CN108941177A - It is a kind of for repairing the eluent and its application method of Cu, Pb, As combined contamination soil - Google Patents
It is a kind of for repairing the eluent and its application method of Cu, Pb, As combined contamination soil Download PDFInfo
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- CN108941177A CN108941177A CN201811051654.1A CN201811051654A CN108941177A CN 108941177 A CN108941177 A CN 108941177A CN 201811051654 A CN201811051654 A CN 201811051654A CN 108941177 A CN108941177 A CN 108941177A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
Abstract
The present invention provides a kind of for repairing the eluent and its application method of Cu, Pb, As combined contamination soil, eluent main component is Tween-80, anionic surfactant and EDTA, wherein anionic surfactant is one of SDS, SDBS, lauric acid, and EDTA, Tween-80, anionic surfactant volume ratio are 1:2:2.After its application method is the following steps are included: (1) mix contaminated soil with water, wet screening, impurities removing and the biggish soil of particle；(2) screening soil is sent to elution pond, stirs 10-12h, precipitates 2-4h, and collection leacheate enters recovery system and recycles；(3) soil after elution is detected, until testing result is qualified；(4) will treated qualified soil water desorption, then backfill.The present invention utilizes the soil of surfactant and chelating agent Combined Treatment Cu, Pb, As combined pollution, can improve the removal rate to Cu, Pb, As in soil, has targetedly application effect to the soil remediation of Cu, Pb, As combined pollution.
Description
Technical field
The invention belongs to contaminated soil remediation technical field, it is related to a kind of for removing heavy metal copper in soil, lead, arsenic
Eluent and application method.
Background technique
In recent years, with the acceleration of urbanization process, heavy metal pollution event constantly occurs, " lead poisoning ", " cadmium major class ",
Contamination accidents such as " heavy metal pollution vegetables " cause the very big concern of compatriots' counterweight (class) metallic pollution, and heavy metal pollution of soil is
One of the problem of as Agricultural Sustainable Development in China.According to the Ministry of Agriculture to " Chinese arable land heavy metal pollution of soil overview "
Investigation show that the contaminated area of Chinese arable land accounts for the 16.7% of the gross area, wherein main pollution element be mercury (Hg), cadmium
(Cd), lead (Pb), chromium (Cr), zinc (Zn), copper (Cu) and nickel (Ni) and metalloid arsenic (As), cadmium, copper, lead, mercury, nickel and
Zinc is considered as most dangerous heavy metal, and is put on the severe pollutant list of EPA (EPA, 1992).Heavy metal has hidden
The characteristics of covering property, chronicity and irreversibility, is not degraded by microorganisms once entering in soil, to influence crop and biology
Growth, or migration and conversion are occurred by food chain, be detrimental to health even life.Therefore, to heavy metal pollution of soil
It repairs and has become the project of China's hot research, at present to there are mainly two types of the modes of the soil of repairing heavy metal pollution: a kind of
It is directly to remove heavy metal from soil；Another kind is to change the existing forms of heavy metal in the soil, and heavy metal is fixed
To reduce its activity and migration in the environment.And mainly there is engineering technology for the method for heavy-metal contaminated soil reparation
Method, physical method chemical method (including including electric driving method, electrothermal way and elution method), stable curing method and biological restoration etc..
Under normal circumstances, pollutant cannot be uniformly distributed in the soil, and particle size is smaller, be exposed to the table of pollutant
Area is bigger, and little particle soil is heavier than other particle contaminations, need to separate independent processing.Clay have particle it is thin,
Plasticity is strong, associativity is good, and thixotropy is excessive, and shrinking is suitable for the processing performances such as refractoriness height, and apparent surface is big and its surface
Electric polarity, it is the higher clay of the content of organic matter, and heavy metal contaminants can tightly be adsorbed on little particle soil, make to drench
Lotion is restricted the repairing effect of contaminated soil.
Elution method is considered as quickly and effectively method in current all remediation of heavy metal-contaminated soil, it is a kind of
Using the aqueous solution of eluent, by method chemically and physically, polluter is separated or is resolved to elution from soil particle
The technology removed in liquid.Type, concentration, pH value, elution time, solid-to-liquid ratio and the dosage of eluent will affect and elute to it
The effect of heavy-metal contaminated soil.The selection of eluent at present has correlative study to show one mostly on single eluent
Under the conditions of a little, single eluent is poor for soil pollutant elution effect, and different types of eluent optimizes again
Match, can reach the solubilized effect of collaboration, realize the invigoration effect to pollutant in soil maximum material removal rate, can also save eluent
Usage amount reduces destruction of the eluent to soil.In recent years, using the metal of natural surfactant removal contaminated soil
An apparent trend is had become, but most of eluents are unsatisfactory to the removal effect of As.Therefore, for different heavy metals
Exceeded soil selects different elution agent prescriptions, the heavy metal that can be effectively removed in soil, moreover it is possible to not destroy soil physical chemistry
Property causes secondary pollution to environment.
