preferably 2:1.
The consumption of above-mentioned sepiolite is preferably the 1% of soil weight.
Above-mentioned quick lime consumption is preferably the 0.18% of soil weight.
Above-mentioned Rate of Organic Fertilizer is preferably the 0.5% of soil weight.
Beneficial effect：
(1) present invention uses nature leaching formula drip washing, and compared with existing stirring drip washing, the eluent residence time is long, anti-
Answer abundant, utilization rate high, and operation sequence is simple.
(2) the selected ferric chloride solution of the present invention has preferably to polluted heavy metals such as the cadmium in soil, lead, zinc, copper
Removal effect, remediation efficiency are high.
(3) in the present invention, the purpose of Soil leaching process is the quick removal most active cadmium of soil, and non-immediate is made
Cadmium in Soil total amount reaches reparation terminal, therefore eluent consumption and drip washing low intensity, compared with simple Soil leaching, it is to avoid
The low problem of drip washing later stage remediation efficiency, cost is substantially reduced, and notable with the destructiveness of biological property to soil physical chemistry
Reduce.
(4) present invention is rinsed using clear water, reduces the residual of eluent and heavy metal in soil, is conducive to later stage plant
Growth.
(5) hyperaccumulator plant Sedum plumbizincicola used by the present invention, to strong environmental adaptability, grows fast, biomass greatly, and
And it is strong to the accumulation ability of Cadmium in Soil, remediation efficiency is high.
(6) soil improvement of the invention and companion's ore deposit red-spotted stonecrop planting process, can be such that the properties such as soil texture, fertility obtain entirely
Recover in face.
(7) present invention combining by chemical leaching and Phytoextraction, compared with simple Phytoextraction reparation, Ke Yi
The reparation to severe contaminated soil is completed in short period.
Brief description of the drawings
Fig. 1 washes out liquid heavy metal, Cl concentration and pH change schematic diagrams.
Specific embodiment
Below by way of case study on implementation, the invention will be further described, is not intended to limit the present invention.
Embodiment 1
Materials and methods
Non-ferrous metal metallurgy area of zhuzhou,hunan city periphery farming operation floor is picked up from respectively for examination soil, and soil types is red
Earth rice soil, soil is in highly acid, and Cd concentration is 3.12mg kg-1, fundamental property is shown in Table 1.Soil natural dries, crosses 2mm
Sieve, earth pillar is inserted by 15kg soil.Earth pillar internal diameter 30cm, soil body height 18cm, unit weight about 1.18g cm-3, soil body lower section laying Buddhist nun
A metafiltration paper is also laid in imperial net and filter paper, soil body top, and earth pillar bottom sets flow-guiding mouth and silicone tube, collects filtrate.The soil body is first used
Deionized water infiltrates one week from bottom.At room temperature, 45L (liquid soil ratio=3) 20mmol L are poured slowly into by several times from earth pillar top-1
FeCl3Eluent carries out drip washing to earth pillar, treats FeCl3After leacheate all oozes out, 30L (liquid soil ratio=2) deionization is added
Water, leacheate and water layer thickness are maintained at 2~5cm；Timed collection eluate, determines eluate volume, metal and Cl-Concentration.
After whole drip washing terminates, soil in earth pillar is taken out and is dried, physiochemical properties of soil and heavy metal concentration is measured by sampling.Earth pillar
Experiment is repeated 3 times.
Table 1 is for examination soil labile organic matter
Soil carries out farming area in Zuogong after drip washing, and plants and carry out absorption reparation with ore deposit red-spotted stonecrop.Zhuzhou soil is set at 5
Reason：(1) CK (non-washed off soil, control)；(2) W (soil after drip washing)；(3) W+S (soil+1wt.% sepiolites after drip washing)；
(4) W+S+COF (soil+1wt.% sepiolite+0.5wt.% organic commercial fertilizers after drip washing)；(5) W+L+COF (soil after drip washing+
0.18wt.%CaO+0.5wt.% organic commercial fertilizers).Organic commercial fertilizer used contains organic matter 45.6%, full N3.07%, full phosphorus
P2O51.10%th, full potassium K2O 0.7%.Urea, dipotassium hydrogen phosphate, potassium chloride (N are applied in each treatment：P2O5：K2O=200：
200：132mg kg-1) as base manure.Each treatment repeats 4 basins, per basin 1.2kg soil.Planted with ore deposit red-spotted stonecrop, phase after stablizing one week
Between keep soil moisture content 70% or so of field capacity, harvested after being grown 120 days with ore deposit red-spotted stonecrop, determine overground part biological
Amount, heavy metal concentration etc., collection soil test CaCl2Extract state heavy metal concentration.
