CN106269832A - A kind of restorative procedure of lower valency heavy-metal contaminated soil - Google Patents
A kind of restorative procedure of lower valency heavy-metal contaminated soil Download PDFInfo
- Publication number
- CN106269832A CN106269832A CN201610827640.9A CN201610827640A CN106269832A CN 106269832 A CN106269832 A CN 106269832A CN 201610827640 A CN201610827640 A CN 201610827640A CN 106269832 A CN106269832 A CN 106269832A
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- China
- Prior art keywords
- soil
- polyglutamic acid
- lower valency
- heavy metal
- chitosan
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Classifications
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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
Abstract
The invention discloses the restorative procedure of a kind of lower valency heavy-metal contaminated soil, including (1) using water as eluent, first pass through in the soil that injector well is injected into lower valency heavy metal pollution, by extraction well, the leacheate being enriched lower valency heavy metal is extracted from soil again, collect leacheate, in sedimentation, extraction supernatant to process tank；(2) polyglutamic acid chitosan gel rubber is directly added in process tank; stirring and adsorbing more than 3 hours; after solid-liquid separation; recycle process fluids also pumps into injector well and continues washed off soil as eluent; the present invention can efficiently remove soil state heavy metal at a middle or low price; to environment non-secondary pollution, macromolecular material has the advantages such as biodegradable, biocompatibility, can be widely applied environmental protection protection field.
Description
Technical field
The invention belongs to environmental protection technical field, relate to a kind of drip washing-suction for lower valency heavy-metal contaminated soil
Attached restorative procedure.
Background technology
Along with the fast development of national economy, heavy metal in soil pollution condition is on the rise.The heavy metal that soil contains
Being mostly the heavy metal of lower valency, lower valency heavy metal includes the bivalence such as copper, cadmium, lead, zinc, arsenic, hydrargyrum, ferrum or trivalent gold
Belong to.The features such as the more difficult migration of heavy metal in soil, has the residence time long, and disguise is strong, toxicity is big, and may be through crop
Absorb laggard enter food chain, or entered in water, air by some migration pattern, thus threaten the health of the mankind and other
Multiplying and living of animal, riverbed sediments and the soil of therefore administering heavy metal pollution are always the focus and difficulty attracted attention both at home and abroad
Point research topic.The bio-toxicity of heavy metal is not only relevant with its total amount, is determined by its fractions distribution to a greater extent.Different
Form produce different environmental effect, directly influence the toxicity of heavy metal, migration and the circulation at nature.
Most of heavy metals are transitional elements, and its distinctive electron structure of atom of transitional element so that it is
Chemical behavior in soil environment has a series of feature.Heavy metal can occur redox reaction in certain amplitude, tool
Having variable valence, because the valence state of heavy metal is different, its activity and toxicity are the most different；Heavy metal easily hydrolyzes in soil environment
Reaction, generates hydroxide, it is also possible to some inorganic acid reactions in soil, generate sulfide, carbonate, phosphate etc..
The solubility product of these compounds is smaller so that Heavy Metal Accumulation, in soil, is difficult to migrate, contamination hazard expanded range
Probability is less, but the harm cycle in making Polluted area is elongated, and the extent of injury strengthens.
Heavy metal in soil pollution amelioration is faced with stern challenge.The technology removing removing heavy metals at present includes phytoremediation
Method, microorganism remediation method, fixation, drip washing repairing method, electro reclamation method etc..Heavy metal hyperaccumulative plant reparation is applicable to big face
Long-pending contaminated soil remediation, its cycle is longer, and microorganism remediation is often used in combination with other recovery techniques and reaches to repair purpose,
But the cultivation of strain and universality are difficult points.Wherein elution method has technique simply, and remediation efficiency is high, strong adaptability,
Moderate cost, the advantage such as strong operability.Become soil environment in this year and repair one of the study hotspot in field.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of with low cost, simple to operate, remediation efficiency is high
New soil restorative procedure, combines Soil leaching technology and bioabsorbable polymer material Adsorption of Heavy Metals technology and reaches efficiently to go
Purpose except heavy metal in soil.
It is an object of the invention to be achieved through the following technical solutions:
The restorative procedure of a kind of lower valency heavy-metal contaminated soil, comprises the following steps:
(1) drip washing
Using water as eluent, first pass through in the soil that injector well is injected into lower valency heavy metal pollution, then incited somebody to action by extraction well
The leacheate being enriched lower valency heavy metal extracts from soil, collects leacheate, through sedimentation, extracts supernatant to processing
In tank；
(2) absorption
Polyglutamic acid-chitosan gel rubber is directly added in process tank, stirring and adsorbing more than 3 hours, after solid-liquid separation, returns
Receive treatment fluid and pump into injector well and continue washed off soil as eluent.