Summary of the invention
The invention aims to refine the selection of the eluent of the chemical leaching reparation of variety classes heavy-metal contaminated soil,
The thinner clay of particle is targetedly repaired；Meanwhile enhancing eluent to the removal effect of heavy metal As, provide one
Plant the eluent and its application method for repairing Cu, Pb, As combined contamination soil, the leaching to heavy metal Cu, Pb, As in clay
Wash significant effect.
The technical scheme is that a kind of for repairing the eluent of Cu, Pb, As combined contamination soil, including surface
Activating agent and chelating agent, the surfactant include Tween-80, anionic surfactant, and the chelating agent is EDTA, leaching
Lotion PH=7, EDTA, Tween-80, anionic surfactant volume ratio are 1:2:2.
Further, the Tween-80 mass concentration is 0.5%, and anionic surfactant mass concentration is 0.3%,
EDTA concentration is 0.03mol/L；
Further, the anionic surfactant is one of SDS, SDBS, lauric acid；
The present invention also provides a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil, including following step
It is rapid:
(1) after the soil of heavy-metal composite pollution being mixed with water, wet screening, impurities removing, and remove the biggish soil of degranulation
Earth；
(2) by step (1) treated screening soil send to elution pond, inject leacheate circulation stirring 10-12h after, precipitate 2-
4h, collection leacheate enter recovery system and recycle；
(3) step (2) are repeated, the soil after elution is detected, until testing result is qualified；
(4) by step (3) treated qualified soil water desorption；
(5) by step (4) treated qualified soil backfill.
Further, in step (1), the standard of the screening is soil particle diameter < 80um.
Further, in step (2), the volume ratio of the screening soil and leacheate is 1:10.
Further, in step (2), the recovery system can be using electrochemical techniques recycling heavy metal and elution
Liquid.
Further, in step (3), the standard of the testing result qualification is copper content≤200mg/kg, lead content≤
300mg/kg, arsenic content≤50mg/kg.
Further, in step (4), the standard of the dehydration is moisture content≤50%.
Further, in step (5), after treated the qualified soil backfill, super enriching plant, counterweight can be planted
Metallic pollution is further repaired.
Compared with the relevant technologies, beneficial effects of the present invention:
(1) EDTA can change its existing forms in the soil, to heavy metal in soil in conjunction with the heavy metal ion in soil
The removal effect of Cu, Pb are significant, have preferable application effect to the severe combined contamination soil of Cu, Pb；
(2) Tween-80 is good builder and solubilizer, and dirt-removing power is strong, and will not destroy protein structure, Tween-80 with
EDTA, which is used in combination, can reach the solubilized effect of collaboration, promote heavy metal ion As3+Transfer, enhance to heavy metal in soil As's
Removal effect solves the problems, such as that As removal rate is low；
(3) anionic surfactant can clarify evolution pollutant, can promote the sedimentation and filtering of heavy metal ion, improve clay
The removal effect of middle heavy metal.
(4) EDTA can be achieved to go pollutant in soil maximum with Tween-80, being used in combination for anionic surfactant
Except the invigoration effect of rate, repairing has specific aim, can effectively remove Cu, Pb, As in soil, not destroy soil physico-chemical property,
Secondary pollution will not be caused to environment simultaneously；
(5) the higher clay of organic matter (little particle soil) content is separated into independent processing, to the thinner clay of particle into
Row is targetedly repaired, and has preferable application effect for the severe combined pollution clay of Cu, Pb, As.
Detailed description of the invention
Fig. 1 is removal rate of the 1 various concentration EDTA of the embodiment of the present invention to three heavy metal species combined contamination soils
Fig. 2 is removal rate of the 2 various concentration Tween-80 of the embodiment of the present invention to three heavy metal species combined contamination soils
Fig. 3 is removal rate of the 3 various concentration SDS of the embodiment of the present invention to three heavy metal species combined contamination soils
Fig. 4 is 4 difference EDTA of the embodiment of the present invention: Tween-80 is with the removal rate for comparing three heavy metal species combined contamination soils
Fig. 5 is 5 difference EDTA:SDS of the embodiment of the present invention with the removal rate for comparing three heavy metal species combined contamination soils
Fig. 6 is 6 difference EDTA of the embodiment of the present invention: Tween-80: SDS with the removal for comparing three heavy metal species combined contamination soils
Rate.