Result and analysis
(1) lessivation monitoring
Fig. 1 illustrates heavy metal, Cl concentration and pH change in whole lessivation eluate.As can be seen that with drip washing
Carrying out, heavy metal concentration is raised rapidly in eluate, Cd, Zn, Pb, Cu concentration respectively liquid soil than for 0.6,0.8,2.0,
Maximum is reached when 2.0, be then respectively maintained at 0.56,12.5,7.43,1.01mg L-1Left and right, and under starting over time
Drop.In eluate Cd liquid soil than for 1.5 when from begin to decline, when liquid soil is than reaching 3.0, when concentration drops to highest
40% or so, Zn concentration also drop to 74% or so during highest.This explanation, FeCl3The removal efficiency of eluent heavy metal
It has been be decreased obviously that, now stopped FeCl3Drip washing, and use deionized water instead and rinsed.By 2 times of drifts of the water of soil volume
Wash, in eluate the concentration of Cd, Zn, Pb, Cu eventually dropped to 0.001,0.60,0.16,0.05mg L-1。
K, Ca, Mn concentration reach maximum when liquid soil is than being 0.45 in eluate, and hereafter K is maintained to liquid soil ratio 2.0 or so
Slow decline afterwards, Ca is then the rapid decline after liquid soil ratio 0.45, and Mn also declines rapidly after maintaining to arrive liquid soil than 1.5.Wash out
Cl is close steady until FeCl when liquid soil is than 0.75 in liquid3Drip washing terminates, and Fe is then to be slowly raised maximum.By 2
The rinsing of volume of water, K, Ca, Mn, Fe, Cl drop to very low level in eluate.5.8 drops of the other eluate pH from starting
It is low to liquid soil than 0.75 when 2.4, then steadily, by after 2 times of rinsings of the water of soil volume, being increased to 3.3.
By above-mentioned comparing, using 3 times of 20mmol L of soil volume-1FeCl3+ 2 times of deionized waters of soil volume
It is optimal drip washing scheme, can so makes FeCl3Eluent and washings all keep utilization rate higher, it is to avoid continue drip washing and
Rinsing causes the wasting of resources, at utmost reduces cost, reduction environmental risk.
(2) removal efficiency of the chemical leaching to heavy metal-polluted soil
As can be seen from Table 2, the eluent by 3 times of soil volumes and 2 times of drip washing of the water of soil volume, soil Cd,
The clearance of Cu, Zn, Pb is respectively 45.2%, 13.0%, 20.0%, 23.6%.The result is adopted under being even better than Isodose
It is and easy to operate, small to the destruction of soil texture with the clearance of vibration drip washing.
Heavy metal concentration change before and after the Soil leaching of table 2
(3) changes of soil properties and ameliorative measure optimize after drip washing
As can be seen from Table 3, FeCl3Lessivation causes certain influence on soil property, soil pH is reduced by 5.22
To 4.32, available N, P, K concentration also decrease, it is necessary to carry out appropriate farming area in Zuogong, the present invention is by adding 1% Hai Pao
Stone, the organic commercial fertilizer of 1% sepiolite+0.5%, 0.18% quick lime, three kinds of evolutionary approach of+0.5% organic commercial fertilizer are to soil pH
Slightly improve, but it is not notable, add the treatment CaCl of quick lime2State Cd concentration is extracted to decrease (table 4).