So circulation is until soil and leacheate are all up to state standards.
The dosage of described polyglutamic acid-chitosan gel rubber is 25 ~ 50kg/ ton.
Polyglutamic acid-chitosan gel rubber absorption at a low price resolves with 0.1 ~ 1mol/L hydrochloric acid solution after heavy metal, makes
Lower valency metal ion reclaims, and polyglutamic acid-chitosan gel rubber after treatment is reusable.
The preparation of polyglutamic acid-chitosan gel rubber:
Weigh the gamma-polyglutamic acid-of 0.1-0.8g in 100ml beaker, add 30-60g deionized water, be placed in magnetic agitation
Stir on device until being completely dissolved；
Weighing 3-6g chitosan, gamma-polyglutamic acid-and chitosan mol ratio are 1:4-100, are slowly added into equipped with polyglutamic
In the beaker of acid solution, add while stirring and make chitosan be uniformly dispersed in polyglutamic acid solution；
Weigh 30-60g 0.4mol/L acetum, the most at the uniform velocity add in beaker, stop stirring, react 10 minutes, crosslinking
After obtain polyglutamic acid gel；
By soak in 3mol/L sodium hydroxide solution 4 hours, then rinse by phosphate buffered solution, obtain γ-poly-
Glutamic acid-chitosan gel rubber, can be soaked in phosphate buffered solution storage.
Lower valency heavy-metal contaminated soil is through repeatedly drip washing, and the solution of each drip washing is all the filter after last drip washing
Liquid filtrate after lower valency heavy metal adsorption processes obtains；Described lower valency heavy metal adsorption processing procedure is repeatedly
After drip washing, filtrate reaches " integrated wastewater discharge standard " through bioabsorbable polymer material adsorption treatment lower valency content of beary metal
Limit.
Advantages of the present invention:
Hinge structure, the original position ELUTION METHOD of the present invention uses water as eluent, it is to avoid use chemical agent is carried out
Drip washing, not only reduces cost but also soil will not be brought secondary pollution.Polyglutamic acid-chitosan gel rubber that the present invention selects has
Biocompatibility, degradability, do not use poisonous chemical cross-linking agent during crosslinking, environment does not exist secondary pollution.
Polyglutamic acid-the chitosan gel rubber that the present invention selects lower valency heavy metal ion process in absorption water need not
PH or the temperature of regulation filtrate i.e. can reach high clearance, simple to operate.By original position washed off soil and bioabsorbable polymer material
Absorption filtrate state heavy metal at a middle or low price, does not results in secondary pollution to soil, reaches " standard of soil environment quality " (GB15618-
2008), filtrate reaches " integrated wastewater discharge standard " after macromolecular material adsorption treatment.The present invention can efficiently remove soil
Earth state heavy metal at a middle or low price, to environment non-secondary pollution, macromolecular material has the advantages such as biodegradable, biocompatibility,
Environmental protection protection field can be widely applied.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the scope of the invention.
Limit, rice field, Hunan lower valency heavy metal soil is repaired in embodiment 1 drip washing-absorption
The preparation of polyglutamic acid-chitosan gel rubber:
Weigh the gamma-polyglutamic acid-of 0.5g in 100ml beaker, add 40g deionized water, be placed on magnetic stirring apparatus stirring
Uniformly until being completely dissolved；
Weighing 5g chitosan, gamma-polyglutamic acid-and chitosan mol ratio are 1:6, are slowly added into equipped with polyglutamic acid solution
Beaker in, while stirring add make chitosan be uniformly dispersed in polyglutamic acid solution；
Weigh 50g 0.4mol/L acetum, the most at the uniform velocity add in beaker, stop stirring, react 10 minutes, after crosslinking
Obtain polyglutamic acid gel；
By soak in 3mol/L sodium hydroxide solution 4 hours, then rinse by phosphate buffered solution, obtain γ-poly-
Glutamic acid-chitosan gel rubber, can be soaked in phosphate buffered solution storage.
Limit, rice field, Hunan lower valency heavy metal soil is repaired in drip washing-absorption
1, drip washing
Limit, rice field, Hunan lower valency heavy-metal contaminated soil, is injected into 2 tons of water in contaminated soil by injector well and carries out drip washing, drenches
Collected the leacheate being enriched lower valency heavy metal after washing by extraction well, through sedimentation, extracting supernatant is to process tank；
2, absorption
Adding polyglutamic acid-chitosan gel rubber in process tank, consumption is 25kg/ ton, and stirring and adsorbing 3 hours is passed through after filtration
Water pump loops back injector well and continues washed off soil, repeat the above steps washed off soil 5 times, and final soil and filtrate all reach country
Standard.