Specific embodiment
With reference to embodiments, invention is described in detail, selected anionic surface in following embodiment
Activating agent is SDS.
Embodiment 1
Removal rate of the EDTA to three heavy metal species combined contamination soils
Step method is as follows:
(1) prepare the EDTA containing various concentration eluent solution, concentration be respectively 0.01mol/L, 0.02mol/L, 0.03mol/L,
0.04mol/L,0.05mol/L；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 1, by data in attached drawing 1 it is known that EDTA and water are no to the removal rate of Cu very
Big variation takes the lead in declining after improving, EDTA concentration is gone in 0.03mol/L with the raising of EDTA concentration to the removal of Cu
Except rate is up to 79.3%；The removal rate of Pb, As increase with the increase of EDTA concentration, when concentration is 0.03mol/L, Pb,
As is respectively 80.2%, 36.5%；When concentration is higher than 0.03mol/L, removal rate is remained unchanged.Therefore, select EDTA concentration for
0.03mol/L。
Embodiment 2
Removal rate of the Tween-80 to three heavy metal species combined contamination soils
Step method is as follows:
(1) prepare the eluent solution of the Tween-80 containing various concentration, mass concentration is respectively 0. 1%, 0.2%, 0.3%, 0.4%,
0.5%；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 2, by data in attached drawing 2 it is known that Tween-80 and water do not have the removal rate of Cu
It varies widely.Tween-80 increases the removal rate of Cu, Pb, As with the raising of mass concentration, and Tween-80 quality is dense
Degree is at 0.5%, to the removal rate highest of Cu, Pb, As, respectively 78.4%, 20.7%, 50.4%.Therefore, Tween-80 matter is selected
Measuring concentration is 0.5%.
Embodiment 3
Removal rate of the SDS to three heavy metal species combined contamination soils
Step method is as follows:
(1) eluent solution of the SDS containing various concentration is prepared, mass concentration is respectively 0. 1%, 0.2%, 0.3%, 0.4%, 0.5%；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 3, by data in attached drawing 3 it is known that SDS and water are no to the removal rate of Cu very
Big variation.SDS increases the removal rate of Cu, Pb, As with the raising of mass concentration, and increasing degree is gradually reduced, SDS
Mass concentration > 0.3% tends towards stability to the removal rate of three heavy metal species, and SDS mass concentration is at 0.5%, to Cu, Pb, As
Removal rate highest, respectively 82.6%, 45.1%, 44.6%.Therefore, selecting SDS mass concentration is 0.3%.
Embodiment 4
Different EDTA: Tween-80 is with the removal rate for comparing three heavy metal species combined contamination soils
Step method is as follows:
(1) prepare and contain EDTA: the eluent solution of Tween-80 proportion, ratio is respectively 1:1,1:2,1:3,1:4,1:5；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 4, by data in attached drawing 4 it is known that the eluent is to Cu's when ratio is 1:4
Removal rate highest, up to 82.4%；When ratio is 1:5, the eluent is to the removal rate highest of Pb, up to 86.7%；When ratio is 1:2,
The eluent is to the removal rate highest of As, up to 69.6%.Therefore, select EDTA: Tween-80 proportion is 1:2.
Embodiment 5
Different EDTA:SDS are with the removal rate for comparing three heavy metal species combined contamination soils
Step method is as follows:
(1) eluent solution matched containing EDTA:SDS is prepared, ratio is respectively 1:1,1:2,1:3,1:4,1:5；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 5, by data in attached drawing 5 it is known that the eluent is to Cu when ratio is 1:2
Removal rate highest, up to 84.1%；When ratio is 1:1, the eluent is to the removal rate highest of Pb, up to 86.7%；Ratio is 1:2
When, the eluent is to the removal rate highest of As, up to 59.6%.Therefore, selecting EDTA:SDS proportion is 1:2.
Embodiment 6
Different EDTA: Tween-80: SDS is with the removal rate for comparing three heavy metal species combined contamination soils
Step method is as follows:
(1) eluent solution for containing EDTA: Tween-80: SDS proportion is prepared, ratio is respectively 1:1:1,1:1:2,1:2:1,1:2:
2；
(2) soil for taking heavy-metal composite pollution is measured the content of Cu, Pb, As in the soil；
(3) to soil particle wet screening, impurities removing, and the biggish soil of degranulation is removed；
(4) by treated, screening soil is sent to elution pond, after injecting leacheate circulation stirring 10-12h, precipitates 2-4h, collection
Leacheate enters recovery system and recycles；
(5) soil after elution is detected, until testing result is qualified；
(6) content of Cu, Pb, As are measured in the soil qualified to detection, and calculate removal rate.