Soil part physical and chemical properties change before and after the drip washing of table 3
Influence of the modifying agent of table 4 to soil pH and available state Cd
(4) remediation efficiency is drawn with ore deposit red-spotted stonecrop
From table 5, different disposal with ore deposit red-spotted stonecrop the upperground part biomass difference, with plant biological on non-washed off soil
Amount highest, up to 7.6g basins-1, non-improved treatment biomass is minimum after drip washing, only 3.3g basins-1；Improved treatment especially adds quick lime
5.3g basins are brought up to biology after organic fertilizer-1.Different disposal is 146~190mg kg with ore deposit red-spotted stonecrop overground part Cd concentration-1, Zn
Concentration is 3585~4522mg kg-1.Companion's ore deposit red-spotted stonecrop overground part is 0.38mg to the uptake of Cd in non-improved soil after drip washing
kg-1, adding sepiolite treatment makes Cd uptakes bring up to 0.58mg kg-1, addition sepiolite+organic fertilizer, quick lime+organic fertilizer
Treatment the uptake of Cd is all improve compared with the treatment not improved, the uptake difference of Cd does not show between three improved treatments
Write.Each treatment is 7.8~20.9mg kg to the uptake of Zn-1。
With the absorption of ore deposit red-spotted stonecrop the upperground part biomass and heavy metal after the leaching of table 5
As can be seen from Table 6, with after ore deposit red-spotted stonecrop, soil Cd concentration is by 3.12mg kg for non-washed off soil plantation-1Fall below
2.02mg kg-1；Non- improved soil Cd concentration is by 1.71mg kg after drip washing-1Fall below 1.33mg kg-1, draw and repair clearance
It is 22.2%；After drip washing+sepiolite process soil Cd concentration by 1.71mg kg-1Fall below 1.13mg kg-1, draw reparation and go
Except rate brings up to 33.9%；Under addition sepiolite+organic fertilizer, two treatment of quick lime+organic fertilizer, draw reparation clearance and also divide
31.6%, 32.2% is not reached.Chemically drip washing-Phytoextraction total removal rate sees, non-improved soil cadmium total removal rate after drip washing
It is 57.4%, and is processed by farming area in Zuogong, cadmium total removal rate has brought up to 62.5%~63.8%.
The removal effect of the chemical leaching of table 6 and Phytoextraction to soil Cd
As seen from Table 7, chemical leaching process makes soil CaCl2Extract 0.89mg kg of the state Cd concentration by original soil-1Drop to
0.33mg kg-1, further reduced by farming area in Zuogong available state Cd concentration, it is reduced in quick lime and organic fertilizer treatment
0.14mg kg-1.After plantation companion's ore deposit red-spotted stonecrop, soil CaCl2Extracting state Cd concentration further reduces, in drip washing+quick lime+organic
In fertilizer treatment, soil CaCl2Extract state Cd concentration and be reduced to 0.04mg kg-1。
The chemical leaching of table 7, farming area in Zuogong, Phytoextraction are to soil CaCl2Influence (the mg kg of-Cd concentration-1)
(5) chemical leaching and Phytoextraction combine d bioremediation efficiency
It can be seen from the results above that pure chemistry drip washing is 45.2% (table 2), simple Phytoextraction to the clearance of Cd
Clearance to Cd is 35.3% (table 6), and passes through chemical leaching, sepiolite improvement, three joints of process of Phytoextraction, Cd
Clearance has brought up to 63.8%.
Conclusion
(1) found by the monitoring to lessivation, the clearance of Cd begins to decline when liquid soil is than being 1.5, works as liquid
When soil is than reaching 3.0, clearance drops to 40% or so during highest, now stops FeCl3Drip washing, and use deionized water instead and enter
Row rinsing.Rinsed by 2 times of water of soil volume, the concentration of Cd, Zn, Pb, Cu, K, Ca, Mn, Fe, Cl is all dropped in eluate
Very low level.Therefore using 3 times of 20mmol L of soil volume-1FeCl3+ 2 times of drip washing of the deionized water of soil volume
Mode is optimal.
(2) after to drip washing soil farming area in Zuogong, the growth with ore deposit red-spotted stonecrop can be effectively facilitated, suction to Cd is improved
Remediation efficiency is taken, can be drawn by comparing, 1% sepiolite, the organic commercial fertilizer of 1% sepiolite+0.5%, 0.18% quick lime+
0.5% three kinds of organic commercial fertilizer evolutionary approach can promote to be grown with ore deposit red-spotted stonecrop, and the commodity of 0.18% quick lime+0.5% are organic
Fertilizer treatment biomass highest, but the treatment of 1% sepiolite is not apparent from reducing soil Cd validity, and the efficiency that Phytoextraction is repaired is also most
Height, and cost is minimum, therefore, the preferred plan that soil improvement is fostered and apply fertilizer after drip washing is 1% sepiolite of addition.
(3) clearance of pure chemistry drip washing Cd is 45.2%, and simple Phytoextraction is 35.3% to the clearance of Cd, and
By chemical leaching, sepiolite improvement, three joints of process of Phytoextraction, Cd clearances have brought up to 63.8%.