Before drip washing, Copper In The Soil, cadmium, Zn content are 132mg/kg, 1.7mg/kg, 610mg/kg respectively, drop respectively after drip washing
It is respectively 67.4% to 43mg/kg, 0.32mg/kg, 185mg/kg Copper In The Soil, cadmium, zinc clearance, 81.2%, 70.8%.Filtrate
Before absorption, in filtrate, copper ion, cadmium ion, zinc ion are 44.80mg/L, 0.69mg/L, 215.25mg/L respectively, by poly-paddy
After propylhomoserin-chitosan gel rubber absorption, in filtrate, copper ion, cadmium ion, zinc ion are 0.28mg/L, 0.0045mg/L respectively,
0.83mg/L, clearance is respectively 99.37%, and 99.35%, 99.61%.After original position drip washing and biopolymer gels are adsorbed
Soil and filtrate are all up to state standards.
Polyglutamic acid-chitosan gel rubber after absorption resolves with 0.1 ~ 1mol/L hydrochloric acid solution, makes lower valency metal
Ion reclaims, and polyglutamic acid-chitosan gel rubber after treatment is reusable.
Embodiment 2
The preparation of polyglutamic acid-chitosan gel rubber:
With embodiment 1；
Limit, rice field, Hunan lower valency heavy metal soil is repaired in drip washing-absorption
1, drip washing
Limit, rice field, Hunan lower valency heavy-metal contaminated soil, is injected into 2 tons of water in contaminated soil by injector well and carries out drip washing, drenches
By extraction well, the leacheate being enriched lower valency heavy metal is extracted from soil after washing, collect leacheate, through sedimentation,
Extracting supernatant is in process tank；
2, absorption
Adding polyglutamic acid-chitosan gel rubber in process tank, feeding quantity is 40kg/ ton, the water after solid-liquid separation, after processing
Loop back injector well by water pump and continue washed off soil, repeat the above steps washed off soil 5 times
Before drip washing, Copper In The Soil, cadmium, Zn content are 132mg/kg, 1.7mg/kg, 610mg/kg respectively, are down to respectively after drip washing
43mg/kg, 0.32mg/kg, 185mg/kg Copper In The Soil, cadmium, zinc clearance are respectively 67.4%, and 81.2%, 70.8%.Filtrate is inhaled
In attached front filtrate, copper ion, cadmium ion, zinc ion are 44.80mg/L, 0.69mg/L, 215.25mg/L respectively, pass through polyglutamic
After acid-chitosan absorption, in filtrate, copper ion, cadmium ion, zinc ion are 4.58mg/L, 0.22mg/L, 45.25mg/L respectively, go
Except rate is respectively 89.78%, 68.12%, 78.98%.After original position drip washing and biopolymer gels are adsorbed, soil reaches country
Standard.
Polyglutamic acid-chitosan gel rubber after absorption resolves with 0.1 ~ 1mol/L hydrochloric acid solution, makes lower valency metal
Ion reclaims, and polyglutamic acid-chitosan gel rubber after treatment is reusable.
Embodiment 3
The preparation of polyglutamic acid-chitosan gel rubber:
With embodiment 1；
Limit, rice field, Hunan lower valency heavy metal soil is repaired in drip washing-absorption
1, drip washing
Limit, rice field, Hunan lower valency heavy-metal contaminated soil, is injected into 2 tons of water in contaminated soil by injector well and carries out drip washing, drenches
By extraction well, the leacheate being enriched lower valency heavy metal is extracted from soil after washing, collect leacheate, through sedimentation,
Extracting supernatant is in process tank；
Measure copper, cadmium, Zn content in filtrate.Collect filtrate and use 50kg(dry weight).
2, drip washing
Adding polyglutamic acid-chitosan gel rubber in process tank, feeding quantity is 50kg/ ton, stirring and adsorbing 5 hours, logical after filtration
Cross water pump and loop back injector well continuation washed off soil, repeat the above steps washed off soil 5 times.