Concrete outcome is as shown in Fig. 6, by data in attached drawing 6 it is known that above-mentioned leacheate is to the big of the removal rate of Cu
It is small to be successively: water < 1:1:1 < 1:2:1 < 1:1:2 < 1:2:2；Size to the removal rate of Pb is successively: water < 1:2:1
< 1:1:1 < 1:1:2 < 1:2:2；Size to the removal rate of As is successively: water < 1:1:2 < 1:1:1 < 1:2:1 < 1:2:
2。
In conjunction with above-mentioned 6 embodiment interpretations of result, various concentration difference eluent is to the removal rate of Cu directly without significant
Difference, it is little with removal rate difference of the water to it；EDTA is best to the removal rate effect of Pb, when concentration is 0.03mol/L, Pb
Removal rate up to 80.2%；And above-mentioned SDS, Tween-80 and EDTA be not significant to the removal rate effect of As, removal rate highest only exists
When Tween-80 concentration is 0.5%, removal rate 50.4%.Therefore, EDTA and Tween-80, SDS are mixed with the ratio of 1:2:2
It closes, prepares a kind of compound eluent for being directed to Cu, Pb, As combined contamination soil (especially clay).
Above-described embodiment card can be used for the explanation and illustration present invention, rather than limit the invention, of the invention
In spirit and scope of protection of the claims, to any modifications and changes that the present invention makes, protection model of the invention is both fallen within
It encloses.
Claims (10)
1. a kind of for repairing the eluent of Cu, Pb, As combined contamination soil, including surfactant and chelating agent, the table
Face activating agent includes Tween-80, anionic surfactant, and the chelating agent is EDTA, EDTA, the eluent PH=7 is spat
Temperature -80, anionic surfactant volume ratio are 1:2:2.
2. a kind of for repairing the eluent of Cu, Pb, As combined contamination soil according to claim 1, which is characterized in that institute
Stating Tween-80 mass concentration is 0.5%, and anionic surfactant mass concentration is that 0.3%, EDTA concentration is 0.03mol/L.
3. anionic surfactant is one of SDS, SDBS, lauric acid according to claim 1.
4. it is according to claim 1 for repairing the application method of the eluent of Cu, Pb, As combined contamination soil, it is special
Sign is, comprising the following steps:
(1) after the soil of heavy-metal composite pollution being mixed with water, wet screening, impurities removing, and remove the biggish soil of degranulation
Earth；
(2) by step (1) treated screening soil send to elution pond, inject leacheate circulation stirring 10-12h after, precipitate 2-
4h, collection leacheate enter recovery system and recycle；
(3) step (2) are repeated, the soil after elution is detected, until testing result is qualified；
(4) by step (3) treated qualified soil water desorption；
(5) by step (4) treated qualified soil backfill.
5. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
It is characterized in that, the standard of step (1) described screening is soil particle diameter < 80um.
6. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
It is characterized in that, the volume ratio of step (2) the screening soil and leacheate is 1:10.
7. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
It is characterized in that, step (2) recovery system is using electrochemical techniques recycling heavy metal and leacheate.
8. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
It is characterized in that, the standard of step (3) the testing result qualification is copper content≤200mg/kg, lead content≤300mg/kg, arsenic
Content≤50mg/kg.
9. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
It is characterized in that, the standard of step (4) described dehydration is moisture content≤50%.
10. it is a kind of for repairing the application method of the eluent of Cu, Pb, As combined contamination soil according to claim 4,
Be characterized in that, after treated qualified soil backfill that step (5) is described, super enriching plant can be planted, to heavy metal pollution into
Row is further repaired.
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| CN110201998A (en) * | 2019-06-05 | 2019-09-06 | 上海大学 | A kind of method that sudangrass repairs pyrene and nickel combined contamination soil |
| CN110305668A (en) * | 2019-04-11 | 2019-10-08 | 苏州市宏宇环境科技股份有限公司 | Heavy metals in paddy soils eluent and preparation method thereof |
| CN111250535A (en) * | 2020-02-18 | 2020-06-09 | 四川省蜀通岩土工程公司 | Heavy metal composite contaminated site soil remediation method |
| CN112457854A (en) * | 2019-09-06 | 2021-03-09 | 中国石油化工股份有限公司 | Degradable soil leaching composition and method for repairing heavy metal soil |
| CN114381277A (en) * | 2022-01-29 | 2022-04-22 | 中节能（连云港）清洁技术发展有限公司 | Soil conditioner and preparation thereof |
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