(4) for the cadmium heavily contaminated Red Paddy Soil used by the present invention, optimal reparation pattern is：Chemical leaching+change
Good+Phytoextraction combine d bioremediation of fostering and apply fertilizer, wherein chemical leaching use nature leaching formula elution method, eluent to select 3 times of soil masses
Long-pending 20mmolL-1FeCl3+ 2 times of deionized water rinsings of soil volume, farming area in Zuogong can add 1% sepiolite, Ran Houzai
Plantation carries out absorption reparation with ore deposit red-spotted stonecrop, is finally reached the purpose for thoroughly repairing Cd pollutions.
(5) pattern had both avoided the big problem of pure chemistry drip washing high cost, environmental risk, also overcomed heavily contaminated soil
Deficiency long of simple phytoremediation cycle on earth, to south China mining and metallurgy area and periphery cadmium serious pollution Red Paddy Soil etc.
Reparation is with a wide range of applications and researching value.
Claims (6)
1. the chemical leaching of southern china non-ferrous metal mining and metallurgy area cadmium heavily contaminated acid soil-Phytoextraction combined remediation method,
It is characterized in that step is：
（1）Heavy-metal contaminated soil is levigate, and the mm of mistake 2 ~ 5 is sieved, and is filled into earth pillar, and soil body thickness is 10 ~ 20cm, and unit weight is
1.0~1.2 g cm-3；
（2）By 2 ~ 50 mmol L-1Ferric chloride solution be poured on soil body top, leacheate water layer thickness is maintained at 2 ~ 5 cm, liquid
Flowed out from earth pillar bottom natural with gravity, the ratio between leacheate volume used and soil quality 1.5: 1 ~ 4:1, to remove soil
Most active cadmium；
（3）Treat step（2）After soil body top leacheate all penetrates into soil, deionized water is poured into soil body top, water layer is thick
Degree is maintained at 2 ~ 5 cm, and liquid flows out with gravity from earth pillar bottom natural, the ratio between deionized water volume used and soil quality
1.5: 1 ~ 2.5:1, to remove the cadmium and eluent that are remained in the soil body；
（4）Soil after above-mentioned drip washing is dried, it is levigate, cross 2 ~ 5 mm sieve, addition account for the quick lime of soil weight 0.05 ~ 0.2%,
The total nutrient that 0.5 ~ 2% sepiolite, 0.2 ~ 1% organic commercial fertilizer and being applied by chemical fertilizer accounts for soil weight 0.02 ~ 0.12% enters
Row improvement, the total nutrient is N+P2O5+ K2O；
（5）Continuous plantation harvests overground part completion reparation with the season of ore deposit red-spotted stonecrop 1 ~ 5.
2. chemical leaching-Phytoextraction combined remediation method according to claim 1, it is characterised in that leacheate volume and soil
Earth mass ratio 3:1.
3. chemical leaching-Phytoextraction combined remediation method according to claim 1, it is characterised in that deionized water volume with
The ratio between soil quality 2:1.
4. chemical leaching-Phytoextraction combined remediation method according to claim 1, it is characterised in that the consumption of sepiolite is
The 1% of soil weight.
5. chemical leaching-Phytoextraction combined remediation method according to claim 1, it is characterised in that quick lime consumption is soil
The 0.18% of earth weight.
6. chemical leaching-Phytoextraction combined remediation method according to claim 1, it is characterised in that Rate of Organic Fertilizer is soil
The 0.5% of earth weight.
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| CN105363769A (en) * | 2015-12-17 | 2016-03-02 | 中国有色桂林矿产地质研究院有限公司 | Method for restoring cadmium-contaminated farmland soil |
| CN107138511B (en) * | 2017-05-11 | 2020-07-21 | 南京大学 | Method for combined remediation of heavy metal contaminated soil |
| CN107900094A (en) * | 2017-11-16 | 2018-04-13 | 湖南大学 | A kind of method with chemical leaching and passivating technique renovation of heavy metal polluted soil with combined |
| CN108811579A (en) * | 2018-06-13 | 2018-11-16 | 南京农业大学 | A kind of method that agricultural land soil soil fertility is restored after chemical oxidation is repaired |
| CN110899323A (en) * | 2019-12-27 | 2020-03-24 | 宁土建工(苏州)环境修复科技有限公司 | Method for restoring farmland heavy metal contaminated soil by combining chemical leaching and phytoremediation |
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