Before drip washing, Copper In The Soil, cadmium, Zn content are 132mg/kg, 1.7mg/kg, 610mg/kg respectively, drop respectively after drip washing
It is respectively 48.48% to 68mg/kg, 0.73mg/kg, 320mg/kg Copper In The Soil, cadmium, zinc clearance, 57.06%, 47.54%.Inhale
In attached front filtrate, copper ion, cadmium ion, zinc ion are 64.10mg/L, 0.97mg/L, 290.5mg/L respectively, pass through polyglutamic
After acid-chitosan gel rubber absorption, in filtrate, copper ion, cadmium ion, zinc ion are 11.56mg/L, 0.39mg/L respectively,
60.48mg/L, clearance is respectively 81.97%, and 59.79%, 79.18%.After original position drip washing and biopolymer gels are adsorbed
Soil and filtrate are all up to state standards.
Polyglutamic acid-chitosan gel rubber after absorption resolves with 0.1 ~ 1mol/L hydrochloric acid solution, makes lower valency metal
Ion reclaims, and polyglutamic acid-chitosan gel rubber after treatment is reusable.
Claims (4)
1. a restorative procedure for lower valency heavy-metal contaminated soil, comprises the following steps:
(1) drip washing
Using water as eluent, first pass through in the soil that injector well is injected into lower valency heavy metal pollution, then incited somebody to action by extraction well
The leacheate being enriched lower valency heavy metal extracts from soil, collects leacheate, through sedimentation, extracts supernatant to processing
In tank；
(2) absorption
Polyglutamic acid-chitosan gel rubber is directly added in process tank, stirring and adsorbing more than 3 hours, after solid-liquid separation, returns
Receive treatment fluid and pump into injector well and continue washed off soil as eluent.
2. restorative procedure as claimed in claim 1, the dosage of described polyglutamic acid-chitosan gel rubber is 25 ~ 50kg/ ton.
3. restorative procedure as claimed in claim 1, uses after heavy metal in described polyglutamic acid-chitosan gel rubber absorption at a low price
0.1 ~ 1mol/L hydrochloric acid solution resolves, and makes lower valency metal ion reclaim, and polyglutamic acid-shell after treatment gathers
Sugar gel is reusable.
4. restorative procedure as claimed in claim 1, described polyglutamic acid-chitosan gel rubber adopts and prepares with the following method:
Weigh the gamma-polyglutamic acid-of 0.1-0.8g in 100ml beaker, add 30-60g deionized water, be placed in magnetic stirring apparatus
On stir until being completely dissolved；
Weighing 3-6g chitosan, gamma-polyglutamic acid-and chitosan mol ratio are 1:4-100, are slowly added into equipped with polyglutamic acid
In the beaker of solution, add while stirring and make chitosan be uniformly dispersed in polyglutamic acid solution；
Weigh 30-60g 0.4mol/L acetum, the most at the uniform velocity add in beaker, stop stirring, react 10 minutes, crosslinking
After obtain polyglutamic acid gel；
By soak in 3mol/L sodium hydroxide solution 4 hours, then rinse by phosphate buffered solution, obtain γ-poly-paddy
Propylhomoserin-chitosan gel rubber, can be soaked in phosphate buffered solution storage.
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| CN201610827640.9A CN106269832A (en) | 2016-09-18 | 2016-09-18 | A kind of restorative procedure of lower valency heavy-metal contaminated soil |
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Cited By (4)
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|---|---|---|---|---|
| CN108126977A (en) * | 2017-12-27 | 2018-06-08 | 环境保护部南京环境科学研究所 | The restorative procedure of lead-contaminated soil |
| CN109250882A (en) * | 2018-10-12 | 2019-01-22 | 江西省科学院生物资源研究所 | A kind of method of animal waste heavy metal removing |
| CN111285497A (en) * | 2020-03-10 | 2020-06-16 | 周葆华 | Heavy metal settlement separation device for soil |
| CN115430699A (en) * | 2022-08-26 | 2022-12-06 | 上海化工院环境工程有限公司 | Heavy metal polluted paddy field in-situ leaching system and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108126977A (en) * | 2017-12-27 | 2018-06-08 | 环境保护部南京环境科学研究所 | The restorative procedure of lead-contaminated soil |
| CN109250882A (en) * | 2018-10-12 | 2019-01-22 | 江西省科学院生物资源研究所 | A kind of method of animal waste heavy metal removing |
| CN111285497A (en) * | 2020-03-10 | 2020-06-16 | 周葆华 | Heavy metal settlement separation device for soil |
| CN115430699A (en) * | 2022-08-26 | 2022-12-06 | 上海化工院环境工程有限公司 | Heavy metal polluted paddy field in-situ leaching system and application thereof |
| CN115430699B (en) * | 2022-08-26 | 2023-08-29 | 上海化工院环境工程有限公司 | Heavy metal polluted paddy field in-situ leaching system and application thereof |
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Application publication date: 20170104 |